Temperature-dependent reaction pathways for the anomalous hydrocracking of triglycerides in the presence of sulfided Co-Mo-catalyst.

Source CSIR-Indian Institute of Petroleum, Dehradun 248 005, India. Abstract Kinetic studies and product profiling was done to understand the anomalous cracking of jathropha oil triglycerides in the presence of sulfided Co-Mo/Al(2)O(3) catalyst. At temperatures between 320 and 340 C, only deoxygenation and oligomerization reactions took place whereas at temperatures above 340 C, internal conversions between the products and direct conversion to lighter and middle distillates were favored High pressures (80 bar) and H(2)/feed ratios (>1500) were necessary to minimize oligomerization of the products and to increase the lifespan of the catalyst. Lumped kinetic models were validated with experimental results. Activation energies for the formation of lighter (83 kJ/mol) and middle fractions (126 kJ/mol) were higher than those for the heavy (47 kJ/mol) and deoxygenated (47 kJ/mol) products. Jatropha oil triglycerides hydroconversion pathways were dependent on temperature and the triglycerides could be hydrocracked to lower range hydrocarbons (C5-C14) by increasing the reaction temperatures. Copyright 2012 Elsevier Ltd. All rights reserved.

The effect of temperature, pressure and S/C ratios on vegetable oil steam reforming process has been studied using process simulation in ChemCad 6.4. The data show that the main reforming products under the operating conditions used are H2, CO2, CO, CH4 and carbon. Higher H2 formation happens at low pressure, high temperatures and high S/C ratios. Lower operating temperatures and pressures must be avoided to prevent significant carbon formation. Higher S/C ratio reduces carbon formation.

Catalytic Oxidative dehydrogenation The new technology of catalytic oxidative dehydrogenation (ODH) may completely change theway some of the most important organic chemicals are manufactured. The conversion of alkanes likeethane (a by-product of petroleum processing and present in natural gas) to olefins (ethylene, propylene, the butenes, and butadiene) is in great demand in worldwide chemical industry. Highoperational costs and environmental issues have made this conversion profitable only on a very largescale. With successful development of ODH, high yields of olefins will be possible through theconversion of much smaller volumes of alkanes.Compared with the conventional steam-cracking method of dehydrogenating alkanes to olefins andcurrent catalytic dehydrogenation processes, ODH could reduce costs, lower greenhouse gasemissions, and save energy. Capital and operational efficiencies are gained by eliminating the need for a furnace and for decoking shutdowns, lowering operating temperatures, lessening material demands,conducting fewer maintenance operations, and using a greater proportion of the alkanes

in the olefinconversion process.Low molecular weight alkenes, such as ethene and propene, can be formed via non-oxidativedehydrogenation of the corresponding alkane. Non-oxidative dehydrogenation reactions areendothermic and lead to the concurrent formation of carbon and of lower molecular weight alkanes, both of which decrease alkene yields. Oxidative dehydrogenation (ODH) of light alkanes offers a potentially attractive route to alkenes, since the reaction is exothermic and avoids the thermodynamicconstraints of non-oxidative routes by forming water as a byproduct. In addition, carbon depositionduring ODH is eliminated, leading to stable catalytic activity. However, the yield of alkenes obtained by ODH on most catalysts is limited by alkene combustion to CO and CO2 (COx) A relevant example concerns catalytic conversion of n-butane to butenes by oxidativedehydrogenation (ODH) as an alternative process to direct dehydrogenation. It is well known thatsupported vanadium pentoxide is a promising catalyst for the ODH of n-butane. MgO supportedvanadium was reported as a very selective catalyst in the oxidative dehydrogenation of propane and n- butane, while -A12O3 supported vanadium catalyst was found to present a good selectivity to olefin products for ethane ODH but a poor selectivity in the ODH of n-butane. The acid-base character of thesupport explained this different behavior. On MgO, a support with basic properties, the interaction between vanadium species and the supports leads to the formation of vanadate compounds. In the caseof more acid supports, such as SiO2 or A12O3 a weak interaction is expected leading to less dispersedvanadium species on the surface which, in turns favors the formation of V2O5 crystallitesCatalytic cracking gives many by-products and is not necessarily optimized with respect to propeneyield. Propane dehydrogenation, on the other hand, yields propene as the main product. The problem isthat the dehydrogenation equilibrium favors propene only at high temperature or low pressure, addingto the overall cost of the process. The need for cryogenic separation of the unconverted propane and produced propene also adds to the process costs. Improvements of the dehydrogenation process tomake it commercially more attractive focus on increasing the yield by shifting the equilibrium throughremoval of one of the reaction products. Thus, in situ removal of hydrogen will shift thedehydrogenation equilibrium to the product side. This can be done either physically by means of amembrane, or chemically by in situ catalytic oxidation using a (post) transition metal or its oxide. Thelatter approach has the additional advantage of energy release by exothermic oxidation where it isneeded to aid the dehydrogenation. However, mixing oxygen, hydrogen, and hydrocarbons at hightemperatures creates a highly dangerous mixture. The risk of explosion may be reduced by separatingthe reactants in space using oxygen-selective membranes.

In the Patent WO/2006/075057, renewable biomass is deoxyg e n a t e d b y r e m o v i n g o x y g e n i n t h e f o r m o f C O 2 a n d C O . T h e invention relates to a catalytic method for the selective manufacture of hydrocarbons for diesel fuel from renewable sources such as plant/vegetable oils and their fats, and animal/ sh oils and their fats, by contacting the starting biomass with a heterogeneous catalyst comprising at least one metal selected from the metalsb e l o n g i n g t o t h e g r o u p V I I I o f t h e P e r i o d i c T a b l e . T h e h e t e r o g e n e o u s catalyst is pre-treated with hydrogen at 150-250C. Hydrocarbon

mixtures are isomerized with catalysts such as ferrierite, Pd, Ni,SiO2, and Al2O3[14].Bio-based oils are very different from crude oils from petroleum sources. The sulfur content of biocrudes is negligible, whereas bio-oils are rich in oxygen-containing molecules. Hydrodeoxygenation(HDO) of bio-oils typically comprises two stages. The rst stage is carried out at lower reaction temperatures in order to avoid polymerization of the oxygen-containing compounds and coking of the catalyst during the following deoxygenation step. At the second stage, under more severe reaction conditions, oxygen removal is efcient and large amounts of hydrogen are consumed. The rst stage can be applied at lower cost to produce partially deoxygenated fuels suitable for the generation of electricity, heating fuels, and production of some chemicals[15].