Modeling Temperature and Species Concentration Profiles on a Continuous-Flow Reactor Applied to Aldol Condensation.

This paper presents the modeling of a continuous-flow reactor used for the synthesis of organic products. The finite element method software, COMSOL Multiphysics, was used to model transport phenomena and reaction kinetics. The temperature is one of the most important kinetic factors that may modify the reaction. A rise in temperature can generate a positive reaction but also secondary side reactions. The design of our system and of many other continuous systems makes it impossible, however, to measure the temperature throughout the reactor. In this paper, we modeled the temperature profile within the reactors as a function of the flow rate, temperature set point, and type of reactor material. The results demonstrated that although it is not a good thermal conductor, polytetrafluoroethylene can be used like other materials. The desired temperature was not reached for any of the reactor material likely to affect the product yield. The model gave the residence time required to reach the stabilized temperature. The comparison of calculated and experimental values of outlet temperature showed good agreement, with a maximum relative difference of only 5%. Knowledge of the temperature profile made it possible to control the concentration distribution of the chemical species in the reactor. The aldol condensation was chosen to determine the kinetic parameters of this reaction as the products of this reaction are found in many natural molecules and drugs. To integrate the chemical model, the kinetic parameters were determined by using experimental data. An equilibrium concentration of 0.2 mol/L was found with initial reactant concentrations of 0.45 mol/L. The chemical modeling gave the species concentrations throughout the reactor. Calculated concentrations were in good agreement with experimental data, with a maximum relative difference of less than 9%. By modeling this reaction, the reaction yield as a function of reactant concentration, temperature, and residence times was estimated.

Comparative pyrolysis studies of lignocellulosic biomasses: Online gas quantification, kinetics triplets, and thermodynamic parameters of the process.

This study focused on the analysis of the pyrolytic behavior of four lignocellulosic biomasses: avocado stone (AS), Agave salmiana bagasse (AB), cocoa shell (CS), and α-cellulose (CEL). According to the triplet kinetics analysis, the order of pyrolytic decomposition was AS < AB < CEL < CS. The AS was dominated by a second-order reaction, while AB followed a 2D diffusion-Valensi model. On the other hand, the pyrolysis of CS starts with an nth-order reaction and ends random nucleation model, and CEL was dominated by one-dimensional diffusion and first-order reaction. Thermodynamic studies reveal that the difference between the activation energy versus enthalpy change was<6.5 kJ/mol for all biomasses, thus showing the ease of pyrolysis reaction of these biomasses. Furthermore, the AS and AB showed that the reactions are close to thermodynamic equilibrium and stability, whereas CS and CEL indicated high reactivity.

Aminations and arylations by direct C-O activation for the design of 7,8-dihydro-6H-5,8-ethanopyrido[3,2-d]pyrimidines.

The design of some novel disubstituted 7,8-dihydro-6H-5,8-ethanopyrido[3,2-d]pyrimidine derivatives is reported. The series was developed from quinuclidinone, which afforded versatile platforms bearing one lactam function in position C-2 that were then used to create C-N or C-C bonds for S N Ar or palladium-catalyzed cross-coupling reactions by in situ C-O activation. The reaction conditions were optimized under microwave irradiation, and a wide range of amines or boronic acids were used to determine the scope and limitations of each method. To complete this study, the X-ray crystallographic data of 7,8-dihydro-6H-5,8-ethanopyrido[3,2-d]pyrimidine derivative 49 were used to formally establish the structures of the products.

Comparative data of molecular weight distribution of agave fructans fractions using MALDI-ToF and HPLC-SEC.

A comparative data of two generally accepted mass techniques for estimate the molecular weight distribution of polysaccharides are presented. The data were obtained from agave fructans samples of different molecular weight, which were analyzed authored independently. The two analytical techniques used were Matrix-Assisted Laser Desorption/Ionization Time-Of-Flight Mass Spectrometry (MALDI-ToF) and High Pressure Size Exclusion Chromatography (HP-SEC). The data set here are related to the research paper entitled "Size-exclusion chromatography (HPLC-SEC) technique optimization by simplex method to estimate molecular weight distribution of agave fructans" by Moreno-Vilet et al. [1]. This article present the comparative figures as histograms obtained from mathematically processed MALDI-ToF spectra and HPLC-SEC chromatograms. And also, the calculated polymer parameters as number and mass molecular weight, number and mass average degree of polymerization and dispersity index.

Size-exclusion chromatography (HPLC-SEC) technique optimization by simplex method to estimate molecular weight distribution of agave fructans.

Agave fructans are increasingly important in food industry and nutrition sciences as a potential ingredient of functional food, thus practical analysis tools to characterize them are needed. In view of the importance of the molecular weight on the functional properties of agave fructans, this study has the purpose to optimize a method to determine their molecular weight distribution by HPLC-SEC for industrial application. The optimization was carried out using a simplex method. The optimum conditions obtained were at column temperature of 61.7°C using tri-distilled water without salt, adjusted pH of 5.4 and a flow rate of 0.36mL/min. The exclusion range is from 1 to 49 of polymerization degree (180-7966Da). This proposed method represents an accurate and fast alternative to standard methods involving multiple-detection or hydrolysis of fructans. The industrial applications of this technique might be for quality control, study of fractionation processes and determination of purity.

Optimization of the isolation and quantitation of kahweol and cafestol in green coffee oil.

Kahweol and cafestol are two diterpenes that exist mainly as esters of fatty acids in green coffee oil. To recover them under their free form they have to be either saponified or trans-esterified. These two compounds are well known to be sensitive to heat, and reagents, therefore experimental conditions used in the transesterification reaction are critical. In this paper, a Doehlert experimental design plan is used to optimize the transesterification conditions using some key variables such as the temperature of the reaction, the reagent base concentration and the duration of the reaction. Therefore, the optimal parameters determined from the Doehlert design are equal to 70 °C, temperature of the reaction; 1.25 mol L(-1) concentration of the reagent base; and 60 min reaction time. The contour plots show that the extracted quantity of kahweol and cafestol can depend greatly from the experimental conditions. After transesterification, the free form of the diterpernes is extracted from the lipid fraction using liquid-liquid extraction and analyzed using GC-FID without prior derivatization. The amount of kahweol and cafestol obtained from green coffee oil obtained by cold mechanical press of Catuai coffee bean is equal to 33.2±2.2 and 24.3±2.4 g kg(-1)oil, respectively. In an attempt to streamline the process, the transesterification reaction is performed in an in-flow chemistry reactor using the optimal conditions obtained with the Doehlert experimental design. The amount of kahweol and cafestol obtained from the same green coffee oil is equal to 43.5 and 30.072 g kg(-1)oil, respectively. Results are slightly higher compared to the ones obtained with the batch procedure. This can be explained by a better mixing of the coffee oil with the reagents and a faster transesterification reaction.

Interest of a chemometric approach in understanding the retention behaviour of three columns in hydrophilic interaction liquid chromatography: application to the separation of glycerol carbonate, glycerol and urea.

A chemometric approach was used to study the retention behaviour of glycerol, urea and glycerol carbonate in hydrophilic interaction liquid chromatography (HILIC). First, a simplex method was developed to optimize the sensitivity of an evaporative light scattering detector. A mixture design was then applied to model retention factors as a function of the mobile phase content in acetonitrile, water and methanol on three columns: Atlantis HILIC Silica, ZIC-HILIC and Monochrom diol. Atlantis HILIC Silica exhibits predominantly hydrophobic interactions, while retention on the other two columns is mainly ruled by hydrophilic interactions. Finally, a desirability function is applied on the resolution factors. The use of this function enables the compositions of eluent phases to be determined in order to achieve separation between the three chemicals. Monochrom diol proved to be the most efficient column.

Kinetic modelling of the degradation of the alpha-tocopherol in biodiesel-rape methyl ester.

The aim of this work was to study the influence of three major factors (light, atmospheric oxygen, temperature) responsible for the degradation of tocopherols. The evolution of alpha-tocopherol contents was analysed by high-performance liquid chromatography. Taguchi's experimental design was applied to establish a mathematical model of alpha-tocopherols degradation in function of the studied parameters especially in a domain of temperature between 50 degrees C and 150 degrees C. The results show that the major factor is the temperature, especially above 100 degrees C. Light is a negligible factor, meaning that degradation is mainly due to an autoxidation phenomenon. Moreover, only interactions between temperature and atmospheric oxygen have been observed especially above 100 degrees C. The mathematical model was validated for a temperature of 75 degrees C and permits to calculate a predictive speed of degradation in this domain.

Purification of sugar beet vinasse - adsorption of polyphenolic and dark colored compounds on different commercial activated carbons.

The adsorption on activated carbons of dark colored compounds contained in sugar beet vinasse was studied. Four commercial activated carbons with different properties (particle size, residual acidity and microporous properties) were respectively checked for efficiency at two temperature levels (25 degrees C and 40 degrees C) and at four pH levels (2,3.5,7,10). The adsorption of organic molecules was determined by quantifying the amounts of total polyphenolic compounds and total organic carbon. The results showed that the adsorption capacity of dark colored compounds was enhanced by the decrease in both temperature and pH values of the solution. In this study, it is shown that this capacity depends on activated carbon characteristics which can be classified in the following order: particle size>residual acidity>microporous volume. Three models (Langmuir, Freundlich and Dubinin-Radushkevich) were tested from experimental data and compared. The Langmuir model provided the best correlation on all the activated carbons studied.