Electro-oxidation of hydrazine on electrodes modified with vitamin B12

In this paper we report a kinetic study of the electro-oxidation of hydrazine catalyzed by vitamin B₁₂ pre-adsorbed on an ordinary pyrolytic graphite electrode. Kinetic parameters were determined by linear sweep voltammetry and rotating-disk electrode polarization curves. The order of the reaction is 1 in OH⁻ ions and Tafel plots give slopes of 80 mV/decade. A possible redox-catalysis mechanistic scheme is proposed.     

氯乙烯悬浮聚合温度控制策略

本文在综合剖析氯乙烯两相聚合动力学特征和聚合釜传热的基础上,讨论聚合温度控制问题,并提出温度控制策略。     

Kinetic study of phenolic resin cure by IR spectroscopy

The cure reaction of a commercial phenolic resin (FRD‐5002, Borden Chimie S.A.) has been studied by IR spectroscopy (Fourier transform IR). A phenomenological approach was used to characterize the kinetic of reaction. Various kinetic models, including homogeneous reactions, diffusion‐controlled reactions, phase boundary movement, and nucleation and growth‐type kinetic, have been tested. Kinetic analyses using integral procedures on isothermal data indicate that the cure reaction data can be described above 140°C using the homogeneous first‐order reaction model. The activation energy has been found to be about 49.6 kJ mol⁻¹. At lower temperature, a diffusive mechanism was active, and the kinetic of reaction was well described by the Jander kinetic model. Because of the simple kinetic control active above 140°C, a mechanistic model for the resol cure at these temperatures has been also proposed. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 2703–2715, 1999     

Kinetics and mechanism of the KOH — catalyzed methanolysis of rapeseed oil for biodiesel production

The reaction of rapeseed oil with methanol catalyzed by KOH is described by a model consisting of two sequences of consecutive competitive reactions. The first sequence expresses the methanolysis of rapeseed oil to methyl esters (biodiesel) whereas the second sequence describes the always present side reaction‐saponification of glycerides and methyl esters by KOH. The proposed chemical model is described (after rational simplifications) by a system of differential kinetic equations which are solved numerically by two independent computing methods. The thus obtained theoretical kinetic and equilibrium results are compared numerically and/or graphically with the experimental parameters. The latter were obtained by the determination of the relevant components in the actual reaction mixture by analytical methods. According to the experimental results, the proposed reaction scheme is fulfilled with the probability of ca. 78%. The optimal average rate constants and equilibrium constants of individual reaction steps of the discussed scheme are introduced. The limitations of the proposed reaction model are discussed.     

Investigation of the TiCl4 reaction order in quasiliving styrene polymerization with 1-phenylethyl chloride/TiCl4/Bu2O

Summary The reaction order with respect to TiCl₄ was investigated in the quasiliving polymerization of styrene using a 1-phenylethyl chloride/TiCl₄/Bu₂O initiating system in mixture of 1,2-dichloroethane and n-hexane (55:45 v/v) at -15 °C. It was found out that the reactions order with respect to TiCl₄ was closer to 1. A mechanistic scheme to explain the kinetic behavior of quasiliving styrene polymerization in 1-phenylethyl chloride/TiCl₄/Bu₂O is proposed.     

A kinetic modelling study of ethane cracking for optimal ethylene yield

Current generation steam cracking plants are considered to be mature. As a consequence it is becoming more and more important to know whether the underlying mechanistic cracking process offers still scope for further improvements. The fundamental kinetic limits to cracking yields have recently been researched in detail for different feed stocks with a new synthesis reactor model, d-RMix, incorporating a large scale mechanistic reaction scheme, SPYRO^® [M.W.M. van Goethem, S. Barendregt, J. Grievink, J.A. Moulijn, P.T.J. Verheijen “Model-based, thermo-physical optimisation for high olefin yield in steam cracking reactors”, Chemical Research and Engineering Developments 88 (2010) 1305–1319]. Mathematical optimization revealed for ethane cracking a maximum ethylene yield of about 67 wt%. with a linear-concave optimal temperature profile along the reaction coordinate with a maximum temperature between 1200 and 1300 K. Further mechanistic analysis of these results showed that the linear-concave shape not only suppresses the successive dehydrogenation and condensation reactions of ethylene, but mainly reduces the role of the ethane initiation reaction to form two methyl radicals.     

添加结焦抑制剂的轻柴油裂解反应和结焦反应模型

本文研究了有结焦抑制剂YZS1存在时的轻柴油裂解和结焦反应动力学.考虑了结焦抑制剂的功能,组合了裂解反应新的反应图式,提出了添加结焦抑制剂YZS1的轻柴油裂解反应动力学模型.实验证明裂解反应的结焦前兆体是乙烯、丙烯和芳烃,进而提出了简化的结焦动力学模型.     

Thermooxidative ageing of polyoxymethylene,part 1: Chemical aspects

The thermal oxidation of unstabilised POM homopolymer has been studied at 90, 110, and 130°C under various oxygen pressures ranging from 0 to 2.0 MPa by gravimetry and IR spectrometry. This latter reveals essentially the formation of formate (F) groups and alcohols in smaller quantities. The formate growth and mass loss rates increase pseudo hyperbolically with oxygen pressure, the asymptotic level being reached at pressures up to 0.5 MPa. These results lead to propose a mechanistic scheme of radical chain oxidation in which depolymerization is initiated by hydroperoxide unimolecular decomposition, one formate and one chain scission being formed per decomposition event whereas the kinetic chain length of the depolymerization zip is of the order of 100. A kinetic model derived from the mechanistic scheme, taking into account substrate consumption, simulates correctly the shape of kinetic curves and the effect of temperature and oxygen pressure. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Reaction scheme and kinetic modelling for the MTO process over a SAPO-18 catalyst

A kinetic model for simulation of the MTO process over SAPO-18 catalyst in a wide range of operating conditions has been proposed. The kinetic model predicts the experimental evolution of reaction products with time on stream, which follows three consecutive periods: initiation (where olefin production increases), a period of maximum olefin production and a period in which this production decreases. The kinetic scheme takes into account these three steps that evolve with time on stream: formation of active intermediate compounds, an step where olefins are formed by reaction of oxygenates (methanol/DME) with these intermediates and deactivation of intermediates by degradation to coke. The presence of water in the reaction medium attenuates the reaction rate of these steps. Discrimination of kinetic equations and calculation of the parameters of best fit have been carried out by solving the mass conservation equations of the individual components of the kinetic scheme together with the kinetic equation for deactivation and taking into account the effect of water on the kinetics of each step.     

Systematic determination of intrinsic reaction parameters in enzyme immobilizates

For the rational design of processes using immobilized enzymes a mechanistic kinetic model is required, which accounts for all kinetic and thermodynamic phenomena, including the enzyme reaction, the mass transfer of the reactants between both phases, and their diffusion inside the immobilizate. For the example of enzymes immobilized in hydrogel beads suspended in an organic solvent, such a mechanistic kinetic model was obtained by a model-based experimental analysis approach. It was proven that the usually applied concentration measurements in the bulk phase are not sufficient to draw mechanistic conclusions. The most suitable measurement technique was found to be the quantification of the concentration along the radius of the hydrogel bead. These line scans, achieved by two-photon laser scanning microscopy, for the first time allowed to estimate intrinsic reaction and mass transfer parameters simultaneously. Thus, the obtained intrinsic parameter estimates for the biphasic hydrogel system could be directly compared with those obtained in individual systems. This comparison revealed for the first time that the enzyme reaction was not significantly affected by the mild hydrogel encapsulation. However, a significant impact on the transport parameters was found that underlines the need for analyzing the real reaction system using mechanistic models.     

ROLE OF WATER IN THE KINETIC MODELING OF METHANOL TRANSFORMATION INTO HYDROCARBONS ON HZSM-5 ZEOLITE

The attenuating effect of reaction-medium water (feed and/or reaction product) on the kinetics of the steps of methanol transformation into hydrocarbons on a HZSM-5 zeolite catalyst was studied by means of a kinetic model. In this model, the effect of water was quantified in all the steps of the kinetic scheme by means of a kinetic parameter, which is constant with temperature under the conditions of the MTG process. At low temperature, under conditions in which only methanol dehydration occurs, the kinetics of this reaction is attenuated by the presence of water, and the coefficient that quantifies the attenuation decreases as temperature is increased. In addition to considering the effect of water content in the reaction medium, another innovation of the kinetic model proposed, compared to those proposed in the literature consisting of lumps, is the fact that the higher reactivity of dimethyl ether over methanol is taken into account. A step of cracking of gasoline lump hydrocarbons to produce light olefins (ethene and propene) was also taken into account. The kinetic model proposed was verified by using the results obtained in an integral isothermal fixed bed reactor, in the 573-723 K range, for an ample range of space time values. The results revealed that the effect of water is due to its adsorption on the active sites by competition with the intermediate compounds of the kinetic scheme.     

ROLE OF WATER IN THE KINETIC MODELING OF METHANOL TRANSFORMATION INTO HYDROCARBONS ON HZSM-5 ZEOLITE

The attenuating effect of reaction-medium water (feed and/or reaction product) on the kinetics of the steps of methanol transformation into hydrocarbons on a HZSM-5 zeolite catalyst was studied by means of a kinetic model. In this model, the effect of water was quantified in all the steps of the kinetic scheme by means of a kinetic parameter, which is constant with temperature under the conditions of the MTG process. At low temperature, under conditions in which only methanol dehydration occurs, the kinetics of this reaction is attenuated by the presence of water, and the coefficient that quantifies the attenuation decreases as temperature is increased. In addition to considering the effect of water content in the reaction medium, another innovation of the kinetic model proposed, compared to those proposed in the literature consisting of lumps, is the fact that the higher reactivity of dimethyl ether over methanol is taken into account. A step of cracking of gasoline lump hydrocarbons to produce light olefins (ethene and propene) was also taken into account. The kinetic model proposed was verified by using the results obtained in an integral isothermal fixed bed reactor, in the 573–723 K range, for an ample range of space time values. The results revealed that the effect of water is due to its adsorption on the active sites by competition with the intermediate compounds of the kinetic scheme.     

Thermal deactivation studies of coconut shell pyrolysis

The kinetics of pyrolysis of predried coconut shell sample has been investigated in the temperature range of 523 K to 1023 K in an inert atmosphere by captive sample technique. A kinetic scheme has been proposed where two parallel reactions are given for the production of volatiles and char. The reaction rate constants are found to decrease with high temperatures above 673 K due to chemical and physical changes of the reactant during devolatilisation reaction. Several deactivation models have been proposed to give good agreement with the experimental data.     

Asymmetric Hydrogenation of Activated Ketones on Platinum: Relevant and Spectator Species

The heterogeneous enantioselective hydrogenation of activated ketones over chirally modified platinum is reviewed with emphasis on identifying the role of the various species observed in this catalytic system. The past years have witnessed a continuous broadening of the scope of this catalytic system including new reactants and modifiers affording over 97% ee. New reaction pathways have been uncovered and the kinetic and mechanistic studies have been faced with a number of complicating factors caused by spectator species and interactions in solution and on the Pt surface. The previously proposed mechanistic models are critically assessed in the light of these new findings.     

聚乙烯醇水溶液中H_2O_2的催化分解反应动力学研究

研究了在聚乙烯醇 ( PVA)水溶液中 H2 O2 的催化分解反应动力学 ,讨论了 PVA浓度、反应温度、搅拌速率等对 H2 O2 分解反应的影响。结果表明由于小分子在 PVA水溶液中的扩散影响 ,致使 H2 O2 的分解反应动力学行为明显偏离经典的 H2 O2 分解反应动力学曲线 ,其偏离程度依赖于扩散的影响     

Systematics and modelling representations of LPG thermal cracking for olefin production

Pyrolysis of hydrocarbons is an important commercial process for the production of ethylene, propylene and 1,3 butadiene. These low molecular weight olefins are among the most important base chemicals for the petrochemical industries for polymer production. A simulation program of the reaction kinetics and coke formation inside the coils of a thermal cracking unit can provide information on the effects of operating conditions on the product distribution. The aim of this study was to develop a mechanistic reaction model for the pyrolysis of LPG that can be used to predict the yields of the major products from a given LPG sample with commercial indices. A complete reaction network, using a rigorous kinetic model, for the decomposition of the LPG feed has been developed, which is used for the simulation of industrial LPG crackers. This model has been adapted using industrial data for the pyrolysis yields of LPG. The present paper attends on the asymptotic coking mechanism and describes the development of a kinetic coking model in the pyrolysis of LPG. Detailed and accurate information about the product distribution, growth of coke layer, the evolution of the tube skin temperatures can be obtained from this simulation. Simulations of this kind can be used to optimize the furnace operation. They can be used as a guide for the adaptation of the operating variables aiming at prolonging the run length of the furnace. The reactor model, as well as kinetic scheme, is tested in an industrial cracking furnace.     

Chemical kinetic modeling of i‐butane and n‐butane catalytic cracking reactions over HZSM‐5 zeolite

A chemical kinetic model for i‐butane and n‐butane catalytic cracking over synthesized HZSM‐5 zeolite, with SiO₂/Al₂O₃ = 484, and in a plug flow reactor under various operating conditions, has been developed. To estimate the kinetic parameters of catalytic cracking reactions of i‐butane and n‐butane, a lump kinetic model consisting of six reaction steps and five lumped components is proposed. This kinetic model is based on mechanistic aspects of catalytic cracking of paraffins into olefins. Furthermore, our model takes into account the effects of both protolytic and bimolecular mechanisms. The Levenberg–Marquardt algorithm was used to estimate kinetic parameters. Results from statistical F‐tests indicate that the kinetic models and the proposed model predictions are in satisfactory agreement with the experimental data obtained for both paraffin reactants. © 2011 American Institute of Chemical Engineers AIChE J, 58: 2456–2465, 2012     

Photocatalytic intrinsic reaction kinetics. II: Effects of oxygen concentration on the kinetics of the photocatalytic degradation of dichloroacetic acid

The effect of oxygen on the reaction kinetics of the photocatalytic oxidation of dichloroacetic acid at pH below the titanium dioxide isoelectric point (pH from 5 to 4) was studied. A kinetic scheme based on the direct hole attack to the dichloracetate ion in conjunction with the classical role of oxygen acting as an electron acceptor is proposed. Oxygen also intervenes in a direct addition reaction to one of the intermediate reaction products. Experiments were conducted in a well-mixed, small, flat plate reactor employing Aldrich titanium dioxide as the photocatalyst in the suspension mode and using polychromatic irradiation with energy in the range from 275 to 385 nm in wavelength. A complete mathematical model, including the effect of the absorbed radiation intensities and catalyst concentration was developed. Experimental data agree well with theoretical predictions employing just two kinetic parameters derived from the proposed reaction mechanism.     

Optimization of polyester sheet molding compound. Part II: Theoretical modeling

A mechanistic kinetic and heat transfer model is used to describe the cure of sheet molding compounds (SMC). Kinetic parameters such as rate constant of initiator decomposition and rate constant of propagation are estimated from the induction time and the time to reach the peak exotherm of isothermal reaction curves measured by the differential scanning calorimetry (DSC). Temperature and conversion profiles inside plate sections of SMC parts during molding are measured. The predicted results compare well with the experimental data except the limiting conversion. A set of predictive parameters are proposed from this model as guidelines for the optimal molding of SMC. Several moldability diagrams are also constructed which can be easily used to design the optimum SMC recipe for a given processing condition.     

Mechanism and kinetics of hydrochloric acid initiated ɛ-caprolactam polymerization

Summary A mechanistic scheme is suggested for lactam polymerisation initiated by hydrochloric acid on the basis of the general mechanism put forward earlier by Bertalan et al. According to this mechanism during the polymerization conditions are created which can initiate further polymerizations resulting in a characteristic inflection type kinetic curve. Experimental results can be well interpreted qualitatively on the basis of this mechanism, and therefore it can serve as a starting point also for a quantitative kinetic model.Presented at 31st IUPAC macromolecular symposium, 30 June 1987, Merseburg, German Democratic Republic, I/43