Heat-integrated reactor concepts for catalytic reforming and automotive exhaust purification

Optimal solutions in environmental catalysis require a well-coordinated development of catalysts and of process design. This contribution is devoted to energy integrated design concepts for fuel reforming and for automotive exhaust purification. The examples presented demonstrate the importance of an innovative process design for optimal utilization of existing catalysts and show the potential of future developments.

New concepts for steam reforming through the efficient coupling of the endothermic reforming reaction with an exothermic combustion reaction are discussed in the first part. These concepts have been implemented for methanol steam reforming in a counter-current reactor with distributed side feed of burner gas and for methane steam reforming in a modular reactor with a co-current reaction section for the endothermic and the combustion reaction and attached counter-current heat exchangers. Both applications employ the so-called folded sheet reactor design, which ensures an excellent heat transfer between the reforming and combustion channels and efficient heat recovery.

A similar design solution is introduced for the apparently different case of automotive exhaust purification. The proposed concept aims at decoupling exhaust after-treatment from engine control. Its main component is a counter-current heat exchanger with integrated purification stages for HC-oxidation, NO_X storage and reduction and soot filtering. A small catalytic burner at the hot end of the heat exchanger provides both heat and oxidizing or reducing agents on demand. A new soot filter design allows for safe soot filter regeneration.     

Untersuchungen zur Tautomerie von o,o'-Dihydroxy-azofarbstoffen der Eriochrom-Reihe

Investigations on the Tautomerism of o,o'-Dihydroxy Azo Dyes of the Eriochrome Type Investigation of the u.v.-vis-, ¹H- and ¹³C-n.m.r. spectra of the title substances and the isomers 3 and 3p at different pH-values and in different solvent mixtures as well as of O,O'-dimethyl derivatives of 2 and 3 show that in aqueous solution as well the monoanions as the trianions exist in the azo forms only. The dianions exist in dependence on the solvents as mixtures of tautomers. The results of PPP calculations for different prototropic structures are in good accordance with the experimental results.     

Quantenchemische Untersuchungen zur Molekül- und Elektronenstruktur einfacher Azomethinimine und verwandter Verbindungen

Quantum Chemical Investigations of the Molecular and Electronic Structure of Simple Azomethine Imines and Related Compounds The molecular and electronic structure of simple azomethinimines are investigated by means of MINDO/3 and CNDO/2 calculations. The calculated molecular geometry is compared with X-ray results obtained for these compounds. Except for the NN-bond lengths MINDO/3 satisfactorily describes the molecular structure of azomethinimine and related π-electronic systems. The charges at the atoms along the conjugated chain are alternating as in polymethines. The terminal carbon atom carries a negative charge. This charge brings about an appreciable shielding of this carbon atom such as found in the ¹³C-n.m.r. spectrum. This result does not contradict a stabilization of azomethinimines in the crystal via = CH…︁OC interactions.     

Occurrence, sources, and fate of benzothiazoles in municipal wastewater treatment plants

A set of six benzothiazoles was determined in effluents of three municipal wastewater treatment plants. Total concentrations of benzothiazoles ranged from 1.9 to 6.7 microg/ L, with benzothiazole-2-sulfonate (BTSA) being most prominent (35 - 70%), followed by benzothiazole, 2-hydroxybenzothiazole, and 2-methylthi benzothiazole (MTBT). The removal of benzothiazoles in tertiary municipal wastewater treatment was investigated in more detail in one of the plants during two sampling periods of several weeks. Total benzothiazole concentration decreased by 5-28% only. This very limited removal was primarily due to BTSA and MTBT that were either hardly removed or even increased in concentration. In street runoff benzothiazoles exceeded the wastewater concentrations by 1 order of magnitude, showing that surface runoff can be a significant source of benzothiazole emission. In household wastewater total concentrations were in the range of 50-80% of that found in municipal wastewater. These investigations outline that benzothiazoles, a class of polar and biologically active industrial chemicals, are regularly released with treated municipal wastewater and exhibit a considerable lifetime in surface waters.     

Electro-dissolution of 30Nb–Ti alloys in methanolic sulfuric acid—Optimal conditions for electropolishing

The electro-dissolution behaviour of a (30 at.%) Niobium–Titanium (NbTi) alloy in non-aqueous methanolic sulfuric acid solution using the rotating disc electrode (RDE) was ascertained. The optimal condition for electropolishing and the mechanism were proposed. The influence of the rotation rate, process temperature and sulfuric acid concentration on the dissolution kinetics was investigated. The dissolution rate (limiting current) increases linearly with increase in rotation rate and follows a Levich behaviour confirming a mass transport controlled process. The temperature dependence in terms of Arrhenius plot renders an activation energy value of E_a = 16.1 kJ mol⁻¹ for the process. The dissolution rate shows a strong dependence on the sulfuric acid concentration (1 M, 3 M and 5 M). Higher sulfuric acid concentrations lead to decreased dissolution rates (limiting current). The dissolution process is mass transport controlled in all concentrations of sulfuric acid. From an electrochemical perspective, a 3 M sulfuric acid was chosen as optimum owing to better controllability of the material removal rate. The dissolving ions are the probable rate limiting species, indicating a compact salt-film mechanism. The average root mean square (RMS) roughness value for an electropolished surface was approximately 10 nm, which is significantly lower than a mechanically polished surface.     

Upward-looking ground-penetrating radar for monitoring snowpack stratigraphy

Operational remote monitoring of snowpack stratigraphy, melt water intrusions and their evolution with time for forecasting snowpack stability is not possible to date. Determination of the spatial variability of snowpack conditions on various scales requires a number of point measurements with various methods. These methods are either destructive or do not provide information about the internal structure of the snowpack. The application of a remotely controlled non-destructive sensor system would help to gain a higher spatio-temporal resolution about information of the snowpack. In this study we present results from upward-looking ground-penetrating radar (GPR) surveys from horizontal caves dug in the front wall of snow pits at the bottom of the snowpack. GPR data are compared with vertical profiles of snow hardness and density, obtained in the snow pit. Data were acquired in different areas with varying snow conditions with various GPR impulse systems, frequencies and polarizations. Radar experiments with high frequencies (> 1 GHz) detect internal layers in the snowpack in dry snow, but fail to provide clear reflections at the upper snow-air transition because of attenuation. In wet snow, the radar signals < 1 GHz are capable to penetrate a meter-thick snowpack and detect the snow surface, although the signal is strongly attenuated. Analysis of reflection phases and magnitudes allows interpretation of their physical origin in terms of changes in electrical permittivity. Varying antenna polarization causes a strongly different signal response, likely caused by the snow-pit wall present in our set-up. Forward calculation of density-based reflection coefficients between neighboring layers of varying hardness yields ambiguous results in terms of correspondence with observed radar reflections apart except for interferences of neighboring reflections. Moreover, we identify several pitfalls for future applications. The system set-up used here represents a basis for further developments towards a system, which is capable of improving information on the spatial and temporal snowpack characteristics.     

Ozonolysis of Unsaturated Acids in Aqueous Solution: Acrylic,Methacrylic, Maleic,Fumaric and Muconic Acids

The rate constants of ozone with acrylic, methacrylic, fumaric, maleic, muconic and dichloromaleic acids in aqueous solution were determined. Substituent effects and state of protonation strongly influence these rate constants. The reactions follow largely the Criegee mechanism (formation of carbonyl compound plus hydroxyalkylhydroperoxide). There is a pronounced regioselectivity in the decay reactions of the ozonide. Depending on their structures, the hydroxyhydroperoxidic intermediates decay by various routes: decarboxylation, H₂O₂ elimination or water elimination. Preliminary data on dicloromaleic acid indicate than an additional decay leading to chlorine atoms route must be envisaged.