Chromate leaching from inhibited primers: Part I. Characterisation of leaching

Leaching and characterisation studies have been undertaken on two chromate-inhibited epoxy polyamide primers. Leaching was carried out in 5% (w/v) NaCl solutions at different pH values (1, 3, 5 and 7) and the amount of Cr released into solution was monitored over time. Cr release was initially high, but as the immersion time increased the leaching from the primers slowed. Prior to and after immersion, the primers were characterised by a number of techniques including electron microprobe analysis, X-ray microdiffraction, Raman spectroscopy, and positron annihilation lifetime spectroscopy. The unexposed primers were found to contain the inorganic phases SrCrO₄, BaSO₄ and TiO₂ (anatase or rutile). Upon immersion, water uptake by the primers was observed, together with a decrease in the amount of SrCrO₄ in the primers. These studies provide insights into the mechanism of chromate leaching from inhibited primers.     

Simultaneous removal of asphaltenes and water from water-in-bitumen emulsion: II. Application feasibility

Application feasibility of the accelerated deasphaltening process for simultaneous removal of asphaltenes and water from a water-in-bitumen emulsion has been examined with a pilot plant having capacity of 1.590 m3/day. The solvent (n-pentane) was injected into the emulsion from three locations with progressively increasing temperature from 423 K. The first solvent injection precipitated the asphaltenes in bitumen, the second broke the emulsion and facilitated the phase separation, and the third extracted the oil that remained in heavy asphaltenes/water phase. The effects of operation parameters such as temperature, solvent/bitumen ratio, feed rate and feedstock composition on the quality of DAO (Deasphaltening oil) were investigated. The DAO with the yield of ~ 80 wt.% and asphaltene content of < 0.5 wt.% was produced under optimal operating conditions, and the residual product was a porous solids containing 38% sulfur, 47% nitrogen, 64% MCR, and 85% metals (nickel and vanadium) of the bitumen. For a real application in oil industry, other important aspects including energy efficiency, solvent recovery and water purification have been discussed.     

Coal liquefaction by hydrogen produced from methanol: 3. Examination of reaction conditions

Coals were liquefied in a 50 ml autoclave using hydrogen produced from methanol with decomposition and hydrogenation catalysts under various conditions. The conversion increased with increasing reaction temperature and time. This reaction is more suitable for the liquefaction of lower-rank coals. The hydrogen pressure had little effect on the conversion in the range of the ratio of methanol to coal of 2 g/g. The use of a solvent is very effective in increasing the liquefaction, especially at short times.     

Chemistry of hydrogen sulphide under coal liquefaction conditions: 1. Modelling hydrogen transfer catalysis

The work reported here represents initial attempts to develop a complete kinetic and mechanistic understanding of the reaction chemistry of H₂S under coal liquefaction conditions, using both model systems and coal. Hydrogen sulphide was found to promote/catalyse the transfer of hydrogen from tetralin to 2-hydroxyquinoline (2-HOQ). The presence of H₂S can increase the rate of hydrogen transfer from tetralin to 2-HOQ by a factor of 10 compared with the same reaction run in the absence of H₂S. The energy of activation for hydrogen transfer was found to decrease by ≈5 kcal mol⁻¹ in the presence of H₂S. The presence of H₂S was also found to promote loss of oxygen from 2-HOQ to form small amounts of quinoline. No evidence of CC or CN bond cleavage in 2-HOQ was noted under any of the reaction conditions studied. These results suggest that the presence of H₂S reduces the temperatures necessary to promote effective hydrogen transfer from tetralin by 50–75 °C. Moreover, they imply that similar effects occur in H₂S-promoted coal liquefaction.     

Infrared spectroscopic studies of adsorption and catalysis: IV. Aliphatic ketones on silica-supported nickel

The adsorption and decarbonylation of acetone, acetone-d₆, and diethylketone on silica-supported nickel have been studied between 25 and 200 °C using infrared spectroscopy. After a short period of adsorption, two surface species were observed spectroscopically at 25 °. The main one is considered to be the associatively adsorbed ketone R₂CM-OM (M = surface metal atom). The minor one is a carbonyl-containing species possibly involving a complete acetone molecule held to a metal site through a relatively weak σ-bonded interaction with the carbon atom of the carbonyl group, or a π-bonded interaction with the carbonyl group as a whole. Over longer periods of time, bands were observed which are attributable to R₂CH · OSi groups (Si = surface silicon atom of the support). These probably result from the reduction of the ketone to R₂CHOH molecules which then react with OH groups of the silica surface. The hydrogen needed for the reduction process may arise from disproportionation of some of the dissociatively adsorbed species.