Development of a TG-FTIR system for investigations with condensable and corrosive gases

A thermogravimetric analyzer and a Fourier-transform infrared (FTIR) spectrometer were combined and redesigned for investigations with corrosive and condensable reactive gases. The standard gas inlet and outlet of the thermogravimetric analyzer were changed in order to heat the gas tubes, which are lead through the flanges, and avoid condensation in these parts of the system. Furthermore, all tubes upstream and downstream of the thermogravimetric analyzer were trace heated up to 180°C. The gas measuring cell of the FTIR spectrometer was designed such that an optimum compromise between the small flow rates through the thermogravimetric analyzer and a short residence time of the gases in the gas measuring cell could be achieved. The gas supply allows the dosage of different gas compositions containing nitrogen, oxygen, water, NH3, and NO2, for example. The system was validated by analyzing the composition of a diesel particulate matter (PM) sample with a temperature-programmed desorption followed by oxidation (TPD/O) experiment, which showed good agreement with the established analysis methods. The reactivity of the PM sample was investigated by temperature-programmed oxidation (TPO) experiments with different reactive gas mixtures of oxygen, water, and NO2 in nitrogen. By adding NO2, the soot oxidation started at lower temperatures and the addition of water lead to a shift of the maxima of the carbon oxidation rates to lower temperatures. The ratio of formed CO2 and CO was shifted to higher values by the addition of NO2 and water whereby the influence of water was much more pronounce

Basic investigation of the chemical deactivation of V2O5/WO3-TiO2 SCR catalysts by potassium, calcium, and phosphate

The influence of the combustion products of different lubrication oil additives and impurities in fuel or urea solution on the activity and selectivity of V2O5/WO3-TiO2 catalysts in the selective catalytic reduction (SCR) of nitrogen oxides by ammonia was investigated. Focusing on the deactivation by calcium, phosphate, and potassium, the DeNO x activity followed the order K ≫ Ca >PO4. This trend was investigated on the structural level of the catalyst by means of temperature programmed desorption of ammonia (NH3-TPD) and a DRIFT characterization of the adsorbed ammonia species. The results suggest that the studied elements strongly reduce the acidity of the SCR catalyst in the order K ≫ Ca >PO4 by mainly affecting the Brønsted acidity of the surfac

NO x reduction in the exhaust of mobile heavy-duty diesel engines by urea-SCR

A DeNO x demonstration system for a diesel engine used in construction machineries and mobile cranes was setup. In preliminary experiments various extruded and coated SCR catalysts were evaluated with and without oxidizing pre-catalyst. The data from stationary tests with two selected catalysts were used to establish various model-based control algorithms for the optimum dosage of urea in the ESC and ETC. A NO x conversion of >93% at <10ppm average ammonia slip could be achieved at a converter-to-swept volume ratio of <2.

Detection of Key Transient Cu Intermediates in SSZ-13 During NH₃-SCR deNOₓ by Modulation Excitation IR spectroscopy

The small pore zeolite Cu-SSZ-13 is an efficient material for the standard selective catalytic reduction of nitrogen oxides (NOₓ) by ammonia (NH₃). In this work, Cu-SSZ-13 has been studied at 250 °C under high conversion using a modulation excitation approach and analysed with phase sensitive detection (PSD). While the complementary X-ray absorption near edge structure (XANES) spectroscopy measurements showed that the experiments were performed under cyclic Cu^{+}/Cu^{2+} redox, Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS) experiments provide spectroscopic evidence for previously postulated intermediates Cu–N([double bond, length as m-dash]O)–NH_{2} and Cu–NO_{3} in the NH_{3}-SCR deNO_{x} mechanism and for the role of [Cu^{2+}(OH^{−})]^{+}

Mechanochemistry-assisted hydrolysis of softwood over stable sulfonated carbon catalysts in a semi-batch process

The hydrolysis of lignocellulose is the first step in saccharide based bio-refining. The recovery of homogeneous acid catalysts imposes great challenges to the feasibility of conventional hydrolysis processes. Herein, we report a strategy to overcome these limitations by using stable sulfonated carbons as solid acid catalysts in a two-step process, composed of mechanocatalytic pretreatment and secondary hydrolysis in a semi-batch reactor. Without mechanocatalytic pre-treatment the hydrolysis of the insoluble substrate largely occurs through homogeneously catalyzed reactions. Ball-milling induced amorphization promotes a substantially higher substrate reactivity, because homogeneous hydrolysis occurs preferentially from less ordered structural domains in cellulose. In contrast, concerted ball-milling (CBM) of cellulose with the sulfonated carbon promotes a heterogeneously catalyzed hydrolysis to soluble oligosaccharides. By performing an in-depth physicochemical characterization of cellulose subjected to CBM treatment with different carbons, we reveal the crucial role of strong Brønsted acid sites in facilitating mechanocatalytic depolymerization. Recyclability experiments confirmed that despite being subject to profound structural changes during repeated pre-treatment/semi-batch hydrolysis cycles, the sulfonated carbon retained its catalytic activity. The combination of mechanocatalytic pretreatment with strong solid acids and hydrolysis in the semi-batch reactor was successfully extrapolated for the first time to the hydrolysis of real lignocellulose to achieve quantitative yields in C5 and high yields in C6 derived products

NOxReduction in the Exhaust of Mobile Heavy-Duty Diesel Engines by Urea-SCR

A DeNO x demonstration system for a diesel engine used in construction machineries and mobile cranes was setup. In preliminary experiments various extruded and coated SCR catalysts were evaluated with and without oxidizing pre-catalyst. The data from stationary tests with two selected catalysts were used to establish various model-based control algorithms for the optimum dosage of urea in the ESC and ETC. A NO x conversion of >93% at <10 ppm average ammonia slip could be achieved at a converter-to-swept volume ratio of <2.0