Carbonization and liquid-crystal (mesophase) development. 12. Mechanisms of the co-carbonization of coals with organic additives

In industrial situations, coals interact with solvents or additives to produce liquid fuels, solvent-refined coal, coal extract and metallurgical coke. In these processes there occurs a wide variation in effects or modifications of the coal by these additives. This paper describes the modifications which can occur, using a wide range of rank of coal, when these coals interact and are co-carbonized with a wide range of additives of different chemical properties. The optical texture of the resultant cokes is given special attention. The objective of the paper is to summarize the current state of knowledge of the mechanisms of these interactions. Possible mechanisms of interactions are summarized, kinetic and chemical structural aspects of reactions are outlined, the importance is mentioned of the formation of liquid phases enabling anisotropic optical textures in modified cokes to be created, and the industrial relevance of its possible development is discussed.     

Analysis of Indentation Crack as a Wedge-Loaded Half-Penny Crack

Surface cracks produced by indentation with a Vickers indenter were modeled as half-penny cracks extended by symmetric disk-shaped wedges. The wedge diameter was assumed to be equal to the hemispherical plastic zone size, and the wedge thickness was calculated by equating the wedge volume to the hardness-impression volume. The resulting equilibrium relation between the indentation load and the radius of the half-penny crack is in good quantitative agreement with similar relations obtained from fracture toughness calibration.     

2,2′-oxo-1,1′-azobenzene: microbial transformation of rye (Secale cereale L.) allelochemical in field soils byAcinetobacter calcoaceticus: III

Acinetobacter calcoaceticus, a gram-negative bacterium isolated from field soil, was found to be responsible for the biotransformation of 2(3H)-benzoxazolinone (BOA) to 2,2-oxo-1,1-azobenzene (AZOB). Experiments were conducted to evaluate the transformation of BOA to AZOB by this microbe in sterile and nonsterile soil. Transformation studies with soils inoculated withA. calcoaceticus indicated that the production of AZOB increased linearly with the concentration of BOA in sterile soil and showed a quadratic trend in nonsterile soils. This also indicated that all soil types studied for the transformation experiments might containA. calcoaceticus capable of the conversion of benzoxazolinones.     

Measurement of the size, shape and orientation of convex bodies

Different types of solid bodies (particles) with specific shape and size are needed for industrial processes. For spherical particles, ‘sizer’ measurements are usually reported as sphere diameters. For non-spherical particles, particle shape and especially orientation must be taken into account. Particles of a specific shape will present different views when looked at from different directions.We have employed a Camsizer^® instrument to measure the distribution of projected area under different physical conditions for solid cylindrical particles:

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Under ‘ideal’ conditions, corresponding to a uniform distribution of particle orientation, measurements agreed with predictions. The celebrated theorem of Cauchy applies only to this case.

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For two other situations, measured and predicted results differed. However, from the experimental data it was possible to infer the particle orientations and hence theoretically predict the projected area distribution. Excellent agreement between theory and practice was then restored.

     

Carbonization and liquid-crystal (mesophase) development. 8. The co-carbonization of coals with acenaphthylene and decacyclene

Several coals of different rank have been carbonized singly and also co-carbonized with acenaphthylene and decacyclene. The resultant cokes were mounted in resin and polished surfaces were examined for optical texture using a polarized-light optical microscope fitted with a half-wave retarder plate. The optical texture can be assessed qualitatively (visually) or quantitatively by a point-counting technique in terms of size and shape of constituent isochromatic anisotropic units. Some cokes from coals were Isotropic. Acenaphthylene was only able to exert a smaller influence than decacyclene on the optical texture of the resultant cokes from co-carbonizations. Decacyclene was able to modify the optical texture for both the low-rank non-fusible and the caking coals. The effects of changing the proportions of coal to additive were examined. Results are interpreted in terms of ‘depolymerization’ of the coal by the action of the additive (as solvent) and also by the action of the additive in modifying the processes of formation of semi-coke via nematic liquid crystals.     

Influence of alginite on the reflectance of vitrinite from Joadja,NSW, and some other coals and oil shales containing alginite

Reflectance data for vitrinite occurring in torbanites indicate that the mean maximum reflectance and the range of reflectance values are significantly lowered by the presence of alginite. This is the probable cause of apparently anomalous rank gradients in some deep oil exploration wells. Intermaceral effects need to be considered in assessing rank or maturity from vitrinite reflectance, and by inference, in most other methods. The interpretation of the cause of the effect is open to further study but the findings are highly significant in relation to coal utilization, oil and gas exploration, and studies of oil shales.     

Synthetic hydrogels 3. Solvent effects on poly(2-hydroxyethyl methacrylate) networks

Poly(2-hydroxyethyl methacrylate) networks were synthesized in aqueous solutions of propylene glycol, ethylene glycol, ethylene glycol monomethyl ether, or ethylene glycol dimethyl ether and the influences of solvent on phase separation during the polymerization process studied. Results from conversion-phase diagrams, turbidity measurements, swelling studies, and viscosity measurements show that the phase separation process is dependent upon the solubility parameter of the organic solvent, the instantaneous monomer concentration at each stage of the gel formation process, and the crosslinker content of the reaction mixture.     

SOLUBILITY OF CO2 AND H2S IN A HINDERED AMINE SOLUTION

The solubility of H₂S and CO₂ in aqueous solutions of the sterically hindered amine, 2-amino-2-methyl-1-propanol (AMP), was determined at 40 and 100°C. Partial pressures of C)₂ ranged from approximately 2 to 6000 kPa and of H₂S from 2 to 2200 kPa. The solubility results were compared with previously reported acid gas solubilities in aqueous monoethanolamine (MEA) solutions.     

Solubility of Propane in Sulpholane at Elevated Pressures

The solubility of propane in sulpholane has been determined at temperatures in the range 298‐403 K at pressures up to 17.6 MPa. The experimental results were correlated by the Peng‐Robinson equation of state, and binary interaction parameters have been obtained for this system. The parameters in the Krichevsky‐Ilinskaya equation were calculated from these interaction parameters.     

A New Indole Synthesis Promoted by Metal Triflates

A new synthesis of 4- and 7-carbon-substituted indoles is described. The overall sequence involves the addition of a nitrile oxide to 1 carboethoxy-2-(or 3-) allylpyrrole, hydrogenation of the intermediate isoxazoline to β-hydroxy ketone and cyclization of the ketol using magnesium or zinc triflate to the substituted indole. This new indole-forming strategy can also accommodate the introduction of oxygen functionality into the indole 6-position. Possible mechanistic aspects of the reaction are detailed.