Analysis of the NOx storage behaviour during cold start of modern SCR flow-through substrates and SCR on-filter substrates

Selective catalytic reduction (SCR) systems are the state-of-the-art technology to reduce nitrogen oxide emissions (NOx) of modern diesel engines. The system behaviour is well understood in the common temperature working area. However, the system properties below light-off temperature are less well known and offer a wide scope for further investigations. Vehicle measurements show that under specific conditions during cold start, NOx can be partially stored and converted on on-filter and flow-through SCR catalysts. The purpose of this work was in a first step to analyse the main influence parameters on the NOx storage behaviour. Therefore, synthetic gas test bench measurements have been carried out, varying the gas concentrations, temperature, and gas hourly space velocity (GHSV). These investigations showed that the NOx storage effect strongly depends on the NH3 level stored in the catalyst, GHSV, the adsorbed water (H2O) on the catalyst, and the temperature of the catalyst. Further influence parameters such as the gas composition with focus on carbon monoxide (CO), short-chain hydrocarbons and long-chain hydrocarbons have been analysed on a synthetic gas test bench. Depending on operating conditions, a significant amount of NOx can be stored on a dry catalyst during the cold start phase. The water vapor from the combustion condenses on the cold exhaust pipe during the first seconds, or up to a few minutes after a cold start. As the water vapor reaches the surface of the catalyst, it condenses and adsorbs onto it, leading to a sudden temperature rise. This exothermal reaction causes the stored NOx to be desorbed, and furthermore it is partially reduced by the NH3 stored in the catalyst.

Oscillating Combustion—Primary Measure to Reduce Nitrogen Oxide in a Grate Furnace–Experiments and Simulations

The emission from industries and the mobility sector is under strong legal regulations in many countries worldwide. In Germany, the amendment to the 17th BlmSchV (Federal pollution control ordinance), which has been in force for waste incineration plants since 2013, has given rise to a new limit for nitrogen oxides of 150 mg/m3 as the daily mean level from 2019 on. A similar focus is on biomass-fired plants. According to the MCP (medium combustion plant) guideline of the EU, as a consequence, existing plants are required to either increase their consumption of ammonia water for nitrogen oxide reduction (SNCR process) or back fit SCR catalysts as secondary measures, which is a costly procedure. This paper presents a novel two-stage process in which an oscillating supply of secondary air allows nitrogen oxides to be reduced by approx. 50% at a good burnout level, which may obviate the need for secondary measures. Besides experimental investigations in a fixed bed reactor, CFD simulations confirm a high potential for reduction of nitrogen oxides. Together with the company POLZENITH, this process is under development for scale-up in a biomass incineration plant as a next step.

Optimization of Roasting Parameters for Recovery of Vanadium and Tungsten from Spent SCR Catalyst with Composite Roasting

Every year, large amounts of selective catalytic reduction (SCR) catalysts with losing catalytic activity and failing to be regenerated need to be regenerated, which will result in acute pollution. Recycling valuable metals from spent SCR catalysts can not only solve environmental problems, but also save resources. The process of sodium roasting and water leaching is able to effectively extract vanadium (V) and tungsten (W) from spent SCR catalysts. To improve the efficiencies of V and W, different sodium additives were first investigated in the roasting process. The results revealed that the process of NaCl-NaOH composite roasting and water leaching showed superior leaching efficiencies of V and W, which can reach 91.39% and 98.26%, respectively, and simultaneously, it can be found that adding low melting point NaOH promoted mass transfer as compared with the melting points of different sodium additives. Next, a single-factor experiment was conducted to investigate different roasting conditions, such as roasting temperature, roasting time, mass ratio of sodium additive and catalyst, and mass ratio of NaCl and NaOH, on the leaching efficiencies of V and W. Then, a three-level and four-factor orthogonal experiment and a weight matrix analysis were used to optimize the roasting parameters. The results showed that roasting temperature had the most significant effect on the leaching efficiencies of V and W, and the optimal roasting conditions were as follows: the roasting temperature was 750 °C, the roasting time was 2.5 h, the mass ratio of sodium additive and catalyst was 2.5, and the mass ratio of NaCl and NaOH was 1.5. Under the optimal roasting conditions, the leaching efficiencies of V and W were 93.25% and 99.17%, respectively. The results of XRD analysis inferred that VO2 coming from the decomposition of VOSO4 in spent SCR catalysts may first oxidize into V2O5 and then react with sodium additives to produce NaVO3. The formation of titanium-vanadium oxide ((Ti0.5V0.5)2O3) was a part reason of hindering the leaching of vanadium. With the increase of roasting temperature, TiO2 converted into Na2Ti3O7, which indicated that the main structure of the catalyst was destroyed, and simultaneously, more characteristic peaks of sodium metavanadate and sodium tungstate appeared, thus enhancing the leaching of V and W. Finally, it can be seen that the process of NaCl-NaOH roasting and water leaching remained higher leaching efficiencies of V and W and lower roasting temperature by comparing with leaching efficiencies of V and W in different processes of recycling SCR catalyst. The process of NaCl-NaOH composite roasting and water leaching provided a strategy with a highly efficient and clean route to leach V and W from spent SCR catalyst. The orthogonal experiment and weight matrix analysis in our study can be used as a reference to optimize the reaction conditions of a multiple indexes experiment.

Low-Temperature Selective Catalytic Reduction DeNOX and Regeneration of Mn–Cu Catalyst Supported by Activated Coke

The activated coke is a promising support for catalysts, and it is important to study the performance of the activated coke catalyst on the removal of NOx. In the current research, a series of the activated coke-supported Mn–Cu catalysts are prepared by the incipient wetness impregnation method. The effects of the molar ration of Mn/Cu, the content of Mn–Cu, the calcination temperature, and reaction space velocity on NO conversion are investigated, and it was found that the 8 wt.% Mn0.7Cu0.3/AC had the best catalytic activity when the calcination temperature was 200 °C. The existence of SO2 caused the catalyst to deactivate, but the activity of the poisoning catalyst could be recovered by different regeneration methods. To uncover the underlying mechanism, BET, XPS, XRD, SEM and FTIR characterizations were performed. These results suggested that the specific surface area and total pore volume of the poisoning catalyst are recovered and the sulfite and sulfate on the surface of the poisoning catalysts are removed after water washing regeneration. More importantly, the water washing regeneration returns the value of Mn3+/Mn4+, Cu2+/Cu+, and Oα/Oβ, related to the activity, basically back to the level of the fresh catalyst. Thus, the effect of water washing regeneration is better than thermal regeneration. These results could provide some helpful information for the design and development of the SCR catalysts.