Effect of Reaction Conditions on the Kinetics of Living Isobutylene Polymerization at High Initiator/TiCl4Ratios

2000 ◽  
Vol 33 (13) ◽  
pp. 4634-4638 ◽  
Author(s):  
C. Paulo ◽  
J. E. Puskas ◽  
S. Angepat
1981 ◽  
Vol 46 (3) ◽  
pp. 693-700 ◽  
Author(s):  
Milan Strašák ◽  
Jaroslav Majer

The kinetics of oxidation of alkenes by thallic sulphate in aqueous solutions, involving the two reaction steps-the hydroxythallation and the dethallation - was studied, and the effect of salts on the kinetics was examined; this made it possible to specify more precisely the reaction mechanism and to suggest a qualitative model of the reaction coordinate. It was found that in homogeneous as well as in heterogeneous reaction conditions, the reaction can be accelerated appreciably by adding tetraalkylammonium salts. These salts not only operate as catalysts of the phase transfer, but also exert a significant kinetic effect, which can be explained with a simplification in terms of a stabilization of the transition state of the reaction.


Foods ◽  
2020 ◽  
Vol 9 (12) ◽  
pp. 1809
Author(s):  
Zhanzhi Liu ◽  
Ying Li ◽  
Jing Wu ◽  
Sheng Chen

d-mannose has exhibited excellent physiological properties in the food, pharmaceutical, and feed industries. Therefore, emerging attention has been applied to enzymatic production of d-mannose due to its advantage over chemical synthesis. The gene age of N-acetyl-d-glucosamine 2-epimerase family epimerase/isomerase (AGEase) derived from Pseudomonas geniculata was amplified, and the recombinant P. geniculata AGEase was characterized. The optimal temperature and pH of P. geniculata AGEase were 60 °C and 7.5, respectively. The Km, kcat, and kcat/Km of P. geniculata AGEase for d-mannose were 49.2 ± 8.5 mM, 476.3 ± 4.0 s−1, and 9.7 ± 0.5 s−1·mM−1, respectively. The recombinant P. geniculata AGEase was classified into the YihS enzyme subfamily in the AGE enzyme family by analyzing its substrate specificity and active center of the three-dimensional (3D) structure. Further studies on the kinetics of different substrates showed that the P. geniculata AGEase belongs to the d-mannose isomerase of the YihS enzyme. The P. geniculata AGEase catalyzed the synthesis of d-mannose with d-fructose as a substrate, and the conversion rate was as high as 39.3% with the d-mannose yield of 78.6 g·L−1 under optimal reaction conditions of 200 g·L−1d-fructose and 2.5 U·mL−1P. geniculata AGEase. This novel P. geniculata AGEase has potential applications in the industrial production of d-mannose.


2007 ◽  
Vol 72 (9) ◽  
pp. 1269-1283 ◽  
Author(s):  
Jiří Raška ◽  
František Skopal ◽  
Karel Komers ◽  
Jaroslav Machek

Biotransformation of glycerol to 1,3-dihydroxyacetone was carried out in an isothermal isochoric batch reactor with Gluconobacter oxydans immobilized in poly(vinyl alcohol) gel capsules. The reaction course was described with a three-step kinetic model. Two reaction schemes were proposed and compared with 8 kinetic experiments at 25 °C. The experimental dependences of glycerol and dihydroxyacetone concentrations on reaction time were simulated very well by the autocatalytic model. The effects of reaction temperature and initial concentrations of yeast extract and glycerol were studied. Temperature 25-30 °C, initial yeast extract concentration 2-4 g l-1 and initial glycerol concentration 20-50 g l-1 were found as optimal. The determined rate constants can be used to advantage for industrial production of dihydroxyacetone from glycerol.


2021 ◽  
Vol 37 (2) ◽  
pp. 467-475
Author(s):  
Marina G. Xavier

Batch adsorption studies were done on aqueous solutions of Pb(NO3)2 at varying solute concentration, adsorbent dose, contact time, temperature, calcination temperatures and pH. Residual concentrations of the solute were found out using AAS and optimum conditions were studied. Adsorbent used in this study is locally available silicate rich mineral which closely resembles zeolites. The net negative charge on the framework of hydrated aluminosilicates is responsible for ion exchange property. Freundlich model was used to validate the results obtained from batch experiments plotting lnCe vs lnqe. Objective of this work is to study the kinetics of adsorption considering the interplay of particle diffusion in addition to proving the effectiveness as an adsorbent. A diffusion model also was also applied apart from kinetic model to analyze the experimental results more specifically. For maximizing the efficiency of the adsorption process and minimizing the time involved, variables like temperature, reactants and pH were manipulated using kinetic studies. It establishes the optimum reaction conditions for various experimental parameters in the process of adsorption.


2011 ◽  
Vol 239-242 ◽  
pp. 161-167
Author(s):  
Xiao Zhen Wang ◽  
Yi Feng Zhu ◽  
Xiao Nian Li

A 2 wt % Pd/C catalyst has been prepared by chemical impregnation and used to catalyze the hydrogenation of o-chloronitrobenzene (o-CNB) to o-chloroaniline (o-CAN) in solvent-free conditions. The effects of reaction temperature, H2 pressure, and stirring intensity on the hydrogenation kinetics have been investigated. The hydrogenation reaction showed very high selectivity with dehalogenation side products as low as 0.3% of total yield. The favorable reaction conditions were found to be temperature T = 383 K, stirring speed = 900 rpm, and feeding ratio CNB/catalyst = 200/1 (m/m). The recycled Pd/C still retained more than 98% of its original selectivity after 12 repeat used, indicating the catalyst had strong potentials for commercial application at industrial scale.


1960 ◽  
Vol 33 (3) ◽  
pp. 696-698
Author(s):  
S. E. Bresler ◽  
M. I. Mosevitskiĭ

Abstract For the study of the mechanism of polymerization by means of complexes of aluminum organic compounds with titanium chlorides, data on the kinetics of polymerization is of great interest. Up to the present time, the rate of polymerization of propylene has been studied but the interpretation of the kinetic data is difficult because the polymer, which is practically insoluble in the reaction medium, entraps the catalyst resulting in a rate of reaction which is dependent on the diffusion of monomer through the polymer to the active sites. In this work the polymerization of isoprene, which yields polymers soluble in the monomer, in saturated hydrocarbons and in benzene, was studied. The rate of the polymerization reaction was measured by the thermal effect in a calorimeter consisting of a 3.5 1. Dewar flask, with a lid, immersed in a thermostated air bath maintained at approximately the temperature of the reaction. Low viscosity spindle oil, heated to the temperature of the reaction (about 32°), served as the calorimeter fluid. The ampoule holder extended outside of the calorimeter and was connected to a shaking apparatus. The ampoule was divided by a thin partition into two sections each holding 45–50 cc. Into one section previously purified monomers and solvent were distilled. The other section was filled with catalyst components from a Shlenk container. The change in temperature of the calorimeter was determined with a Beckman thermometer with an accuracy of 0.01 °. When the temperature of the calorimeter containing the ampoule remained constant to within 0.01–0.02° for 30–40 minutes, the shaking apparatus was connected and the partition was broken with a striker. Intensive shaking was continued during the entire experiment resulting in mixing of the reaction mixture and of the calorimeter fluid. The rate of reaction was determined by the rate of heat evolution ; in other words, by the temperature rise in the calorimeter. For a rise of 0.1–0.5° the reaction conditions remained practically isothermal. This rise permits the kinetics of the reaction to be observed with sufficient accuracy. Adiabaticity of the calorimeter and the effect of mechanical heat were controlled in separate experiments.


2014 ◽  
Vol 665 ◽  
pp. 241-246
Author(s):  
Jun Wen Wang ◽  
Kan Zhang ◽  
Xi Ying Mao ◽  
Xue Hua Zhao ◽  
Chuan Min Ding

With different content of thiophene in coking crude benzene, the Orthogonal design experiments of thiophene hydrodesulfurization on a Ti modified Co-Mo-P/γ-Al2O3 catalyst were carried out in a micro-reactor under the reaction conditions of 2.3~2.7MPa,275~335°C, 0.5h-1LHSV and H2/Oil 600~750. The kinetic parameters and the intrinsic kinetics were acquired by 4-order Runge-Kutta method and the modified Simplex method. The power-law type kinetic model was established and consistent with the experiment data and highly acceptable and reliable.


Author(s):  
Iztok Hace

Free radical polymerization kinetics of diallyl terephthalate (DAT) in solution was investigated with two different peroxide initiators: dicyclohexyl peroxydicarbonate (CHPC) and benzoyl peroxide (BPO) in temperature range from 50°C to 110°C, where ortho-xylene was used as a solvent. Conversion points were measured using Fourier Transform Infrared (FTIR) measurements. Previously developed kinetic model for bulk DAT polymerization, was extended to solution DAT polymerization. The ratio of solvent chain - transfer rate constants to propagation rate constants of the polymerization system were found between 1.25 10-4 to 1.68 10-4 for various reaction conditions. They were obtained using the calculated initial polymerization rates and the number average molecular weight measurements made by GPC. The effect of different solvent fractions and initiator concentrations on the diffusion limitations were investigated. Only two kinetic parameters, kpd0 and ktd0 were obtained by fitting the kinetic model onto measured conversions for various reaction conditions at 0.2, 0.5 and 0.8 solvent fractions. Thus obtained kpd0 and ktd0 kinetic parameters were extrapolated to zero solvent fractions and from obtained values of kinetic parameters the conversion points for bulk DAT polymerization were calculated and compared to measured conversion points.


Catalysts ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 435
Author(s):  
Aso A. Hassan ◽  
Joseph D. Smith

This work investigates the non-catalyzed supercritical methanol (SCM) process for continuous biodiesel production. The lab-scale setup was designed and used for biodiesel production in the temperature range of 520–650 K and 83–380 bar with an oil-to-methanol molar ratio ranging from 1:5 to 1:45. The experiments were performed in the coiled plug flow tubular reactor. The volumetric flow rate of the methanol/oil ranged from 0.1–10 mL/min. This work examines a new reactor technology involving preheating and pre-mixing of the methanol/oil mixture to reduce setup cost and increase biodiesel yield under the same reaction conditions. Work performed showed that FAME’s yield increased rapidly with temperature and pressure above the methanol critical points (i.e., 513 K and 79.5 bar). The best methyl-ester yield using this reaction technology was 91% at 590 K temperature and 351 bars with an oil-to-methanol ratio of 39 and a 15-min residence time. Furthermore, the kinetics of the free catalyst transesterification process was studied in supercritical methanol under different reaction conditions.


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