Improving the Performance of BaMnO3 Perovskite as Soot Oxidation Catalyst Using Carbon Black during Sol-Gel Synthesis

A series of BaMnO3 solids (BM-CX) were prepared by a modified sol-gel method in which a carbon black (VULCAN XC-72R), and different calcination temperatures (600 °C–850 °C) were used. The fresh and used catalysts were characterized by ICP-OES, XRD, XPS, FESEM, TEM, O2-TPD and H2- TPR-. The characterization results indicate that the use of low calcination temperatures in the presence of carbon black allows decreasing the sintering effects and achieving some improvements regarding BM reference catalyst: (i) smaller average crystal and particles size, (ii) a slight increase in the BET surface area, (iii) a decrease in the macropores diameter range and, (iv) a lower temperature for the reduction of manganese. The hydrogen consumption confirms Mn(III) and Mn(IV) are presented in the samples, Mn(III) being the main oxidation state. The BM-CX catalysts series shows an improved catalytic performance regarding BM reference catalyst for oxidation processes (NO to NO2 and NO2-assisted soot oxidation), promoting higher stability and higher CO2 selectivity. BM-C700 shows the best catalytic performance, i.e., the highest thermal stability and a high initial soot oxidation rate, which decreases the accumulation of soot during the soot oxidation and, consequently, minimizes the catalyst deactivation.

Challenging Conditions for Gasoline Particulate Filters (GPFs)

The emission limit of non-volatile particles (i.e., particles that do not evaporate at 350 °C) with size >23 nm, in combination with the real driving emissions (RDE) regulation in 2017, resulted in the introduction of gasoline particulate filters (GPFs) in all light-duty vehicles with gasoline direct injection engines in Europe. Even though there are studies that have examined the particulate emissions at or beyond the current RDE boundary conditions, there is a lack of studies combining most or all worst cases (i.e., conditions that increase the emissions). In this study, we challenged a fresh (i.e., no accumulation of soot or ash) “advanced” prototype GPF at different temperatures (down to −9 °C), aggressive drive cycles and hard accelerations (beyond the RDE limits), high payload (up to 90%), use of all auxiliaries (air conditioning, heating of the seats and the rear window), and cold starts independently or simultaneously. Under hot engine conditions, the increase of the particulate emissions due to higher payload and lower ambient temperature was 30–90%. The cold start at low ambient temperature, however, had an effect on the emissions of up to a factor of 20 for particles >23 nm or 300 when considering particles <23 nm. We proposed that the reason for these high emissions was the incomplete combustion and the low efficiency of the three-way oxidation catalyst. This resulted in a high concentration of species that were in the gaseous phase at the high temperature of the close-coupled GPF and thus could not be filtered by the GPF. As the exhaust gas cooled down, these precursor species formed particles that could not be evaporated at 350 °C (the temperature of the particle number system). These results highlight the importance of the proper calibration of the engine out emissions at all conditions, even when a GPF is installed.

Thermochemical Recuperation to Enable Efficient Ammonia-Diesel Dual-Fuel Combustion in a Compression Ignition Engine

A thermochemical recuperation (TCR) reactor was developed and experimentally evaluated with the objective to improve dual-fuel diesel–ammonia compression ignition engines. The novel system simultaneously decomposed ammonia into a hydrogen-containing mixture to allow high diesel fuel replacement ratios and oxidized unburned ammonia emissions in the exhaust, overcoming two key shortcomings of ammonia combustion in engines from the previous literature. In the experimental work, a multi-cylinder compression ignition engine was operated in dual-fuel mode using intake-fumigated ammonia and hydrogen mixtures as the secondary fuel. A full-scale catalytic TCR reactor was constructed and generated the fuel used in the engine experiments. The results show that up to 55% of the total fuel energy was provided by ammonia on a lower heating value basis. Overall engine brake thermal efficiency increased for modes with a high exhaust temperature where ammonia decomposition conversion in the TCR reactor was high but decreased for all other modes due to poor combustion efficiency. Hydrocarbon and soot emissions were shown to increase with the replacement ratio for all modes due to lower combustion temperatures and in-cylinder oxidation processes in the late part of heat release. Engine-out oxides of nitrogen (NOx) emissions decreased with increasing diesel replacement levels for all engine modes. A higher concentration of unburned ammonia was measured in the exhaust with increasing replacement ratios. This unburned ammonia predominantly oxidized to NOx species over the oxidation catalyst used within the TCR reactor. Ammonia substitution thus increased post-TCR reactor ammonia and NOx emissions in this work. The results show, however, that engine-out NH3-to-NOx ratios were suitable for passive selective catalytic reduction, thus demonstrating that both ammonia and NOx from the engine could be readily converted to N2 if the appropriate catalyst were used in the TCR reactor.

Light-off Investigation of Oxymethylene Ether (OME) Considering the Presence of the Exhaust Components Heptane, Carbon, and Nitrogen Monoxide

Synthetic fuels and fuel blends like OMEs can contribute to tank-to-wheel CO2 emission savings. At the same time, it is known that these fuels have a lower exhaust temperature compared to conventional diesel. This effect has major impact on the exhaust after-treatment system, particularly in cold start conditions. This paper investigates the light-off behavior of exhaust gases containing OMEs by temperature-programmed oxidation experiments using a state-of-the-art oxidation catalyst. The main side product of catalytic oxidation of OMEs between 100 °C and the oxidation temperature T50, which was around 160 °C, was shown to be formaldehyde. While alkane oxidation, in this case heptane, was little influenced by OME oxidation, the oxidation temperature T50 of CO increases by more than 10 °C by OME addition. Nitrogen monoxide impeded the oxidation of OME in a similar way to the other components investigated. Due to the amount of FA produced and its toxicity, it could be concluded that it is necessary to heat up exhaust after-treatment systems of OME diesel engines even faster than conventional diesel exhaust after-treatment systems. The relatively high reactivity of OME on oxidation catalyst can be used by active thermal management approaches.