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Paulo Debiagi Coskun Yildiz Marcel Richter Jochen Ströhle Bernd Epple Tiziano Faravelli Christian Hasse 《Proceedings of the Combustion Institute》2021,38(3):4053-4061
Coal combustion releases elevated amounts of pollutants to the atmosphere including SOX. During the pyrolysis step, sulfur present in the coal is released to the gas phase as many different chemical species such as H2S, COS, SO2, CS2, thiols and larger tars, also called SOX precursors, as they form SOX during combustion. Understanding the sulfur release process is crucial to the development of reliable kinetic models, which support the design of improved reactors for cleaner coal conversion processes. Sulfur release from two bituminous coals, Colombian hard coal (K1) and American high sulfur coal (U2), were studied in the present work. Low heating rate (LHR) experiments were performed in a thermogravimetric analyzer coupled with mass spectrometry (TG-MS), allowing to track the mass loss and the evolution of many volatile species (CO, CO2, CH4, SO2, H2S, COS, HCl and H2O). High heating rate (HHR) experiments were performed in an entrained flow reactor (drop-tube reactor – DTR), coupled with MS and nondispersive infrared sensor (NDIR). HHR experiments were complemented with CFD simulation of the multidimentional reacting flow field. A kinetic model of coal pyrolysis is employed to reproduce the experiments allowing a comprehensive assessment of the process. The suitability of this model is confirmed for LHR. The combination of HHR experiments with CFD simulations and kinetic modeling revealed the complexity of sulfur chemistry in coal combustion and allowed to better understand of the individual phenomena resulting in the formation of the different SOX precursors. LHR and HHR operating conditions lead to different distribution of sulfur species released, highly-dependent on the gas-phase temperature and residence time. Higher retention of total sulfur in char is observed at LHR (63%) when compared to HHR (37–44%), at 1273 K. These data support the development of reliable models with improved predictability. 相似文献
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Jannis W. Ochsmann Sebastian Lenz Sebastian G. J. Emmerling Ralf S. Kappes Sebastian K. Nett Maria C. Lechmann Stephan V. Roth Jochen S. Gutmann 《Journal of polymer science. Part A, Polymer chemistry》2010,48(14):1569-1573
Thin films of PS-b-PEO block copolymers were utilized as structured reservoirs for localized nanoscale precipitation reactions. By consecutively immersing the film into solutions of thioacetamide and cadmium chloride, we were able to obtain a monolayer of cadmium sulfide nanostructures on top of the block copolymer film. AFM and grazing incidence small angle X-ray scattering revealed spherical nanostructures (d = 15 nm) corresponding to the dimensions given by the block copolymer film. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1569–1573, 2010 相似文献
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Stefan M. Kast Jochen Heil Stefan Güssregen K. Friedemann Schmidt 《Journal of computer-aided molecular design》2010,24(4):343-353
The “embedded cluster reference interaction site model” (EC-RISM) approach combines statistical-mechanical integral equation
theory and quantum-chemical calculations for predicting thermodynamic data for chemical reactions in solution. The electronic
structure of the solute is determined self-consistently with the structure of the solvent that is described by 3D RISM integral
equation theory. The continuous solvent-site distribution is mapped onto a set of discrete background charges (“embedded cluster”)
that represent an additional contribution to the molecular Hamiltonian. The EC-RISM analysis of the SAMPL2 challenge set of
tautomers proceeds in three stages. Firstly, the group of compounds for which quantitative experimental free energy data was
provided was taken to determine appropriate levels of quantum-chemical theory for geometry optimization and free energy prediction.
Secondly, the resulting workflow was applied to the full set, allowing for chemical interpretations of the results. Thirdly,
disclosure of experimental data for parts of the compounds facilitated a detailed analysis of methodical issues and suggestions
for future improvements of the model. Without specifically adjusting parameters, the EC-RISM model yields the smallest value
of the root mean square error for the first set (0.6 kcal mol−1) as well as for the full set of quantitative reaction data (2.0 kcal mol−1) among the SAMPL2 participants. 相似文献
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Heiko Rinderhagen Dr. Jochen Mattay Prof. Rafael Nussbaum Thomas Bally Prof. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(24):7121-7124
In contrast to the structurally and configurationally stable alkyl‐ or aryl‐substituted cyclopropyl radical cations, cyclopropyl silyl ethers undergo spontaneous ring opening upon oxidation whereby the endocyclic C? C(O‐TMS) bond is cleaved with remarkable selectivity. DFT calculations on 1‐trimethylsilyloxybicyclo[4.1.0]heptane show that this selectivity arises from the topology of the potential surface of the corresponding radical cation which is initially generated in a very steep region of the potential surface from where the steepest descent leads to cleavage of the endocyclic rather than the lateral C? C(OTMS) bond. Cleavage of the lateral bond leads to interesting conformational changes which are explored in detail. 相似文献
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