连续搅拌槽式反应器(CSTR)——定态非绝热操作的热稳定性

本文研究了连续搅拌槽式反应器(CSTR)定态非绝热操作,即反应器具有通过器壁的热损失时的临界条件及其有关问题;讨论了如何在分析这类非绝热放热反应器操作条件中热灵敏区间时,采用适当的无量纲参数.使问题的描述具有和相对简单的绝热反应器—致的形式;导出了非绝热系统点火(飞温)和熄火这两个热灵敏边界的数学表达:还证明了当满足xS/v≥QC_0E/RT~2_(ref)(1/4-RT_(ref)/E)-1时,可以避免出现热灵敏区间.由于上式左边的量易于在工程上进行控制,上式在化学工程设计和控制中具有现实意义.     

水合法制丙二醇的CSTR开车模拟及反应器稳定性分析

以水合法制丙二醇为例,对连续搅拌釜式反应器(CSTR)的开车过程进行了动态模拟研究,分析了开车过程中温度、浓度、转化率随时间的变化曲线,确定了影响反应器开车能否成功的主要因素,并对反应器的抗干扰能力进行了分析.研究结果表明,在反应器进料温度(T0)297.15K的条件下,反应器开车失败;而将反应器的进料温度升至300.00K,可使反应器开车成功:影响反应器开车成功与否的主要因素是反应器的进料温度是否高于其点火温度,而该反应体系的点火温度为297.70 K.借助多态理论指导使反应器成功开车后,在T0为297.15 K的条件下稳态操作,当反应器的进料温度升高时,对反应器的操作稳定性影响不大;当进料温度降温幅度低于 3.00 K时,反应器仍能维持在高转化率的状态下操作:但当反应器的进料温度降温幅度大于或等于 4.00 K时,反应器的操作状态将从高转化率跌落至低转化率,导致反应器的白动停车.山此可知,该反应器虽具有一定的抗扰动能力,但其稳定性较差.     

全混流反应器热稳定性的参数敏感性分析

有许多伴随着大量的热量释放的化学反应过程,是在多相反应器(非均相催化反应器、气液反应器)中完成的。从安全的角度来看,它们代表了化学工业中最危险的操作单元。对这类全混流特质反应器,操作参数对对其热稳定性的影响程度可以用参数热敏感性加以表述。本文推到了操作过程中变化的参数V_0、C_(A0)、T_i、T_c、U、(-H_r)、x_A对热稳定性的影响。     

CO氧化偶联反应器模拟与优化

CO与亚硝酸甲酯(MN)氧化偶联制草酸二甲酯(DMO)是合成气制乙二醇过程的关键步骤，现有工业装置存在效率低的问题。采用包括副反应(生成碳酸二甲酯和甲酸甲酯)动力学的动力学模型和二维两相反应器模型，对CO氧化偶联的移热式固定床反应器进行建模，研究了换热方式及操作条件对反应器性能和安全性的影响。结果表明，以温度的二阶导数作为飞温的判据是灵敏和可靠的。与常规的逆流和恒温移热方式相比，并流移热使反应器形成更为均匀的温度分布，有利于提高反应器产能。增加入口MN含量会升高反应器MN转化率和热点温度；但是，由于CO、NO和反应物MN之间存在竞争吸附，增加入口CO和NO含量会导致MN转化率和热点温度降低，所以增加入口压力导致MN转化率降低。且热点温度对MN和NO的含量更为敏感，应严格控制入口MN和NO的含量。采用遗传算法进行反应器工况寻优，确定了最优的反应条件，可提高单台反应器对应的乙二醇(EG)年产能至12万吨。     

管式固定床反应器多态研究——(Ⅲ)多态理论的工程应用

本文实验研究了在列管式固定床反应器中加入惰性铝导热片对反应器性状的影响,以苯催化氧化作为反应对象。由于惰性铝导热片的插入增加了床层的有效热导,结果,加宽了多态区,降低了点火和熄火温度,提高了反应器操作的稳定性,提高了产物收率。     

矩形截面气升式环流反应器中非牛顿流体的气含率与传质系数的研究

研究了一种矩形截面气升式环流反应器,用幂律τ=η_ογ~n(n<1)来表示流体流变学特性的变化.在这类反应器中,假塑性非牛顿流体的气含率ε_g与传质系数K_La的变化规律可用半经验关联式表示ε_g=0.2535(η_ο5000~(n-1))~(-0.161)(1+A_d/A_r)~(-0.434)u_(gr)~(0.856-0.161n)K_La=0.0192(η_ο5000~(n-1))~(-0.902)(1+A_d/A_r)~(-1.228)u_(gr)~(1.955-0.902n)并讨论了该类反应器结构及运行状况,流体性质变化时,反应器传质动力学特性、流动特性和操作弹性变化的规律.     

半间歇釜式反应器安全高效操作的数值优化策略

半间歇釜式反应器内物料积累过多且反应放热过快时,容易引发热失控风险,造成化工安全事故。设计较优的加料操作,既可以避免热失控风险,又可以缩短操作周期、提高生产效率。针对半间歇釜式反应器,以乙酸酐水解为模型反应,基于反应器数学模型,提出了一种安全高效加料操作的数值优化策略。在该策略中,首先确定不同加料方式（如一段、二段和三段加料）下的安全操作温度区间,然后在该温度区间内寻找最短操作周期对应的操作温度,该温度即为最佳的加料操作温度。优化结果表明三段加料的安全操作温度区间和最佳操作温度分别比一段加料宽60.9%和低1.9 K,六段加料已经基本可以实现操作周期最短,增加操作压力也有利于缩短操作周期。     

矩形截面气升式环流反应器中非牛顿流体的气含率与传质系数的研究

研究了一种矩形截面气升式环流反应器,用幂律τ=η_ογ~n(n<1)来表示流体流变学特性的变化.在这类反应器中,假塑性非牛顿流体的气含率ε_g与传质系数K_La的变化规律可用半经验关联式表示ε_g=0.2535(η_ο5000~(n-1))~(-0.161)(1+A_d/A_r)~(-0.434)u_(gr)~(0.856-0.161n)K_La=0.0192(η_ο5000~(n-1))~(-0.902)(1+A_d/A_r)~(-1.228)u_(gr)~(1.955-0.902n)并讨论了该类反应器结构及运行状况,流体性质变化时,反应器传质动力学特性、流动特性和操作弹性变化的规律.     

进行复杂一级反应的非等温管式反应器的计算

对于进行均相(或拟均相)复杂一级反应的非等温操作管式反应器的节塞流模型,提出了一种比较准确简捷的数值解法。当温度浓度分布对于参数和初值条件的变化较为灵敏时,这种方法的优点尤为突出。     

合成直链烷基苯用循环移动床反应器的模拟

循环移动床是一种新型的耦合式反应器,用于合成直链烷基苯.通过试验研究了操作条件对反应的影响,并通过微元物料平衡建立了反应器热态模型.该模型考虑了催化剂失活对反应的影响,同时对反应过程的稳态操作情况和非稳态阶跃操作情况进行了模拟计算.     

Self-sustaining reactions induced by ball milling: An overview

When a highly exothermic powder mixture is activated in a ball mill, a self-propagating process can be ignited after a certain activation time. Exploring the effects of material properties and milling conditions on the ignition time, combined with characterization of reactant mixtures approaching the critical state at ignition, provides useful information on the mechanical activation process. After ignition, the reaction propagates thermally, similar to an SHS process. In this paper, the principles of mechanically induced self-sustaining reactions (MSR) are summarized and their relationships with mechanochemistry and SHS are discussed. Numerous examples are given, some interesting from the point of view of fundamental understanding of the process, others are promising as the bases of practical applications.     

Ignition performance of new and used motor vehicle upholstery fabrics

This paper examines the standards for fire safety in transport systems and in particular the test method for the flammability of materials within passenger compartments of motor vehicles. The paper compares data from ignition tests conducted in the cone calorimeter and the FIST apparatus with tests conducted using the FMVSS 302 horizontal flame spread apparatus. Ten materials were selected as representative of those used as seat coverings of private and commercial passenger vehicles. The time to ignition of new and used materials subject to exposure heat fluxes between 20 kW/m² and 40 kW/m² was measured. The results from the ignition tests were analysed using thermally thick and thermally thin theoretical models. The critical heat flux for sustained piloted ignition was determined from the time to ignition data using the thermally thin approach. Derived ignition temperatures from both the thermally thick and thermally thin methods were compared with measurements using a thermocouple attached to the back surface of materials in selected tests. The flame spread rates in the FMVSS 302 apparatus were determined and a comparison was made between the performance of the materials in the flame spread apparatus, the cone calorimeter and the FIST. The results suggests that a critical heat flux criterion could be used to provide an equivalent pass/fail performance requirement to that specified by the horizontal flame spread test although further testing is needed to support this. Copyright © 2004 John Wiley & Sons, Ltd.     

Steady state multiplicity behavior of an isothermal axial dispersion fixed-bed reactor with nonuniformly active catalyst

An isothermal, heterogeneous fixed-bed reactor packed with nonuniformly active catalyst pellets where a biomolecular Langmuir-Hinshelwood reaction occurs, is studied using an axial dispersion model. A catalyst activity distribution given by a Dirac delta function, where the active catalyst is deposited at a specific location within the pellet, is considered. This includes the common case of externally coated pellets with external mass transfer resistance. The steady state multiplicity behavior of this reactor, and its limiting cases: CSTR, PFR and pseudohomogeneous axial dispersion, are examined in detail. The nonlinearity of the reaction kinetics provides two sources of multiplicity, through the heterogeneous nature of the reactor and the presence of axial dispersion in the fluid phase. Their roles in determining reactor multiplicity behavior are fully explored. It is shown that this system can admit at most nine steady state solutions. The limiting behavior of the heterogeneous axial dispersion model as Pe → 0 or ∞ is not represented fully by the CSTR or PFR models because of ignition phenomenon. Finally, the effects of mixing on reactor conversion are discussed.     

Autocatalytic reactions in the isothermal,continuous stirred tank reactor: Oscillations and instabilities in the system A + 2B → 3B; B → C

The prototype, cubic autocatalytic reaction (A + 2B → 3B) forms the basis for the simplest homogeneous system to display “exotic” behaviour. Even under well-stirred, isothermal, open conditions (CSTR) we may find multistability, hysteresis, extinction, ignition and anomalous relaxation times. Allowing for the finite lifetime of the catalyst (B→inert products) adds another dimension. The dependence of the stationary-states on residence-time now yields isolas or mushrooms. Sustained oscillations (stable limit cycles) are also possible. The onset of oscillation corresponds to a change in the character of the stationary-state (from stable focus to unstable focus) and the conditions for this change can be evaluated analytically. The period of the oscillations and their amplitudes increase as the residence time is lengthened. A total of nine different phase-portraits in the a–b plane has been found.The isothermal system is less complex than the exothermic, first-order reaction in a CSTR, but there are strong analogies between the two.     

Experimental and analytical protocol for ignitabiilty of common materials

In this study, a protocol was developed to increae accuracy, generality and efficiency when determining piloted ignition properties. A new procedure for calibrating the radiative and convective heat flux protiels on exposed speciments, such as Douglas-fir plywood, has been implemented for the lateral ignition and flame spread test (LIFT) apparatus. The boundary conditions needed for heat transfer anylysis are made unambiguous by including a simple, direct measure f surface emissivity. A new aluminum foil shutter improves accuracy for measuring ignition time. A recently developed theroy of ignitanility provides a formula to account for the transition form thick to thin thermal behaior, allowing specimens of finite thicknesses and a fuln range of test irradiances.     

基于动态优化和反馈控制的聚合反应过程牌号切换策略

针对单反应器多牌号聚合物生产过程, 提出一种结合动态优化和反馈控制的牌号切换策略。以实验室规模的连续搅拌釜式反应器中苯乙烯聚合牌号切换为对象, 以原料消耗最少为优化目标, 利用迭代动态规划求得切换过程中反应条件和产品性能指标的优化轨迹。引入针对反应温度的路径约束, 使优化后的切换轨迹更易跟踪实现, 防止过渡过程中变量的剧烈波动。仿真结果表明, 这一切换策略可以显著减少牌号切换过渡时间及过渡过程中原料的消耗量, 并能够有效克服进料温度变化的干扰。     

Calculation of ignition parameters and the transition to combustion in a heterogeneous system

A model for ignition of a heterogeneous condensed system by a pulsed heat flux is studied. Pyrolysis of condensed components and ignition of the pyrolysis products in the gaseous phase are assumed. The dependences of various ignition characteristics on the external parameters are studied. The conditions for stable ignition of a heterogeneous system are investigated. The region of stable transition to self-sustained combustion after removal of the external heat flux is calculated.Tomsk. Translated from Fizika Goreniya i Vzryva, Vol. 29, No. 3, pp. 124–129, May–June, 1993.     

FUZZY GAIN SCHEDULED CSTR WITH GA-BASED PID

In this article, a new control scheme, the gain scheduled genetic algorithm (GA)-based PID is proposed for a continuous stirred tank reactor (CSTR). A CSTR is a highly nonlinear process that exhibits stability in certain regions and instability in other regions. The proposed control scheme implements the characteristics of the genetic algorithm's (GA) global optimization to optimize the PID's three control parameters, k_p, k_i, k_d, to obtain the best control effect by minimizing the integral square error online. The PID controller parameters tuned by the GA for each region are gain scheduled by a fuzzy logic scheduler. Fuzzy gain scheduling is a special form of fuzzy control that uses linguistic rules and fuzzy reasoning to determine the controller parameter transition policy for the dynamic plant subject to large changes in its operating state. Simulation results show the feasibility of using the proposed controller for the control of the dynamical nonlinear CSTR.     

A systematic generation of reactor designs: I. Isothermal conditions

A new method is proposed for systematic generation of conceptual design of reactor networks. Given feed compositions and a kinetic model, the objective is to find the optimal mixing structure and feed distribution. The method aims at finding the optimal sequence and sizes of ideal reactors and the optimal addition of extra feed streams along the reactor path. The total reaction time is calculated so as to maximize the space time yield subject to a minimum yield of the key product component. The method does not have any limitations with respect to the number of components or reactions. A new model formulation is proposed that comprises both CSTR and PFR model equations and the design problem is formulated as an optimal control problem. In this paper, only isothermal conditions are considered.