THE DESIGN AND ANALYSIS OF EXPERIMENTS. By Oscar Kempthorne. New York, John Wiley and Sons, Inc., 1952. 631 pp. $8.50. This book by a teacher of statistics (as well as a consultant for \"experimenters\") is a comprehensive study of the philosophical background for the statistical design of experiment. It is necessary to have some facility with algebraic notation and manipulation to be able to use the volume intelligently. The problems are presented from the theoretical point of view, without such practical examples as would be helpful for those not acquainted with mathematics. The mathematical justification for the techniques is given. As a somewhat advanced treatment of the design and analysis of experiments, this volume will be interesting and helpful for many who approach statistics theoretically as well as practically. With emphasis on the \"why,\" and with description given broadly, the author relates the subject matter to the general theory of statistics and to the general problem of experimental inference. MARGARET J. ROBERTSON

The Design and Analysis of Experiments

The catalytic hydrogenation of d -glucose to d -sorbitol over a 5% Ru/C catalyst was studied in a semi-batch slurry autoclave operating at 373–403 K and 4.0–7.5 MPa hydrogen pressure. The d -glucose concentration was varied between 0.56 and 1.39 mol/l. The kinetic experiments were carried out in the absence of mass transport limitations, which was verified by using measured gas–liquid mass transfer coefficients and estimated diffusion and liquid–solid mass transfer coefficients. Many literature reports suffer from transport limitations. In the operating regime studied the reaction rate showed a first order dependency with respect to hydrogen. A shift in the order of d -glucose was observed. At low d -glucose concentrations (up to ca. 0.3 mol/l) the reaction showed a first order dependency, while at higher concentrations this changed to zero order behavior. No inhibition by sorbitol or mannitol was observed. The kinetic data were modeled using three plausible rate models based on Langmuir–Hinshelwood–Hougen–Watson (LHHW) kinetics assuming that the surface reaction is rate-determining. Model 1 involves non-competitive adsorption of hydrogen and d -glucose. Hydrogen adsorption is either molecular or dissociative, but due to the weak adsorption it results in both cases in a linear hydrogen pressure dependency, i.e. the same rate expression; Model 2 is based on competitive adsorption of molecular hydrogen and d -glucose; and Model 3 assumes competitive adsorption of dissociatively chemisorbed hydrogen and d -glucose. All three models described the data satisfactorily and further statistic discrimination between these models was not possible.

Three-phase hydrogenation of d-glucose over a carbon supported ruthenium catalyst—mass transfer and kinetics

Isothermal reaction calorimetry as a tool for kinetic analysis

An algorithm for predicting the hydrodynamic and mass transfer parameters in bubble column and slurry bubble column reactors

The use of monolithic catalysts in multiphase applications has received increasing interest throughout the last years. In this paper the use of monolithic catalysts in the hydrogenation of edible oils is studied. In comparative experiments the monolithic catalysts have shown a lower tendency to form trans-fatty acids compared to slurry catalysts with equal composition. It is also demonstrated that the monolithic catalyst could be reused several times without significant changes in the product composition. With respect to the effect of the operating parameters on the performance, common knowledge applies. By using a monolithic-catalyst-based technology, the process complexity can be significantly reduced as the separation of the oil and the catalyst becomes straightforward and the filtration and bleach steps are eliminated. An economic evaluation showed a significant reduction in the product cost when monoliths are used instead of a conventional slurry system.

Monolithic Catalysts as an Alternative to Slurry Systems: Hydrogenation of Edible Oil

The kinetics for soybean oil hydrogenation using a commercial Ni/Al2O3 catalyst were investigated in a 2 × 10-3 m3 agitated reaction calorimeter operating under a wide range of temperatures (383−44...

Kinetics, Gas−Liquid Mass Transfer, and Modeling of the Soybean Oil Hydrogenation Process

Almost all available literature correlations to predict the volumetric gas–liquid mass transfer coefficient, kLa in agitated reactors are systems- or operating conditions-dependent. In this study, two back-propagation neural networks (BPNNs), one dimensional and one dimensionless were developed to correlate kLa for numerous gas–liquid systems in both surface-aeration reactors (SAR) and gas-inducing reactors (GIR) operating under wide ranges of industrial conditions. A total of 4435 experimental data points obtained from more than 10 publications for 50 gas–liquid systems were used to train, validate the dimensional and dimensionless BPNNs, which were able to correlate all kLa values with R2 of 90.5 and 88.6%, respectively. The dimensional BPNN was used to predict the effect of various operating parameters on kLa in a number of important industrial processes. The predictions showed that increasing liquid viscosity decreased kLa values in the SAR, while kLa values in the GIR increased and then decreased with increasing liquid viscosity, following the gas holdup behavior. Increasing liquid density decreased kLa in both reactor types. Increasing liquid surface tension increased kLa values in the SAR, whereas in the GIR, kLa decreased due to the increase of bubble size. Increasing gas diffusivity or gas partial pressure or mixing speed, increased kLa in both reactor types. kLa values in the GIR were always higher than those in the SAR and increasing DImp./DT and HF/HL increased kLa in both reactor types.

Prediction of the gas /liquid volumetric mass transfer coefficients in surface-aeration and gas-inducing reactors using neural networks

The critical mixing speed for gas entrainment (NCRE), for gas induction (NCRI), induced gas flow rate (QGI) as well as the wavy gas-liquid interfacial area (aWave) of N2 and air were measured in pure toluene and three mixtures of organic liquids (toluene-benzoic acid-benzaldehyde mixtures) under wide ranges of temperatures, T (300-453K), pressures, P (1-15 bar), mixing speeds, N (13.3-23.3Hz) and liquid heights, H (0.171-0.268m) using a 4-liter, see-through agitated autoclave operating as a surface-aeration reactor (SAR) and gas-inducing reactor (GIR).NCRE and NCRI as well as aWave were estimated by analyzing the videos taken with an on-line high-speed Phantom camera through the reactors Jerguson windows. In the GIR, QGI was determined using a highly sensitive Coriolis mass flow meter. The Central Composite Statistical Design and analysis technique was used to study the effect of operating conditions on these hydrodynamic parameters.NCRE and NCRI appeared to increase with liquid height and decrease with temperature, whereas, the pressure and gas nature did not significantly affect both parameters. The liquid physicochemical properties were found to strongly affect NCRE and NCRI, and QGI. Increasing mixing speed or decreasing liquid height increased QGI. Increasing temperature or decreasing liquid viscosity initially increased and then decreased QGI. Increasing pressure or gas density on the other hand decreased QGI. Increasing mixing speed and temperature or decreasing liquid height significantly enhanced aWave, as compared to the flat liquid surface. At high pressures, however, lower values of aWave were obtained. Empirical and statistical correlations were also developed to accurately predict NCRE, NCRI, QGI and aWave.

Hydrodynamic and Mass Transfer Parameters in Agitated Reactors Part I: Critical Mixing Speed, Induced Gas Flow Rate, and Wavy Surface in SARs and GIRs

The present invention provides methods of forming dialkyl carbonate wherein catalyst buildup in the reaction equipment, the separation equipment, and transfer lines there between is reduced and even eliminated. In one embodiment, the method includes introducing alkanol, carbon monoxide, oxygen, and a catalyst to a reactor having a gaseous head space and a liquid body space. The reactor is operated under conditions to form dialkyl carbonate and water. A product stream containing dialkyl carbonate, water, and residual reactants is removed from the head space of the reactor and introduced to a cyclone with a flushing stream. A liquid bottom stream is captured from the cyclone and introduced to the reactor. The gaseous top stream contains product dialkyl carbonate.

Benoit Fillion

Papers

Kinetics, Gas−Liquid Mass Transfer, and Modeling of the Soybean Oil Hydrogenation Process

Prediction of the gas /liquid volumetric mass transfer coefficients in surface-aeration and gas-inducing reactors using neural networks

Hydrodynamic and Mass Transfer Parameters in Agitated Reactors Part I: Critical Mixing Speed, Induced Gas Flow Rate, and Wavy Surface in SARs and GIRs

Process for manufacturing dimethyl carbonate