Dynamic modeling and reaction invariant control of pH

A systematic treatment of the dynamics and control of acid-base reactions is presented. A state model consisting of mass balances for the species present is formed. Through a linear transformation of the concentration vector a new model is set up. The state vector of this model is partitioned into a reaction invariant and a reaction variant part. The model is thus split into two parts, one describing the physical properties of the reactor system independent of chemical reactions, the other describing the chemical reactions.For fast acid-base reactions the reaction invariant part of the model is sufficient to define the thermodynamic state of the system. The reaction rate vector is thus eliminated from the model. In this case the reaction variant part of the model consists of a static equation, relating pH to the reaction invariant state variables.The model obtained provides a sound basis for design of control loops for feedback and feedforward control of pH. As a direct application a new scheme for adaptive control of pH is proposed.     

Stochastic model of reaction rate oscillations during CO oxidation over zeolite-supported catalysts

The particle size effect on the oscillatory behaviour during CO oxidation over zeolite-supported Pd catalysts is simulated with the help of a deterministic point model and a stochastic mesoscopic model. The point model is developed on the basis of Sales, Turner and Maple (STM) model, which is modified to consider the effects of the oxidation of the Pd bulk upon the catalyst activity. It is demonstrated that the deterministic point model can simulate the main properties of regular reaction rate oscillations. The stochastic model is based on the developed point model and simulates the reaction by a Markovian chain of elementary transitions, which correspond to changes in numbers of atoms and molecules of reagent species on the surface of Pd particle due to elementary steps of reaction. The stochastic model explains the role of statistical fluctuations and correlations in the reaction dynamics on the surface of an nm-sized catalyst particle.     

布朗工艺一段转化炉的模拟计算

在建立炉膛燃烧传热模型和管内气固相催化反应模型的基础上对布朗工艺合成氨装置一段炉辐射段进行模拟计算.炉膛燃烧传热过程采用Hottle区域法建立三维辐射换热模型,与管内的气固相催化反应动力学模型迭代求解,得出了炉膛三维温度分布以及管内温度、压力、组成随高度的分布.计算结果与实测值基本吻合.由于炉膛燃烧传热模型采用三维模型,与传统的一维和二维模型比较,计算结果更为精确.计算方法和结果对于节能降耗以及设备的改进等都有非常重要的意义.     

Computer Simulation of the Microstructure Developed in Reaction-Sintered Silicon Nitride Ceramics

A simulation model of the microstructure developed during the reaction sintering of ultrafine silicon powders is presented. The model employs interactive subroutines that describe particle compaction, sintering, and nitridation. The particle compaction model is based on a random particle packing model, whereas the sintering and reaction sintering models are based on the modified grain model and the sharp interface model (SIM). Microstructural changes due to the competition between chemical reaction and sintering are taken into account in the model. The results predicated by this model show good agreement with experimental data from previous studies.     

Application of flamelet model to large‐eddy simulation of turbulent reacting liquid flows

Large‐eddy simulations using the flamelet models are applied to turbulent reacting liquid flows and validated by comparing with the experiments. The computations are performed for two reaction conditions, namely a rapid reaction and a moderately fast reaction in a grid‐generated turbulent flow. For the flamelet models, both the steady flamelet model and the unsteady Lagrangian flamelet model are tested. A second‐order, irreversible, and isothermal reaction is considered. The results show that the flamelet models inherently developed for turbulent combustion are applicable to turbulent reacting liquid flows, provided that the model coefficient in evaluating the subgrid scale variance of mixture fraction in the scale‐similarity model is set to be 5.0. The rapid reaction can be adequately predicted by both the steady and unsteady Lagrangian flamelet models, whereas the moderately fast reaction can be predicted only by the unsteady Lagrangian flamelet model which is capable to take slow chemical processes into account. © 2010 American Institute of Chemical Engineers AIChE J,, 2011     

Ni—Mo／TiO2-Al2O3催化剂上柴油加氢脱硫反应动力学研究

以混合柴油为原料,采用高压滴流床反应器,在反应温度280—360℃、氢分压5-7MPa、氢油体积比300～900、液时空速1—6h。的条件下,考察了柴油在Ni-Mo／TiO2-Al2O3催化剂上的加氢脱硫反应规律,并建立了柴油加氢脱硫经验型模型。采用Levenberg—Marquard优化方法,对实验数据进行回归,确定了反应动力学模型中的有关参数,得到的反应级数为2．9,加氢脱硫反应的表观活化能为143613J／mol,同时得到了在实验条件范围内Ni—Mo／TiO2-Al2O3催化剂上柴油的加氢脱硫动力学方程。经检验,模型计算结果与实验数据吻合良好。     

Estimation of kinetic triplet of cellulose pyrolysis reaction from isothermal kinetic results

This paper presents a new approach to estimate the Arrhenius parameters as well as the reaction model function of cellulose pyrolysis reaction. Reduced time plot (RTP) was employed to choose a proper form of reaction model function for cellulose pyrolysis reaction. A state-of-the-art thermobalance (TB) that is able to form real isothermal reaction conditions was introduced to construct RTPs from isothermal decomposition kinetic data. The reaction model function of cellulose pyrolysis reaction would be accounted for by Avrami-Erofeev function, n(1-α){-ln(1-a)}^1-1/n where n is determined to be 3.69.     

Empirical modelling and scale-up of a semi-batch polyestrification process

A semi-empirical kinetic model that fits laboratory data and predicts pilot plant data was developed. The model is a modified version of a recently reported third-order kinetic equation for the reaction of nonstoichiometric amounts of hydroxyl and carboxylic groups. The model can be used to quantify the effects of reaction temperature and inert gas flow rate on the reaction rate. The Arrhenius temperature dependence of the rate constant permitted the calculation of the reaction activation energy (53.6 kJ/mol). The gas flow rate dependence is an empirical function of the molar ratio of reactants to inert gas. The same function is simultaneously used as the process scale-up rule. The mathematical model can be potentially used for commercial-sized reactors.     

Modeling of gas-carbon reaction in pore diffusion control regime

A model is developed for pore diffusion controlled gas-carbon reactions where the reaction is limited to a narrow region on the exterior surface of the carbon particle. A planar geometry is used and an isothermal condition is assumed. However, the effects of pore structure change with conversion are included. The model can predict the penetration depth, the porosity profile, the reaction surface area profile and the concentration profile in the reaction zone. The model is an extension of Gavalas model[l] and an improvement over Desai and Yang’s model[2]. The model predictions are compared with available experimental data and wilh those of Desai and Yang’s model.     

Numerical study of pore structure effect on SO2-CaO reactions☆

The effect of varying pore structures on the kinetics of SO2–CaO reactions is not fully understood in the previous studies. Combining fractal pore model, gas molecular movement model and two-stage reaction model, a new desulfurization model is established in this paper. Fractal pore model is used to simulate CaO particle and gas molecular movement model is used to simulate gas diffusion in pores. Fractal dimension is used to characterize complexity of pore structure instead of tortuosity factor. It is found that the reaction is significantly affected by pore structures. A modulus?is introduced to characterize the relationship between varying pore structures and apparent reaction parameters. And this relationship is verified by thermo-gravimetric analysis (TGA) data. Comparing to the previous models, the effect of varying pore structure on the kinetics of the reaction is described more accurately by the desulfurization model.     

微波化学反应的无量纲准数动力学模型研究：以偶氮二异丁脒盐酸盐（AIBA）分解反应为例

微波辅助化学已成为备受关注的研究课题,但微波反应动力学模型缺乏系统的研究严重阻碍了微波在化学工业化上的应用,微波化学反应在化学工程化的放大设计及应用缺乏基础依据。以偶氮二异丁脒盐酸盐（AIBA）分解反应为例,通过选择合适的溶剂调整其复配比例,得到一系列具有不同沸点的混合溶剂作为反应介质,使反应在混合溶剂沸点下进行,以保证反应过程中微波的持续作用来研究微波反应动力学。从微波作用下动量传递、热量传递和质量传递的影响因素进行考虑,选择了对微波化学反应必须和充分的因素,包括微波功率密度 p、黏度 μ、密度ρ、反应物的浓度 C_A、温度 T、热导率 λ、损耗角正切δ 和微波辐射频率f。采用量纲分析方法,通过模型分析建立了微波分解反应动力学模型。通过大量的实验数据进行拟合,回归出特定反应的模型参数。该模型估算值与实验值的误差较小,相关性较高,具有一定的预测能力可解决微波反应过程放大的基础性问题,有望用于指导微波工业化生产。     

分子尺度反应动力学模型构建在催化裂化/裂解过程中的应用进展

随着环保法规的日益严格和成品油质量标准的持续升级,对催化裂化/裂解过程的产品要求和控制逐渐精细到分子级别,可靠的分子尺度反应动力学模型是实现催化裂化/裂解过程分子管理的关键所在。本文简述了催化裂化/裂解的反应机理和反应类型,回顾了近三十年来不同方法对催化裂化/裂解过程反应网络和分子尺度反应动力学模型构建的研究进展。重点对不同模型构建技术的优缺点进行了详细的对比分析,指出了催化裂化/裂解过程分子尺度反应动力学模型构建的研究方向：开发更为精细的石油分子分析表征技术,构建与催化剂失活和反应器模型相结合的分子尺度反应动力学模型,实现基于分子管理的催化裂化/裂解过程反应器设计和工艺工程放大。此外,指出建立对分子集构建、反应网络构建和动力学参数求解的集成化平台是分子尺度反应动力学发展的必然趋势。     

甲烷化梅花状催化剂CFD计算及改进

对合成气甲烷化反应体系进行CFD（计算流体动力学）计算,并对模型提出合理的改进。通过建立合理的甲烷化梅花状催化剂颗粒三维模型进行计算,并验证了模型的有效性。结果表明：甲烷化反应内扩散阻力很大,CO在催化剂表面与内部存在明显的浓度差。且H₂与CO扩散速率不同,导致催化剂内部的氢碳比很高,内部的反应条件与催化剂表面相比发生改变,使用单一的动力学方程无法准确描述实际的反应过程。因此,提出对催化剂的不同区域分别讨论,根据催化剂内CO含量的变化将两种不同的动力学方程分别应用在催化剂的不同区域。计算后发现采用两种动力学控制下催化剂内甲烷化反应的平均反应速率加快,反应进行的程度变大,更加接近实际过程,提高了计算的精确性。     

Application of the zone model to multiple noncatalytic fluid-solid reactions

The effect of intraparticle diffusion on the multiple gas-solid reactions occurring in a porous solid reactant is analyzed by the zone reaction model. In parallel reactions for gases and a consecutive reaction for the solid, the solutions of transient concentration profiles of two solid reactants are given by classifying three zones, viz. Reaction zone and reaction-diffusion zone and diffusion zone in the course of the reaction progression. As an example, the simultaneous reduction-sulfidation of porous iron oxide sorbent in the desuifurization from low BTU coal gases is analyzed by the present model. The Thiele modulus of the reaction governs the behavior of the moving boundary between the reaction zone and the diffusion zone. When the Thiele modulus tends to be infinite, the present model is consistent with the solutions based on the unreacted shrinking core model.     

Simulation of gas-particle turbulent combustion in a pulverized coal-fired swirl combustor

A particle stochastic trajectory model for turbulence-particle reaction interactions is proposed and formulated in the present paper. This model provides the basis for a comprehensive model of pulverized coal combustion. It is applied to the simulation of gas-particle turbulent flow and combustion in a pulverized coal-fired swirl combustor. The results are compared with the measured test data and those obtained by the particle stochastic trajectory model without considering turbulence-particle reaction interactions. The predicted gas temperature and species concentrations in the upstream region of the combustor are improved by utilizing the model with turbulence-particle reaction interactions.     

氯苄双羰基化反应动力学

It is a multi-phase-catalyzed reaction to produce calcium phenylpyruvate by double carbonylation of benzylchloride. Based on the analysis of the reaction mechanism, a kinetic model of the carbonylation reaction was obtained. The model was verified through experiments in which the diffusion effect was neglected with the appropriate operation manner. But it is inevitable that the carbonylation process is controlled by diffusion as the autoclave scaling up.     

Kinetics of reactions involved in pyrolysis of cellulose I. The three reaction model

Kinetics of reactions involved in pyrolysis of cellulose has been modeled in terms of a three reaction model. In this model it is assumed that cellulose decomposes to tars, chars and gaseous products via three competitive first-order reactions. Arrhenius parameters have been obtained to describe the rate constants of these reactions. The three reaction model predicts the weight loss data reasonably well. Product yields of tars, chars and gases predicted by the three reaction model are compared over the temperature range 250 to 360°C. In this communication a technique for analyzing experimental data of a solid state reaction is presented.     

基于EDM、PDF和FR/ED模型的煤粉燃烧过程适应性研究

还原气氛下煤粉反应过程兼具燃烧和气化的特点,是煤粉实现低氮燃烧的关键因素,合适的化学反应模型是准确模拟该过程的基础。笔者基于煤粉双锥燃烧器,对比了EDM模型、PDF模型和FR/ED模型在氧化气氛和还原气氛的模拟结果,通过与试验结果的对比验证,确定了不同反应气氛适合的化学反应模型。研究结果表明,3种模型在煤粉着火位置和逆喷传播距离的预测上存在差别,PDF模型起火点更靠近燃烧器逆喷喷口,EDM模型一次风和煤粉喷出经过一段升温过程后逐渐燃烧,FR/ED模型的升温过程更长,壁面低温区域接近前锥长度一半;使用FR/ED模型模拟时燃烧器内平均温度最高,EDM模型次之,PDF模型最低;EDM模型中未考虑CO反应,燃烧器内基本无CO存在,PDF模型高CO浓度区域集中在煤粉燃烧初期,燃烧器出口CO含量较低,FR/ED模型化学反应动力学参数在煤粉燃烧整个区域内均有较高CO浓度存在。由于考虑了焦炭与氧气气化反应的影响,FR/ED模型模拟燃烧器内氧含量明显低于EDM和PDF模型,当过量空气系数为1.2时,燃烧器出口处氧含量为7.0%,明显低于EDM模型的11.1%和PDF模型的12.0%,燃烧器出口处CO含量为3.5%,明显高于EDM(0)和PDF模型(0.8%);过量空气系数为0.5时,EDM模型对CO成分的预测结果偏差较大,燃烧器出口CO浓度为0.05%,采用PDF和FR/ED模型时燃烧器出口CO含量分别为5.73%和10.7%。从模拟结果与试验结果的对比来看,在氧化气氛下,主要发生煤粉的燃烧反应,EDM模型和PDF模型在温度、CO含量上的预测较为准确,与试验数据偏差较小,FR/ED模型偏差较大;在还原性气氛下,EDM模型模拟的结果几乎不生成CO和H2,并不适合还原性气氛,PDF模型和FR/ED模型有较合理的还原气氛模拟结果,两者的差别在于还原性气体的生成位置,PDF模型喷口位置CO浓度较高,出口浓度偏低,FR/ED模型随着煤粉反应流程的进行,CO浓度逐渐升高,出口浓度更接近试验结果。综合考虑,氧化气氛下双锥燃烧器适合采用EDM模型和PDF模型进行模拟,还原气氛下适合采用FR/ED模型进行模拟。     

Modeling of the non-catalytic semi-batch esterification of palm fatty acid distillate (PFAD)

Biodiesel fuel is one of the most attractive alternatives to the traditional diesel fuel derived from a petroleum refinery. Development of a reliable model for the biodiesel production process requires maximizing economics and enhancing safety in the commercial operation of biodiesel plants. We propose a model which represents effectively the non-catalytic biodiesel production reaction. In the modeling of the reaction, we employ a nonlinear programming scheme to estimate reaction kinetic parameters which minimize a specified objective function. The behavior of the methanol during the reaction is investigated both experimentally and numerically. Imperfect mixing in the liquid phase at the initial reaction stage causes a little discrepancy between the experimental data and results of simulations. Overall, the proposed model represents the biodiesel production reaction effectively.     

Acidization—V: The prediction of the movement of acid and permeability fronts in sandstone

A new model has been developed which describes the acidization of sandstone cores. The results show that the reaction of hydrofloric acid with the dissolvable minerals occurs in a narrow zone which moves as a reaction front through the sandstone core. The width of the reaction front is related to the Damkohler Number and the velocity of the reaction front is related to the acid capacity number. The model has virtually no adjustable parameters and agrees extremely well with the experimental results.