Kinetics of Slurry Phase Fischer-Tropsch Synthesis

The overall objective of this project is to develop a comprehensive kinetic model for slurry-phase Fischer-Tropsch synthesis (FTS) employing iron-based catalysts. This model will be validated with experimental data obtained in a stirred-tank slurry reactor (STSR) over a wide range of process conditions. Three STSR tests of the Ruhrchemie LP 33/81 catalyst were conducted to collect data on catalyst activity and selectivity under 25 different sets of process conditions. The observed decrease in 1-olefin content and increase in 2-olefin and n-paraffin contents with the increase in conversion are consistent with a concept that 1-olefins participate in secondary reactions (e.g. 1-olefin hydrogenation, isomerization and readsorption), whereas 2-olefins and n-paraffins are formed in these reactions. Carbon number product distribution showed an increase in chain growth probability with increase in chain length. Vapor-liquid equilibrium calculations were made to check validity of the assumption that the gas and liquid phases are in equilibrium during FTS in the STSR. Calculated vapor phase compositions were in excellent agreement with experimental values from the STSR under reaction conditions. Discrepancies between the calculated and experimental values for the liquid-phase composition (for some of the experimental data) are ascribed to experimental errors in the amount of wax collected from the reactor, and the relative amounts of hydrocarbon wax and Durasyn 164 oil (start-up fluid) in the liquid samples. Kinetic parameters of four kinetic models (Lox and Froment, 1993b; Yang et al., 2003; Van der Laan and Beenackers, 1998, 1999; and an extended kinetic model of Van der Laan and Beenackers) were estimated from experimental data in the STSR tests. Two of these kinetic models (Lox and Froment, 1993b; Yang et al., 2003) can predict a complete product distribution (inorganic species and hydrocarbons), whereas the kinetic model of Van der Laan and Beenackers (1998, 1999) can be used only to fit product distribution of total olefins and n-paraffins. The kinetic model of Van der Laan and Beenackers was extended to account separately for formation of 1- and 2-olefins, as well as n-paraffins. A simplified form of the kinetic model of Lox and Froment (1993b) has only five parameters at isothermal conditions. Because of its relative simplicity, this model is well suited for initial studies where the main goal is to learn techniques for parameter estimation and statistical analysis of estimated values of model parameters. The same techniques and computer codes were used in the analysis of other kinetic models. The Levenberg-Marquardt (LM) method was employed for minimization of the objective function and kinetic parameter estimation. Predicted reaction rates of inorganic and hydrocarbon species were not in good agreement with experimental data. All reaction rate constants and activation energies (24 parameters) of the Yang et al. (2003) model were found to be positive, but the corresponding 95% confidence intervals were large. Agreement between predicted and experimental reaction rates has been fair to good. Light hydrocarbons were predicted fairly accurately, whereas the model predictions of higher molecular weight hydrocarbons values were lower than the experimental ones. The Van der Laan and Beenackers kinetic model (known as olefin readsorption product distribution model = ORPDM) provided a very good fit of the experimental data for hydrocarbons (total olefins and n-paraffins) up to about C{sub 20} (with the exception of experimental data that showed higher paraffin formation rates in C{sub 12}-C{sub 25} region, due to hydrocracking or other secondary reactions). Estimated values of all model parameters (true and pseudo-kinetic parameters) had high statistical significance after combining parameters related to olefin termination and readsorption into one (total of 7 model parameters). The original ORPDM was extended to account separately for formation of 1- and 2-olefins, and successfully employed to fit experimental data of three major groups of hydrocarbon products (n-paraffins, 1-olefins and 2-olefins). This model is referred to as an extended ORPDM (8 model parameters in its final form). In general, all three groups of products were fitted well, and the estimated model parameters were all positive and the corresponding 95% confidence intervals were small. Even though the extended ORPDM provided a very good fit of experimental data, it can not be used for the prediction of product distributions for a given set of process conditions. This model has several pseudo-kinetic parameters whose values vary with process conditions. Additional work is needed to expand capabilities of the model to predict molar flow rates of all inorganic species and major hydrocarbon products in terms of true kinetic (temperature dependent) constants

Monte Carlo simulations of ion channeling in crystals containing dislocations and randomly displaced atoms

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NOVEL SLURRY PHASE DIESEL CATALYSTS FOR COAL-DERIVED SYNGAS

This report describes research conducted to support the DOE program in novel slurry phase catalysts for converting coal-derived synthesis gas to diesel fuels. The primary objective of this research program is to develop attrition resistant catalysts that exhibit high activities for conversion of coal-derived syngas

Canagliflozin and renal outcomes in type 2 diabetes and nephropathy

BACKGROUND Type 2 diabetes mellitus is the leading cause of kidney failure worldwide, but few effective long-term treatments are available. In cardiovascular trials of inhibitors of sodium–glucose cotransporter 2 (SGLT2), exploratory results have suggested that such drugs may improve renal outcomes in patients with type 2 diabetes. METHODS In this double-blind, randomized trial, we assigned patients with type 2 diabetes and albuminuric chronic kidney disease to receive canagliflozin, an oral SGLT2 inhibitor, at a dose of 100 mg daily or placebo. All the patients had an estimated glomerular filtration rate (GFR) of 30 to <90 ml per minute per 1.73 m2 of body-surface area and albuminuria (ratio of albumin [mg] to creatinine [g], >300 to 5000) and were treated with renin–angiotensin system blockade. The primary outcome was a composite of end-stage kidney disease (dialysis, transplantation, or a sustained estimated GFR of <15 ml per minute per 1.73 m2), a doubling of the serum creatinine level, or death from renal or cardiovascular causes. Prespecified secondary outcomes were tested hierarchically. RESULTS The trial was stopped early after a planned interim analysis on the recommendation of the data and safety monitoring committee. At that time, 4401 patients had undergone randomization, with a median follow-up of 2.62 years. The relative risk of the primary outcome was 30% lower in the canagliflozin group than in the placebo group, with event rates of 43.2 and 61.2 per 1000 patient-years, respectively (hazard ratio, 0.70; 95% confidence interval [CI], 0.59 to 0.82; P=0.00001). The relative risk of the renal-specific composite of end-stage kidney disease, a doubling of the creatinine level, or death from renal causes was lower by 34% (hazard ratio, 0.66; 95% CI, 0.53 to 0.81; P<0.001), and the relative risk of end-stage kidney disease was lower by 32% (hazard ratio, 0.68; 95% CI, 0.54 to 0.86; P=0.002). The canagliflozin group also had a lower risk of cardiovascular death, myocardial infarction, or stroke (hazard ratio, 0.80; 95% CI, 0.67 to 0.95; P=0.01) and hospitalization for heart failure (hazard ratio, 0.61; 95% CI, 0.47 to 0.80; P<0.001). There were no significant differences in rates of amputation or fracture. CONCLUSIONS In patients with type 2 diabetes and kidney disease, the risk of kidney failure and cardiovascular events was lower in the canagliflozin group than in the placebo group at a median follow-up of 2.62 years

Fuel from the synthesis gas--the role of process engineering

The paper presents the conclusions obtained in the investigations of methanol synthesis, Fischer-Tropsch synthesis, and higher alcohols synthesis from syngas as a raw material in slurry reactors. The overview of the role of process engineering was made on the basis of the experience in optimizing process conditions, modeling reactors and working out new technologies. Experimental data, obtained with a laboratory-stirred autoclave and theoretical considerations were used to develop the kinetic models that can describe the product formation and the model of the simultaneous phase and chemical equilibrium for the methanol and Fischer-Tropsch syntheses in the slurry reactors. These models were employed in modeling of the bubble-column slurry reactor (BCSR). Based on these considerations, a computer simulation of the low-pressure methanol synthesis for the pilot-scale, BCSR, was devised. The results of the calculations and the conclusions could be employed in the process for designing an industrial plant.Fuel Synthesis gas

Carbon Dioxide Gasification Kinetics of Char from Rapeseed Oil Press Cake

Rapeseed oil press cake (RPC) is an abundantly available and renewable agricultural waste material for the production of fuels or chemicals. In this study, the rates of carbon dioxide gasification of rapeseed oil press cake char were measured by thermogravimetric analysis measurements performed at various temperatures (800–900 °C) and CO2 mole fractions (0.10–1.00). The char was obtained by slow pyrolysis, where the dried RPC was decomposed at a temperature range of 1000 °C to obtain char free of impurities that can affect the measurements. The random pore model appeared to be suitable for describing the effect of conversion on the reaction rate. The temperature, CO2, and concentration dependence of the reaction rate were given by the Arrhenius equation and a power law (nth order) correlation. The kinetic parameters based on the experimental data were determined by a two-step estimation procedure. For the experimental conditions employed in this study, the parameters E and n were 222.1 kJ/mol and 0.57, respectively

Pyrolysis of Rapeseed Oil Press Cake and Steam Gasification of Solid Residues

A deoiled rapeseed press cake (RPC) was pyrolyzed by heating at a slow heating rate to 1000 °C in a fixed bed reactor, and the produced char was then gasified to obtain data for the kinetic modeling of the process. The gasification experiments were performed in a thermogravimetric analyzer (TGA) under steam/argon mixtures at different temperatures (750, 800 and 850 °C) and steam mole fractions (0.17 and 0.45). The three most commonly used gas-solid kinetic models, the random pore model, the volumetric model and the shrinking core model were used to describe the conversion of char during steam gasification. The objective of the kinetic study was to determine the kinetic parameters and to assess the ability of the models to predict the RPC conversion during steam gasification. A TGA-MS analysis was applied to assess the composition of the product gas. The main steam gasification product of the RPC was hydrogen (approximately 60 mol % of the total product). The volumetric model was able to accurately predict the behavior of the RPC char gasification with steam at temperatures of 750–850 °C and steam concentrations less than 0.45 mole fraction. The activation energy and the reaction order with respect to steam were equal to 166 kJ/mol and 0.5, respectively, and were typical values for the gasification of biomass chars with stea