酸岩反应动力学实验研究方法评述

酸岩反应动力学实验研究是酸压技术的重要组成部分,其实验结果为酸压设计的优化和酸液体系的优选提供准确参数和依据,为获得准确的反应动力学参数,选择合适的实验方法至关重要。本文对目前各种酸岩反应动力学实验研究方法的优缺点进行了比较和评述,为今后酸岩反应动力学实验研究提供了借鉴和参考。     

甲醇在耐高温磺酸树脂催化下的脱水反应动力学

为了开发反应精馏合成二甲醚新工艺,实验在2MPa(G)、120℃～155℃、初始甲醇摩尔分数100%～30%、液空速0.10mL/(min·g催化剂)～0.15mL/(min·g催化剂)条件下,以耐高温磺酸树脂作催化剂,在等温积分反应器内,系统地测定了甲醇脱水生成二甲醚的反应动力学数据。分别用L-H及E-R模型建立了反应动力学方程,并对实验数据进行了拟合。拟合结果表明:在实验范围内,按E-R模型拟合的反应动力学方程与实验结果更吻合。通过对动力学方程进行分析,发现随着反应温度的升高以及甲醇活度与水活度比值的增大,甲醇脱水反应速率都会增大。实验工作可为开发反应精馏合成二甲醚新工艺提供重要的反应动力学数据。     

明胶的酶降解反应动力学研究——Ⅱ.动力学规律和机理

根据文献[1]中的实验数据,结合化学反应动力学的基础理论,计算了明胶的酶降解反应的反应级数、表观活化能、指前因子等有关动力学参数值。得到反应的总速率方程。所求得的反应速率常数与温度的关系表明,在实验温度范围内,符合Arrhenius公式。最后提出了该反应的酶催化反应机理,实验结果与所推得的机理动力学方程相吻合。     

硫酸脲分解磷矿反应动力学

通过硫酸脲分解磷矿的搅拌强度和磷矿粒度实验,探讨其中的传递过程。实验研究表明,硫酸脲分解磷矿为典型的缩芯反应,反应过程受产物形成的固膜扩散所控制,在排除液相扩散和反应粒子表面及微孔影响下,进行反应动力学实验。建立了硫酸脲与磷矿反应的动力学模型,由实验数据求得动力学参数,其反应活化能为12．73kJ／mol。     

月桂酸甲酯烷氧基化反应动力学研究

基于一级反应动力学机理,研究了以月桂酸甲酯、环氧乙烷(EO)、环氧丙烷(PO)为原料,MCT-09为催化剂合威月桂酸甲酯烷氧基化物的反应动力学.建立了反应动力学模型,通过反应动力学实验,将实验数据回归拟合,确定反应动力学参数.讨论了温度对烷氧基化反应速率常数k的影响,求得月桂酸甲酯乙氧基化、丙氧基化反应的活化能分别为50.715 kJ/mol和68.757 kJ/mol,优化月桂酸甲酯烷氧基化反应温度为463 K.     

煤气化反应动力学实验研究方法进展

总结和概括了煤气化反应动力学研究中所使用的方法,对煤气化反应动力学研究中最常用的方法、工作原理及其优点和不足之处进行了详细的叙述,为研究者在进行煤气化反应动力学研究过程中实验方法的选取和实验装置的设计提供指导.     

Pd/α-Al_2O_3催化乙炔选择性加氢微观反应动力学

采用乙炔顺序加氢的反应机理,利用已报道的密度泛函理论(DFT)计算结果进行了乙炔加氢反应的微观反应动力学模拟,所得的乙炔加氢反应动力学具有共同的特征。利用实验获得的Pd/α-Al_2O_3催化乙炔加氢反应动力学数据,对上述DFT数据进行校验,发现经过不超过0.1eV的调整,微观反应动力学模拟结果与实验结果符合很好,说明DFT数据是良好的微观反应动力学参数来源。利用优化后的动力学参数模拟了工业生产范围内的动力学,获得了速率控制步骤和表面物种等信息,可为双曲动力学模型的建立提供参考。     

压力对甲醇合成本征反应速率常数的影响

本文对不同压力下一氧化碳和二氧化碳同时加氢合成甲醇的复合反应本征动力学进行了实验研究。实验在压力3—7MPa,温度215—245 C的条件下进行,采用C301—1型铜基催化剂。本研究以已经获得的以逸度表示的L-H-H-W型复合反应本征动力学方程为基础,依据不同压力下的本征动力学测试数据的处理结果,考察了压力对反应速率常数的影响。实验结果表明:此复合反应动力学方程在实验压力范围内是适用的,反应速率常数与压力无关。     

铬酸钠碳化反应动力学研究

研究了铬酸钠碳化反应动力学,在1个2 L反应釜内,通过监测反应过程中CO2压力的变化,计算反应速率,避免了因逆反应过快造成的溶液取样分析的困难。实验发现反应速率有一个下降-升高-下降的变化过程。通过反应机理分析,导出了动力学方程,并根据动力学方程较好地解释了实验现象。     

明胶的酸水解反应动力学研究 Ⅱ.动力学规律和机理

根据文献的实验数据,计算了明胶的柠檬酸水解反应的反应级数、表观反应速率常数、表观活化能和指前因子等动力学参数,得到了反应速率方程式。并求得实验温度范围内的反应速率常数与温度的关系,符合Arrhenius公式。对明胶的酸催化反应机理进行了探讨,推得的机理动力学方程和实验结果相符合。     

Nonlinear kinetic parameter estimation using simulated annealing

The performance of simulated annealing (S-A) in nonlinear kinetic parameter estimation was studied and compared with the classical Levenberg–Marquardt (L–M) algorithm. Both methods were tested in the estimation of kinetic parameters using a set of three kinetic models of progressively higher complexity. The models describe the catalytic wet air oxidation of phenol carried out in a small-scale trickle bed reactor. The first model only considered the phenol disappearance reaction, while the other two included oxidation intermediate compounds. The number of model parameters involved increased from 3 to 23 and 38, respectively, for the three models. Both algorithms gave good results for the first model, although the L–M was superior in terms of computation time. In the second case the algorithms achieved convergence, but S-A resulted in a better criterion and kinetic parameters with physical meaning. In the more complex model, only S-A was capable of achieving convergence, whereas the L–M failed. For the second and third model the solution of S-A could be further improved, when used as an initial guess for the L–M algorithm.     

Impact of oxygen transport properties on polypropylene thermal oxidation,part 1: Effect of oxygen solubility

A general kinetic model is proposed to describe the polypropylene thermal oxidation of thin polypropylene films in a wide range of temperatures (from 60 to 200°C) and oxygen partial pressures (from 0.02 to 5 MPa) using a single set of parameters. This model was calibrated with several series of experimental data including analyses of primary (hydroperoxides) and secondary oxidation products (carbonyl species), and subsequent changes in macromolecular properties (average molecular masses). It predicts the experimental data previously published in the literature in terms of induction times and maximal oxidation rates. The variability of the oxygen solubility coefficient allows to explain the scattering of induction times and oxidation rates among the whole iPP family, but also the dependence of this latter quantity with oxygen partial pressure. This variability is presumably due to iPP polymorphism in the temperature range where oxygen permeability is commonly measured. It is concluded that the kinetic model can be used to study the direct effect of iPP morphology on its thermal oxidation kinetics (chemistry of oxidation). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41441.     

Kinetics of formation of ZrB2-MoSi2 glass-ceramic heat-resistant coatings on graphite

Coatings on graphite with a high heat resistance at a temperature of 1400°C in an air atmosphere are prepared on the basis of the ZrB₂-MoSi₂-SiO₂ system. It is demonstrated that the sealing vitreous layer is formed through oxidation of the composite components. The kinetic analysis of oxidation processes of the ZrB₂-MoSi₂ composite shows that the coating formation results from a set of concurrent and consecutive chemical reactions. The stages of forming the gas-impermeable layer are revealed, the schemes for oxidation reactions are proposed, and the kinetic parameters of reactions are determined.     

A feasible kinetic model for the hydrogen oxidation on ruthenium electrodes

The hydrogen oxidation reaction (hor) was studied on a polycrystalline ruthenium electrode in H₂SO₄ solution at different rotation rates (ω). The experimental polarization curves recorded on steady state show the existence of a maximum current with a non-linear dependence of the current density on ω^1/2. On the basis of the Tafel-Heyrovsky-Volmer kinetic mechanism, coupled with a process of inhibition of active sites by the reversible electroadsorption of hydroxyl species, it was possible to appropriately describe the origin of the maximum current. The corresponding set of kinetic parameters was also calculated from the correlation of the experimental results with the proposed kinetic model.     

甲苯液相氧化动力学研究

建立了一套甲苯液相空气氧化的连续反应装置,在工业条件下进行了动力学实验研究。在排除氧气、催化剂质量分数等影响因素下,建立了反应动力学模型,并回归得到模型参数。用该模型计算得到的甲苯转化率和实验结果对比,最大误差4.72%,平均误差2.36%。研究结果表明,甲苯转化率受温度和停留时间的影响较大,尤以温度影响更为明显;主产物选择性受温度和停留时间的影响较小,但停留时间延长,会加剧苯甲醛向苯甲酸转化。     

Effects of Oxygen Transfer Limitation and Kinetic Control on Biomimetic Catalytic Oxidation of Toluene

Under oxygen transfer limitation and kinetic control, liquid-phase catalytic oxidation of toluene over metalloporphyrin was studied. An improved technique of measuring dissolved oxygen levels for gas-liquid reaction at the elevated temperature and pressure was used to take the sequential data in the oxidation of toluene catalyzed by metalloporphyrin. By this technique the corresponding control step of toluene oxidation could be obtained by varying reaction conditions. When the partial pressure of oxygen in the feed is lower than or equal to 0.070 MPa at 463 K, the oxidation of toluene would be controlled by oxygen transfer, otherwise the reaction would be controlled by kinetics. The effects of both oxygen transfer and kinetic control on the toluene conversion and the selectivity of benzaldehyde and benzyl alcohol in biomimetic catalytic oxidation of toluene were systematically investigated. Three conclusions have been made from the experimental results. Firstly, under the oxygen transfer limitation the toluene conversion is lower than that under kinetic control at the same oxidation conditions. Secondly, under the oxygen transfer limitation the total selectivity of benzaldehyde and benzyl alcohol is lower than that under kinetic control with the same conversion of toluene. Finally, under the kinetics control the oxidation rate of toluene is zero-order with respect to oxygen. The experimental results are identical with the biomimetic catalytic mechanism of toluene oxidation over metalloporphyrins.     

1,2-环己二醇合成己二酸的氧化动力学

以H_2O_2为氧化剂,磷酸为助剂,采用初始浓度法研究了钨酸催化过氧化氢氧化1,2-环己二醇合成己二酸的氧化动力学,建立动力学模型,得到了反应动力学方程。实验结果表明,1,2-环己二醇的反应级数为0.98,H_2O_2的反应级数为0.30,反应的活化能为46.92 k J/mol,指前因子为9.48×10~4 L~(0.28)/(mol~(0.28)·min)。通过实验验证氧化动力学方程,计算值和实验值的平均相对误差为0.2%,两者基本吻合。     

结炭B-02催化剂烧炭再生本征动力学模型

以工业两段绝热床中运行近4000h的结炭B—02催化剂为研究对象,利用内循环无梯度反应器,求得催化剂烧炭再生本征动力学模型.由于催化剂中的结炭是多核芳烃,因此可简单地以碳氧化和氢氧化的动力学方程表征烧炭再生动力学模型.碳氧化动力学方程为-dN_c/N_Cdt=K_Cp_(O_2)~(0.3)(N_C/N_C)~1.3式中,一段催化剂 K_C=13.37exp[-78.97×10~3/(RT)]二段催化剂 K_C=96.54exp[-89.30×10~3/(RT)]氢氧化动力学方程为-dN_H/N_Hdt=K_H(N_H/N_H)~1.1式中,一段催化剂 K_H=0.48exp[-39.04×10~3/(RT)]二段催化剂 K_H=4.79exp[-52.03×10~3/(RT)]     

Oxidation of toluene to benzaldehyde over VSb0.8Ti0.2O4 Effect of the operating conditions

In the present work, the kinetic toluene oxidation on VSb_0.8Ti_0.2O₄ based catalyst was studied. A reaction network, which involves three steps: the partial oxidation of toluene to benzaldehyde, a consecutive oxidation of benzaldehyde to carbon oxides and a parallel oxidation of toluene to carbon oxides, was proposed. The kinetic parameters were estimated assuming the redox mechanism proposed by Mars and van Krevelen. The products distribution was strongly affected by the reaction temperature. The adjustment of activation energies for total and partial oxidation of toluene led to the same values. The activation energy for the benzaldehyde oxidation was lower than the one for its formation.     

A practical parametrical characterization of the Fenton and the photo‐Fenton sulfamethazine treatment using semi‐empirical modeling

BACKGROUND: Sulfamethazine (SMT) has received little attention in the water treatment literature. Yet, SMT is among the non‐biodegradable substances increasingly found in aqueous media and affecting both public health and wastewater treatments. For a long time, advanced oxidation processes (AOPs) were studied via pure empirical modeling, although the surface response models resulting from lumped information (TOC, COD, etc.) present limitations regarding extrapolation and optimization. Conversely, detailed first‐principles modeling may not be affordable due to the computational burden and the chemical analysis needs. Thus, a balanced approach may be practical in many cases. RESULTS: Experiments on SMT solutions (500 mL, 50 mg L^?1) were performed under conditions set by an experimental design. A set of replicated degradation time‐profiles (TOC and SMT concentrations) was obtained and a semi‐empirical kinetic model was fitted to these data to determine maximum conversion and kinetic rate. CONCLUSIONS: SMT can be completely degraded from water via photo‐Fenton treatment. Conditions for this treatment were investigated and its outcomes were systematically characterized by a simple kinetic model and two lumped parameters, conversion and kinetic rate. Both, the model and the corresponding parametrical characterization are introduced as a means to discriminate the most efficient treatment conditions in a practical and efficient way. Copyright © 2011 Society of Chemical Industry