Thermal degradation of two liquid fuels and detonation tests for pulse detonation engine studies

The use of liquid fuels such as kerosene is of interest for the pulse detonation engine (PDE). Within this context, the aim of this work, which is a preliminary study, was to show the feasibility to initiate a detonation in air with liquid-fuel pyrolysis products, using energies and dimensions of test facility similars to those of PDEs. Therefore, two liquids fuels have been compared, JP10, which is a synthesis fuel generally used in the field of missile applications, and decane, which is one of the major components of standard kerosenes (F-34, Jet A1, ...). The thermal degradation of these fuels was studied with two pyrolysis processes, a batch reactor and a flow reactor. The temperatures varied from 600°C to 1,000°C and residence times for the batch reactor and the flow reactor were, respectively, between 10–30 s and 0.1–2 s. Subsequently, the detonability of synthetic gaseous mixtures, which was a schematisation of the decomposition state after the pyrolysis process, has been studied. The detonability study, regarding nitrogen dilution and equivalence ratio, was investigated in a 50 mm-diameter, 2.5 m-long detonation tube. These dimensions are compatible with applications in the aircraft industry and, more particularly, in PDEs. Therefore, JP10 and decane were compared to choose the best candidate for liquid-fuel PDE studies. This paper was based on work that was presented at the 20th International Colloquium on the Dynamics of Explosions and Reactive Systems, Montreal, Canada, July 31 – August 5, 2005.     

A novel simple pyrolytic approach towards anhydronucleosides

An interesting novel gas phase thermal intramolecular substitution reaction was discovered, which led to the conversion of the 2-β-d-N-glucosyl, 2-β-d-N-galactosyl and 2-β-d-N-ribosyl derivatives of 3-thioxo-2,3-dihydro-1,2,4-triazin-5(4H)-ones into their corresponding 3,2′-anhydro-β-d-mannosyl, 3,2′-anhydro-β-d-talosyl and 3,2′-anhydro-β-d-arabinosyl derivatives. The structures of these new anhydroglycosyls were determined by NMR experiments and by X-ray crystallography.     

Octasilsesquioxane Chemistry II. Hydrosilylation Reaction of Octa(hydrido)silsesquioxane with Unsaturated Substrates and Product Properties

The hydrosilylation reaction of octa(hydrido)silsesquioxane with ω‐halo‐1‐alkenes and other unsaturated substrates allows attachment of 8 long‐chain functionalized alkyls on the cubic Si₈O₁₂ skeleton. Pt/C and H₂PtCl₆ have been adopted as the catalysts, the yields being 74–98% for compounds 2–9 . For terminal alkenes, the hydrosilylation follows the anti‐Markonikov's rule. The morphological state of 2–9 ranges from viscous liquid to crystalline materials. The pyrolysis results indicate that 7 , a material of hard spherical core and soft flexible shell, may likely act as nanometer‐size ball bearings up to more than 400 °C. The X‐ray structure of 9 reveals that the molecule is required to possess a center of symmetry crystallographically. The linear arms on 9 , except for two of them, are virtually all‐trans in conformation, not counting the ω‐C‐Cl bond.     

Preparation of complex carbon-silica adsorbents with different properties

Summary The surface properties of complex adsorbents prepared through the pyrolysis of benzyl and n-heptyl alcohols and their mixtures on the surface of silica gel were investigated. The reactions were carried out in an autoclave at 500°C. A series of adsorbents having different porous structure, chemical nature of the adsorption centers and their topography were obtained. The best resolution of different mixtures was obtained by the carbon-silica adsorbent prepared through the pyrolysis of n-heptanol.     

Degradative analysis of aquatic fulvic acid: CuO oxidation versus pyrolysis after tetramethylammonium hydroxide treatments in air and helium atmospheres

The structural composition of Nordic aquatic reference fulvic acid was investigated using chemical and thermal degradation methods: alkaline CuO oxidation and analytical pyrolysis after tetramethylammonium hydroxide (TMAH) pretreatment. Off-line procedures of the TMAH treatments were carried out under both air and helium atmospheres, with the aim of clarifying the effect of oxygen. Irrespective of the fact that the chemical and thermal degradation methods gave qualitatively quite similar basic products (mainly phenols and phenolic acids together with aromatic and aliphatic carboxylic acids), they also revealed their unique selectivity and efficiency for releasing different kinds of structural constituents. The results verify the formation of additional carboxyl functionality in the CuO oxidation. However, some similar oxidative reactions also appeared to take place during the pretreatment procedures of strongly basic TMAH, especially under an air atmosphere. The use of inert and protective atmosphere during the TMAH pretreatment is therefore recommended for producing more relevant structural information about the complex composition of humic substances.     

Profiling fatty acids in vegetable oils by reactive pyrolysis-gas chromatography with dimethyl carbonate and titanium silicate

A novel methodology in on-line pyrolysis-gas chromatography (Py-GC) for the fast analysis of fatty acids in vegetable oils with minimal sample treatment and the use of non-toxic reagents is described. Pyrolysis at 500 degrees C for 10 s of sub-microgram quantity of vegetable oil dissolved in dimethyl carbonate (DMC) and in the presence of nanopowder titanium silicon oxide resulted in the production of fatty acid methyl esters (FAMEs) as unique products. Pyrolysis performed by means of a resistively heated filament pyrolyser interfaced to a GC-MS apparatus enabled the direct analysis of evolved FAMEs. The DMC/Py-GC-MS analysis was tested on soybean, coconut, linseed, walnut and olive oil and the results compared to the classical BF(3)-methanol as reference methodology. The DMC method exhibited a lower precision and was biased towards lower levels of polyunsaturated fatty acids (PUFA) in comparison to the BF(3)-methanol method, but was more advantageous in terms of reduced sample treatment, waste generation and risk factors of employed chemicals.     

用裂解气相色谱法对几株霉菌的分析

本文用带有PYR-2A管式炉裂解器和C-R2AX计算机的岛津GC-9A气相色谱仪,对3株曲霉和3株青霉进行了裂解气相色谱鉴别。通过对指纹图的分析,能够较好地区分出两属之间和各菌株之间的差异,证明了裂解气相色谱分析法用于霉菌鉴别的可能性。     

Dimethyl carbonate as a novel methylating reagent for fatty acids in analytical pyrolysis

Dimethyl carbonate (DMC) was investigated as a mild, harmless and odorless reagent for pyrolytic methylation of fatty acids. Soybean oil was selected as test material for its high content of (poly)unsaturated fatty acids. Pyrolyses were performed at 500, 700 and 900 degrees C by means of a heated platinum filament pyrolyser on-line and off-line to the GC-MS apparatus. Methyl esters of palmitic, linoleic, oleic and stearic acid were formed as prominent products from off-line pyrolysis of soybean oil in the presence of DMC and zeolite 13X. Fatty acid methyl esters (FAMEs) were not observed at important levels in the absence of zeolite, while on-line Py-GC-MS experiments resulted principally in the formation of free fatty acids and hydrocarbons. The FAME profiles obtained from the DMC/zeolite off-line pyrolysis were compared to those resulting from tetramethylammonium hydroxide (TMAH) thermochemolysis and BF3-methanol procedure. The observed differences between pyrolysis and methanolysis methods were principally attributed to the thermal degradation of unsaturated fatty acids. The effectiveness of the DMC/zeolite pyrolytic methylation was further demonstrated by the analysis of tripalmitine and soybean seeds.     

Influence of the heating rate on the temperature profiles and on the conversion rate of powdery cellulose and pine sawdust

An experimental study of the thermal decomposition of powdered cellulose and pine sawdust has been performed. The influence of the heating rate on the temperature profiles in the sample and on the solid conversion rate has been studied. A mathematical model without adjustable parameters has been used to calculate the temperature at different points in the solid bed and the average total solid conversion. The experimental results have been compared with those calculated by the model. A good agreement has been obtained for sawdust. Some differences are observed for cellulose at high heating rates, and the influence of the thermal conductivity and the reaction heat on the results has been analysed.