The effect of chromium on sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

Sulfur is a major poison to noble metal catalysts for deep aromatic hydrogenation in the petroleum refining industry. In order to study the sulfur resistance of Pd-based catalysts, a series of Pd, Cr, and PdCr catalysts supported on HY-Al2O3 were studied by NH3-TPD, pyridine-adsorption IR, TPR, IR spectra of adsorbed CO, and toluene hydrogenation in the presence of 3000 ppm sulfur as thiophene under the following conditions: 533-573 K, 4.2 MPa, and WHSV 4.0 h(-1). Cr has no influence on the acidity of the catalysts. TPR patterns and in situ IR spectra of adsorbed CO revealed a strong interaction between Cr and Pd, and the frequency shift of linear bonded CO on Pd indicates that the electron density of Pd decreases with the increase of the Cr/Pd atomic ratio. The catalytic performance of Pd, Cr, and PdCr catalysts shows that the sulfur resistance of Pd is strongly enhanced by Cr, and the activity reaches its maximum when the Cr/Pd atomic ratio equals 8. The active phase model "Pd particles decorated by Cr2O3" is postulated to explain the behavior of PdCr catalysts. (C) 2001 Academic Press.

Column switching-back flushing technique for the analysis of aromatic compounds in gasoline

A simple method, based on the technique of capillary column switching-back flushing, has been developed for the detailed analysis of aromatic compounds in gasoline. The sample was first separated on a 30-m long OV-2330 polar precolumn and then backflushed onto a nonpolar analytical column. The early eluting components from the precolumn and the components of interest (aromatic compounds plus heavier compounds) eluting from the analytical column are all directed to the same flame ionization detection system through a T piece, which permits the quantitative analysis of aromatic hydrocarbons in gasoline by a normalization method using correcting factors. The switching time window of the method is +/-5 s, resulting in easier operation and higher reliability. The reproducibility of the quantitative analysis was less than or equal to3% RSD for real gasoline samples. (C) 2002 Elsevier Science B.V. All rights reserved.

Strong effect of transitional metals on the sulfur resistance of Pd/HY-Al2O3 catalysts for aromatic hydrogenation

In order to improve the sulfur resistance of noble metal catalysts in the aromatic hydrogenation of diesel fuel, the alloying effect of non-noble metals with Pd was studied. Toluene hydrogenation over Pd and Pd-M bimetallic catalysts (M = Cr, W,La, Mn, Mo, Ag) on a mixed HY-Al2O3 support was investigated in the presence of 3000 ppm sulfur as thiophene in the feedstock. The results showed that the addition of the second metals strongly affected the activity of toluene hydrogenation, which suggests that the sulfur resistibility of Pd-M bimetallic catalysts is much different from single Pd. La, Mn, Mo and Ag decreased the sulfur resistance of the palladium catalysts. For example, the toluene conversion at 553 K was observed to decrease sharply from 39.4 wt.% on Pd to 1.6 wt.% on Pd-Ag, which is by a factor of 25. One of the important findings in this article is that Cr and W increase hydrogenation activity of Pd catalysts. The reactions occurring on these catalysts include hydrogenation, isomerization and hydrocracking, The addition of the second metals has no noticeable effects on the hydrogenation and isomerization selectivity, but it slightly suppresses hydrocracking reactions. The four typical catalysts, Pd-Cr, Pd-W, Pd-Ag and Pd were characterized by infrared (IR) spectroscopy of pyridine and CO. LR spectra of CO revealed the strong interaction between Pd and the second metal as Cr, W and Ag (or their oxide), indicating that the improvement in sulfur resistance originates from electron-deficient Pd with the addition of second metals. (C) 2001 Elsevier Science B.V. All rights reserved.

Sulfamide-amine alcohol catalyzed enantioselective alkynylation of aromatic ketones

The new readily available sulfamide-amine alcohol 11 was found to be effective in catalyzing enantioselective phenylacetylene addition to aromatic ketones without using another central metal, providing the chiral tertiary propargylic alcohols in good yields (up to 83%) and enantioselectivities (up to 83% e.e.). The conditions of this catalytic process are both mild and Simple, (c) 2005 Elsevier B.V. All rights reserved.

Production of light olefins and aromatic hydrocarbons through catalytic cracking of naphtha at lowered temperature

Naphtha catalytic cracking were carried out at 650 degrees C over modified ZSM-5. Light olefins and BTX could be obtained over the catalysts. The products showed variable distribution with different catalyst modification. Some modification, such as Fe, Cu and La favored the BTX generation and P and Mg modification favored the light olefins production. In N-2 stream cracking catalyzed by LaZSM-5, more than 50% naphtha feed were converted to BTX, while in steam cracking, with an improved modified catalyst, P, La/ZSM-5, naphtha can be converted to light olefins with high activity and long-term stability.

Hydrocarbon Potential of the Infra-salt Strata

This schematic geological cross-section of Angola offshore is representative of the majority of the Atlantic-type divergent margins. It illustrates the main geological features allowing to understand the different petroleum systems occurring, particularly, in South Atlantic divergent margins : (i) Pre-Pangea rocks (Precambrian granite-gneiss basement, volcanic rocks an/ or Paleozoic sediments, more or less, metamorphosed), which lie underneath the pre-rifting unconformity (PRU), in blue in the cross-section ; (ii) The rift-type basins developed during the lengthening of the Pangea supercontinent ; (iii) The breakup unconformity (BUU), which highlight the upper limit of the rift-type basins, in which organic rich lacustrine shales with a parallel internal configuration are potential source-rocks (organic matter type I) ; (iv) The SDRs (seaward dipping reflectors), which, generally, do not have any generating hydrocarbon potential (just 5 m of lacustrine shales are known in Austral basin) ; (v) The BUU is fossilized by SDRs (subaerial volcanism) or by margin infra-salt sediments (forming the mistakenly called by some American geoscientists "sag basin") ; (vi) The Loeme salt basin, which is a twin of the Brazilian salt basin, that is to say, that both basins have always been individualized ; (vii) The transgressive (backstepping) and regressive (forestepping) phases of the post-Pangea continental encroachment cycle ; (v) The interface between these sedimentary phases, correspond to the emplacement of potential marine source-rocks (organic matter type-II) ; (vi) Potential dispersive source rocks (organic matter type III) are possible in the regressive sedimentary interval.

Catalyst, additive and substrate effects in intramolecular aromatic additions of alpha-diazoketones

This thesis is focused on transition metal catalysed reaction of α-diazoketones leading to aromatic addition to form azulenones, with particular emphasis on enantiocontrol through use of chiral copper catalysts. The first chapter provides an overview of the influence of variation of the substituent at the diazo carbon on the outcome of subsequent reaction pathways, focusing in particular on C-H insertion, cyclopropanation, aromatic addition and ylide formation drawing together for the first time input from a range of primary reports. Chapter two describes the synthesis of a range of novel α-diazoketones. Rhodium and copper catalysed cyclisation of these to form a range of azulenones is described. Variation of the transition metal catalyst was undertaken using both copper and rhodium based systems and ligand variation, including the design and synthesis of a novel bisoxazoline ligand. The influence of additives, especially NaBARF, on the enantiocontrol was explored in detail and displayed an interesting impact which was sensitive to substituent effects. Further exploration demonstrated that it is the sodium cation which is critical in the additive effects. For the first time, enantiocontrol in the aromatic addition of terminal diazoketones was demonstrated indicating enantiofacial control in the aromatic addition is feasible in the absence of a bridgehead substituent. Determination of the enantiopurity in these compounds was particularly challenging due to the lability of the products. A substantial portion of the work was focused on determining the stereochemical outcome of the aromatic addition processes, both the absolute stereochemistry and extent of enantiopurity. Formation of PTAD adducts was beneficial in this regard. The third chapter contains the full experimental details and spectral characterisation of all novel compounds synthesised in this project, while details of chiral stationary phase HPLC and 1H NMR analysis are included in the appendix.

Hierbas Aromáticas, medicinales y condimentarias en Colombia : análisis del caso C.I. Organic Aromatic S.A. desde la perspectiva de la nueva economía institucional

Las hierbas aromáticas han tenido en la última década un auge mundial y su demanda cada vez se incrementa más. En Colombia la producción y exportación de estas hierbas viene en aumento. En los últimos 4 años la exportación colombiana creció en 142 por ciento y el principal país de destino fue Estados Unidos a donde se exporto el 74 por ciento de las hierbas aromáticas. En este momento la tendencia del mercado mundial, es hacia los productos orgánicos o limpios, así que algunos productores se han dedicado a buscar los mecanismos para generar producciones y procesos con certificados orgánicos, para acceder a los mercados demandantes. Estas certificaciones son bastante exigentes y requieren un cambio y adaptación de las organizaciones, además de una fuerte inversión económica. El objetivo general de este trabajo es estudiar por medio del caso de la empresa colombiana C.I. Organic Aromatic S.A. la forma de adaptación a la demanda creciente del nuevo mercado internacional de hierbas aromáticas. Se realiza un análisis estructural discreto para el sector y de estar forma comprender el marco general donde se mueve la empresa. Al igual, se describe la empresa y su funcionamiento, los puntos críticos de la misma y de las transacciones que realiza. La cadena del sector esta descrita en el trabajo, los principales actores son: los proveedores, los productores donde se diferencian los pequeños de los medianos y grandes (los grandes productores son los exportadores de la cadena), los importadores o mayoristas, los transformadores, los minoristas, supermercados o tiendas especializadas y por último el cliente final, que cada vez más busca este tipo de productos por salud. C.I. Organic Aromatic S.A., es una empresa dedicada a la producción 100 por ciento orgánica y exportación de hierbas aromáticas y culinarias. La empresa tiene certificación de producto 100 por orgánico, buenas prácticas de manejo y certificación ISO entre otros. Llevan 7 años de funcionamiento, pero con esta razón social trabajan desde 2012 cuando decidieron exportar directamente a Estados Unidos y convertirse en C.I. (comercializadora internacional). Para disminuir la incertidumbre se integran verticalmente hacia adelante, bajo la marca Exotic Organic Herbs, quienes están ubicados en Miami, para manejar la logística de la importación en Estados Unidos.

Hydrocarbon field size distributions: a case study in mixed integer nonlinear programming

Of key importance to oil and gas companies is the size distribution of fields in the areas that they are drilling. Recent arguments suggest that there are many more fields yet to be discovered in mature provinces than had previously been thought because the underlying distribution is monotonic not peaked. According to this view the peaked nature of the distribution for discovered fields reflects not the underlying distribution but the effect of economic truncation. This paper contributes to the discussion by analysing up-to-date exploration and discovery data for two mature provinces using the discovery-process model, based on sampling without replacement and implicitly including economic truncation effects. The maximum likelihood estimation involved generates a high-dimensional mixed-integer nonlinear optimization problem. A highly efficient solution strategy is tested, exploiting the separable structure and handling the integer constraints by treating the problem as a masked allocation problem in dynamic programming.

Use Of Micro-Stereology And Quantitative Cyto-Chemistry To Determine The Effects Of Crude Oil-Derived Aromatic-Hydrocarbons On Lysosomal Structure And Function In A Marine Bivalve Mollusk Mytilus-Edulis

The marine bivalve mollusc,Mytilus edulis (blue mussel), is a noted accumulator of many environmental pollutants and is increasingly used for the chemical and biological assessment of environmental impact. The toxic effects of crude oil-derived aromatic hydrocarbons (30 μg/l total hydrocarbons) on the lysosomal-vacuolar system of the digestive cells have been investigated in cryostat sections of hexane-frozen digestive glands. Exposure to aromatic hydrocarbons reduced the cytochemically determined latency of lysosomal β-N-acetylhexosaminidase; lysosomal volume density and surface density increased while the numerical density decreased. Experimental exposure resulted in the formation of very large lysosomes which are believed to be largely autophagic in function and these results indicate a significant structural and functional disturbance of digestive cell lysosomes in response to hydrocarbons.