Modelling and experimental study of separators for co-solvent recovery in a supercritical extraction process

Co-solvent recovery in supercritical extraction is addressed here through a theoretical description of the behaviour of a CO2 + co-solvent mixture into a cascade of cyclonic separators, such as those existing in conventional fractionation processes based on depressurisation cascades. Conversely to the conventional simplified approach that considers a separator as a plain theoretical stage, our study proposes a dynamic modelling that accounts for the probable droplet entrainment by the light phase and the re-vaporisation phenomenon after the valve. Fractionation experiments of CO2 + n-propyl alcohol mixtures were operated in a three-stage fractionation pilot, and experimental results are compared with simulation ones. The study demonstrates the relevance of our modelling, and points out the importance of entrainment effects, especially for low-pressure operated separators

Turbulent flow in pulsed extraction columns with internals of discs and rings:Turbulent kinetic energy and its dissipation rate during the pulsation

Turbulent energy parameters of single-phase pulsed flow in an extraction column with internals of immobile discs and rings (doughnuts) are studied. Simulation results are obtained by resolution of Reynolds equations coupled with k–ɛ model of turbulence. As far as pulsed flow is concerned, the evolution of space distribution of turbulent kinetic energy k and its dissipation rate ɛ during the pulsation is thoroughly studied. It is observed that the energy distribution on a contact stage changes periodically from rather homogeneous to highly inhomogeneous depending on instantaneous flow velocity. Significant difference between maximal and mean energy parameters is observed. It is supposed that the discrepancy between simulation and experimental results for the size of drops formed in the turbulent field might be attributed to mean energy presentation that smoothes the peak effects of a pulsed flow. Spatial zones and time intervals of high-turbulent kinetic energy are delimited presuming their dominant role for accurate foreseeing of size of drops in this type of equipment. It is shown that an “effective” energy level should be determined by selection over the high-energy time periods and zones in order to compensate the smoothing effect of mean energy level.The results obtained are useful for the calculation of drop size based on energy level at the stage, which is necessary for the determination of parameters of practical interest such as drop residence time and interphase mass transfer surface

Assessment of critical-fluid extractions in the process industries

The potential for critical-fluid extraction as a separation process for improving the productive use of energy in the process industries is assessed. Critical-fluid extraction involves the use of fluids, normally gaseous at ambient conditions, as extraction solvents at temperatures and pressures around the critical point. Equilibrium and kinetic properties in this regime are very favorable for solvent applications, and generally allow major reductions in the energy requirements for separating and purifying chemical component of a mixture

Multiobjective optimization for multiproduct batch plant design under economic and environmental considerations

This work deals with the multicriteria cost–environment design of multiproduct batch plants, where the design variables are the size of the equipment items as well as the operating conditions. The case study is a multiproduct batch plant for the production of four recombinant proteins. Given the important combinatorial aspect of the problem, the approach used consists in coupling a stochastic algorithm, indeed a genetic algorithm (GA) with a discrete-event simulator (DES). Another incentive to use this kind of optimization method is that, there is no easy way of calculating derivatives of the objective functions, which then discards gradient optimization methods. To take into account the conflicting situations that may be encountered at the earliest stage of batch plant design, i.e. compromise situations between cost and environmental consideration, a multiobjective genetic algorithm (MOGA) was developed with a Pareto optimal ranking method. The results show how the methodology can be used to find a range of trade-off solutions for optimizing batch plant design

Analysis of free analyte fractions by rapid affinity chromatography

The invention is generally directed toward an analytical method to determine the concentration of the free analyte fraction in a sample. More particularly, the method encompasses applying a sample comprising a free and bound analyte fraction to an affinity column capable of selectively extracting the free fraction in the millisecond time domain. The signal generated by the free fraction is then quantified by standard analytical detection techniques. The concentration of the free fraction may then be determined by comparison of its signal with that of a calibration curve depicting the signal of known concentration of the same analyte

Electron transfer rates for asymmetric reactions

We use a numerically exact real-time path integral Monte Carlo scheme to compute electron transfer dynamics between two redox sites within a spin-boson approach. The case of asymmetric reactions is studied in detail in the least understood crossover region between nonadiabatic and adiabatic electron transfer. At intermediate-to-high temperature, we find good agreement with standard Marcus theory, provided dynamical recrossing effects are captured. The agreement with our data is practically perfect when temperature renormalization is allowed. At low temperature we find peculiar electron transfer kinetics in strongly asymmetric systems, characterized by rapid transient dynamics and backflow to the donor.Comment: 13 pages, 4 figures, submitted to Chemical Physics Special Issue on the Spin-Boson Problem, ed. by H. Grabert and A. Nitza

Liquid-phase hydrogenation of bio-refined succinic acid to 1,4-butanediol using bimetallic catalysts

open access articleDevelopment of a Crotalaria juncea based biorefinery produce large quantity of waste glycerol after trans-esterification of the juncea seeds. This glycerol, after purification, is used as a substrate for producing succinic acid on a microbial route. Hydrogenation of this bio-refined succinic acid is carried out under high pressure in order to produce 1,4- butanediol (BDO) using a batch slurry reactor with cobalt supported ruthenium bimetallic catalysts, synthesized inhouse. It is demonstrated that, using small amounts of ruthenium to cobalt increases the overall hydrogenation activity for the production of 1,4-butanediol. Hydrogenation reactions are carried out at various operating temperatures and pressures along with changes in the mixing ratios of ruthenium chloride and cobalt chloride hexahydrate, which are used to synthesize the catalyst. The Ru-Co bimetallic catalysts are characterized by XRD, FE-SEM and TGA. Concentrations of the hydrogenation product are analyzed using Gas chromatography-Mass spectrometry (GC-MS). Statistical analysis of the overall hydrogenation process is performed using a Box-Behnken Design (BBD)

DNA Renaturation at the Water-Phenol Interface

We study DNA adsorption and renaturation in a water-phenol two-phase system, with or without shaking. In very dilute solutions, single-stranded DNA is adsorbed at the interface in a salt-dependent manner. At high salt concentrations the adsorption is irreversible. The adsorption of the single-stranded DNA is specific to phenol and relies on stacking and hydrogen bonding. We establish the interfacial nature of a DNA renaturation at a high salt concentration. In the absence of shaking, this reaction involves an efficient surface diffusion of the single-stranded DNA chains. In the presence of a vigorous shaking, the bimolecular rate of the reaction exceeds the Smoluchowski limit for a three-dimensional diffusion-controlled reaction. DNA renaturation in these conditions is known as the Phenol Emulsion Reassociation Technique or PERT. Our results establish the interfacial nature of PERT. A comparison of this interfacial reaction with other approaches shows that PERT is the most efficient technique and reveals similarities between PERT and the renaturation performed by single-stranded nucleic acid binding proteins. Our results lead to a better understanding of the partitioning of nucleic acids in two-phase systems, and should help design improved extraction procedures for damaged nucleic acids. We present arguments in favor of a role of phenol and water-phenol interface in prebiotic chemistry. The most efficient renaturation reactions (in the presence of condensing agents or with PERT) occur in heterogeneous systems. This reveals the limitations of homogeneous approaches to the biochemistry of nucleic acids. We propose a heterogeneous approach to overcome the limitations of the homogeneous viewpoint

Scope and limitations of aliphatic Friedel-Crafts alkylations. Lewis acid catalyzed addition reactions of alkyl chlorides to carbon-carbon double bonds

Lewis acid catalyzed addition reactions of alkyl halides 1 with unsaturated hydrocarbons 2 have been studied. 1:l addition products 3 are formed if the addends 1 dissociate faster than the corresponding products 3; otherwise, polymerization of 2 takes place. For reaction conditions under which 1 and 3 exist mainly undissociated, solvolysis constants of model compounds can be used to predict the outcome of any such addition reactions if systems with considerable steric hindrance are excluded