Studies on the deactivation and reactivation of spent hydroprocessing catalyst

A study is reported on the deactivation of hydroprocessing catalysts and their reactivation by the removal of coke and metal foulants. The literature on hydrotreating catalyst deactivation by coke and metals deposition, the environmental problems associated with spent catalyst disposal, and its reactivation/rejuvenation process were reviewed. Experimental studies on catalyst deactivation involved problem analysis in industrial hydroprocessing operations, through characterization of the spent catalyst, and laboratory coking studies. A comparison was made between the characteristics of spent catalysts from fixed bed and ebullating bed residue hydroprocessing reactor units and the catalyst deactivation pattern in both types of reactor systems was examined. In the laboratory the nature of initial coke deposited on the catalyst surface and its role on catalyst deactivation were studied. The influence of initial coke on catalyst surface area and porosity was significant. Both catalyst acidity and feedstock quality had a remarkable influence on the amount and the nature of the initial coke. The hydroenitrogenation function (HDN) of the catalyst was found to be deactivated more rapidly by the initial coke than the hydrodesulphurization function (HDS). In decoking experiments, special attention was paid to the initial conditions of coke combustion, since the early stages of contact between the coke on the spent catalyst surface and the oxygen are crucial in the decoking process. An increase in initial combustion temperature above 440oC and the oxygen content of the regeneration gas above 5% vanadium led to considerable sintering of the catalyst. At temperatures above 700oC there was a substantial loss of molybdenum from the catalyst, and phase transformations in the alumina support. The preferred leaching route (coked vs decoked form of spent catalyst) and a comparison of different reagents (i.e., oxalic acid and tartaric acid) and promoters (i.e., Hydrogen Peroxide and Ferric Nitrate) for better selectivity in removing the major foulant (vanadium), characterization and performance evaluation of the treated catalysts and modelling of the leaching process were addressed in spent catalyst rejuvenation studies. The surface area and pore volume increased substantially with increasing vanadium extraction from the spent catalyst; the HDS activity showed a parallel increase. The selectivity for leaching of vanadium deposits was better, and activity recovery was higher, for catalyst rejuvenated by metal leaching prior to decoking.

Effect of poor curing conditions and remedies on the durability of steel in concrete

An investigation was undertaken to study the effect of poor curing simulating hot climatic conditions and remedies on the durability of steel in concrete. Three different curing environments were used i.e. (1) Saturated Ca(OH)2 solution at 20°C, (2) Saturated Ca(OH)2 solution at 50°C and (3) Air at 50°C at 30% relative humidity. The third curing condition corresponding to the temperature and relative humidity typical of Middle Eastern Countries. The nature of the hardened cement paste matrix, cured under the above conditions was studied by means of Mercury Intrusion Porosimetry for measuring pore size distribution. The results were represented as total pore volume and initial pore entry diameter. The Scanning Electron Microscope was used to look at morphological changes during hydration, which were compared to the Mercury Intrusion Porosimetry results. X-ray defraction and Differential Thermal Analysis techniques were also employed for looking at any phase transformations. Polymer impregnation was used to reduce the porosity of the hardened cement pastes, especially in the case of the poorly cured samples. Carbonation rates of unimpregnated and impregnated cements were determined. Chloride diffusion studies were also undertaken to establish the effect of polymer impregnation and blending of the cements. Finally the corrosion behaviour of embedded steel bars was determined by the technique of Linear Polarisation. The steel was embedded in both untreated and polymer impregnated hardened cement pastes placed in either a solution containing NaCl or an environmental cabinet which provided carbonation at 40°C and 50% relative humidity.

Heterogeneous catalysis in an oscillatory baffled flow reactor

The first demonstration of heterogeneous catalysis within an oscillatory baffled flow reactor (OBR) is reported, exemplified by the solid acid catalysed esterification of organic acids, an important prototypical reaction for fine chemicals and biofuel synthesis. Suspension of a PrSOH-SBA-15 catalyst powder is readily achieved within the OBR under an oscillatory flow, facilitating the continuous esterification of hexanoic acid. Excellent semi-quantitative agreement is obtained between OBR and conventional stirred batch reaction kinetics, demonstrating efficient mixing, and highlighting the potential of OBRs for continuous, heterogeneously catalysed liquid phase transformations. Kinetic analysis highlights acid chain length (i.e. steric factors) as a key predictor of activity. Continuous esterification offers improved ester yields compared with batch operation, due to the removal of water by-product from the catalyst, evidencing the versatility of the OBR for heterogeneous flow chemistry and potential role as a new clean catalytic technology. © The Royal Society of Chemistry 2013.

Microstructural study of aluminide surface coatings on single crystal nickel base superalloy substrates

Aluminide diffusion coatings are frequently employed to enhance the oxidation resistance of nickel base superalloys. However, there is a concern that the presence of an aluminide coating could influence the properties of the coated superalloy, especially in respect of fatigue behaviour. To understand the nature of the effects of surface coatings on the fatigue properties of superalloys, an understanding of microstructural development within both the coating and the coating/substrate interfacial zone during high temperature fatigue testing is necessary. This paper is concerned with microstructural changes in aluminide diffusion coatings on single crystal γ′ strengthened superalloy substrates during the course of high temperature fatigue testing. The 'edge on' transmission electron microscopy technique is employed to study cross-sections of two stage (aluminization plus diffusion treatment) coated superalloy samples. The paper examines the degradation of the coating produced by phase transformations induced by loss of aluminum from the coating and/or aging of the coating. Aluminum removal both by interdiffusion with the substrate and by oxidation of the coating surface is considered. Microstructural development in the portion of the substrate influenced by interdiffusion with the coating is also discussed.