搅拌反应器中反应热的实时监测：Ⅰ确定性动态模型的量 …

在自制的５升规模反应量热实验装置中，以热平衡为基础建立了搅拌反应器的动态传递模型，并提出了模型参数的确定方法，实验采用计算机对有关的温度，流量信号实时采集，在线求解出搅拌反应器的热量。     

搅拌反应器中反应热的实时监测Ⅱ模拟放热反应过程的状态及参数估计

在自制的５Ｌ规模反应量热实验装置中，以热平衡为基础建立了搅拌反应器的动态热传递模型，应用扩展Ｋａｌｍａｎ参数估计和状态估计的方法在线得到模型参数和模拟反应的放热速率、累积反应热。实验数据和模型估计值比较，预测误差在±７％以内     

搅拌反应器中反应热的实时监测：Ⅱ模拟放热反应过程的？…

在自制的５Ｌ规模反应量热实验 ，以热平衡为基础建立了搅拌反应器的动态热传递模型，应用扩展Ｋａｌｍａｎ参数估计和状态估计的方法在线得到模型参数和模拟反应的放热速率，累积反应热。实验数据和模型估计值比较，预测误差在±７％以内。     

苯乙烯热聚合搅拌反应器的数值模拟

为了解聚合反应过程的传热规律和反应现象,以苯乙烯热聚合搅拌反应器为研究对象,通过计算流体力学(CFD)方法对苯乙烯热聚合反应的动力学模型进行耦合,建立该反应器的三维非稳态模型。通过UDF添加组分输运方程源项和能量方程源项,研究强放热反应体系热点分布及发展历程。重点考察物料黏度、搅拌速度对聚合反应器内速度场和温度场分布的影响。结果表明:物料黏度的增加,阻碍了远离搅拌桨区域内物料的对流传热,易在反应器顶部形成局部高温;提高搅拌速度可以使反应器内温度分布更加均匀,但会加剧聚合反应,造成反应器内平均温度升高。研究结果为揭示典型化工过程系统热失控的演化机理,预防热失控反应的发生提供了理论依据。     

搅拌式浆态光催化反应器对偶氮染料X-3B的降解特性研究

构建了体积为5 L的搅拌式浆态光催化反应器,以偶氮染料活性艳红X-3B为目标污染物,进行光催化降解特性研究。结合对X-3B在小规模反应器中悬浮TiO2表面的吸附行为研究,考察了TiO2投加量、搅拌速率和曝气量等对光催化效果的影响,分析了光催化过程的降解动力学,并从传质的角度对搅拌强度和初始反应速率进行了关联。实验结果表明,在搅拌式浆态光催化反应器中,Langmuir模型和Freundlich模型均能较好地描述TiO2对X-3B的吸附行为;在催化剂最佳浓度0.5 g.L 1的条件下,初始反应速率r0随搅拌雷诺数Re的增加呈现先增大后稳定的趋势,进一步增加空气曝气量可以显著提高初始反应速率。根据相关理论推导得出在该反应器光催化降解X-3B时,氧的传质是影响初始反应速率r0的关键因素。     

泰勒流反应器的流动及反应特性

利用由静态混合器、喷嘴和分气盒组成的新型布气装置在搅拌釜式反应器中诱导生成泰勒流,对反应器流动特性及反应特性进行了实验研究。结果表明,与常规搅拌釜式反应器相比,泰勒流反应器内物料流动更加接近于平推流流型,泰勒流的生成在反应器内构建出局部平推流区域,降低了物料返混程度。反应器反应性能因流动特性改变而得以增强,相同实验条件下,在泰勒流反应器中进行的蔗糖水解反应转化率比在常规搅拌釜式反应器中高出26.7%。在一定操作范围内,局部平推流区域和反应转化率均随搅拌转速或进气量的增加而增大。泰勒流反应器可简化为平推流区和全混流区并联的流动模型,推导出了反应转化率与平推流区域占反应器总体积比率之间的关联关系。     

搅拌管式反应器内流动特性的大涡模拟

采用实验和数值模拟的方法研究搅拌管式反应器内的混合过程,其中数值模拟采用大涡模拟的方法研究了反应器内流体的流动场,并就不同转速条件下流体的混合时间,将大涡模拟数值结果分别与标准k-ε模型的计算结果和实验测量值相比较,结果表明:管式搅拌反应器内的流动是非稳态的,具有不对称性。同时,大涡模拟方法可以预报漩涡,特别是桨叶背面的漩涡。与实验测量值相比,大涡模拟对混合时间的计算精度比标准k-ε模型计算精度高约22.8%,证明大涡模拟方法能够有效地模拟搅拌管式反应器内的流动特性。     

基于介尺度PBM模型的生物反应器放大模拟及实验研究

对于通气搅拌式工业生物反应器的放大设计而言,精确预测气泡尺寸和体积传质系数非常重要,因此需要建立合适的气泡聚并和破碎模型,以保证反应器的高效操作。以5 L通气搅拌式生物反应器为对象,以气泡尺寸和体积传质系数的实验数据为基准,模拟并考察了两种聚并模型和四种破碎模型对生物反应器内流体流动行为以及传质能力的影响。结果表明,基于介尺度理论的修正聚并模型与考虑黏流剪切的破碎模型组合,所得模拟结果与实验数据吻合最好,这为大型生物反应器的桨型优化提供了模型基础。因为工业化生物发酵通常是在大型生物反应器中进行,搅拌桨型对生物反应器效能至关重要,故本研究在选定最优气泡聚并破碎模型的基础上,通过叶轮末端剪切力相等的放大原则将5 L通气搅拌式工业生物反应器放大到400 m³,同时考察了六斜叶圆盘搅拌桨、非对称式抛物线搅拌桨、布鲁马金式搅拌桨以及六直叶圆盘搅拌桨等桨型组合对气泡破碎能力和气体分散效果的影响,并通过综合对比气含率、体积传质系数等参数,得到400 m³通气搅拌式生物反应器的最优桨型组合。     

气-液-固三相搅拌槽反应器模型及模拟研究进展

综述了气-液-固三相搅拌槽反应器模型和模拟的研究进展。讨论了可用于气-液-固三相流的模拟方法,三相流模型适合于气-液-固三相搅拌槽反应器的数值模拟。给出了气-液-固三相搅拌槽反应器数值模拟的研究进展,目前研究中还缺乏基于机理的相间作用力模型,常用的湍流模型不能描述搅拌槽内的各向异性,没有局部性质的实验数据导致气-液-固三相搅拌槽反应器的模型和模拟无法得到充分验证。建议在今后的研究中构建"两尺度"气-液-固三相湍流单元胞模型,扩展两流体显式代数应力模型为三流体模型,开发局部照相探针技术及相应的图像处理软件。     

苯乙烯聚合反应热失控及其紧急抑制的数值模拟

为实现对反应热失控行为的在线监控与紧急抑制,采用计算流体力学方法(CFD)结合苯乙烯热引发本体聚合反应的热动力学模型,建立苯乙烯热聚合反应的三维非稳态模型,并对该反应体系热点分布及发展历程进行研究,分析冷却稀释剂注入位置对反应热失控的抑制效果及热点消除的影响规律。结果表明:随着苯乙烯聚合反应的进行,物料黏度迅速增加,减缓了远离搅拌桨区域内物料的对流传热,造成该区域内热点集聚。反应抑制方面,在桨叶区注入冷却稀释剂时反应器内平均温度最低,而在热点集聚区域注入可以更加有效地控制热点的形成,减缓失控速率。研究通过反应器内温度分布与系统散度判据相结合的方法,为反应器传感器的优化布置、热失控反应的预防与控制提供了理论依据。     

Kinetic parameters estimation for cure reaction of epoxy based vinyl ester resin

A new graphical estimation technique is proposed for the determination of the kinetic parameters describing an autocatalytic reaction. A differential scanning calorimeter was used to monitor the reaction kinetics of an epoxy-based vinyl ester resin. The method utilizes information from a zero initial reaction rate, conversation at vitrification, the ratio of reaction rate constants under different isothermal conditions, and characteristics of the phenomenological kinetic model with assumptions being made about the overall reaction order. By fitting data to the integrated reaction rate equation with adjustments for the isothermal conditions, the kinetic parameters are estimated without using a linear or nonlinear regression method. Different kinetic parameters can be estimated from data before and after the gel point which was obtained from the relationship between the glass transition temperature and the degree of cure.     

Kinetics and thermal characterization of thermoset cure

The differential scanning calorimeter (Perkin-Elmer DSC-1) is used to characterize the cure of a general-purpose polyester during isothermal and scanning experiments. The technique is based on a new proposed model for the kinetics of isothermal cure. The model yields results which are in good agreement with experimental isothermal rate of reaction and integral heat of reaction data. It also gives some information about the residual reactivity of the sample after an isothermal cure experiment. With the aid of the proposed kinetic model, it is possible to obtain integral heats of reaction and rates of heat generation at different temperatures during a scanning experiment. The difference between the rate of heat input to the sample and the heat of reaction at any instant during scanning may be used to calculate the specific heat of the sample at the same instant. Specific heat data show two maxima during each scanning experiment. These maxima may be associated with transitions occurring during cure in the melt and rubbery states.     

Effect of flame heat flux on thermal response and fire properties of char‐forming composite materials

This study evaluates the effect of flame heat flux on the prediction of thermal response and fire properties of a char‐forming composite material. A simplified two‐layer flame model was developed and incorporated into a heat transfer thermal model to predict the thermal response and fire reaction characteristics of a burning material. A typical char‐forming material, E‐glass reinforced polyester composite, was used in the study. A cone calorimeter was used to measure the fire reaction characteristics of the composite. The flame heat flux in a cone calorimeter test setup was estimated using the simplified flame model. Thermal response and fire property predictions with and without the effect of flame heat flux were compared with experimental data obtained from the cone calorimeter tests. Results showed that the average flame heat flux of the composite in a cone calorimeter was 19.1 ± 6 kW/m² from model predictions. The flame had a significant effect on the thermal response and fire properties of the composite around the first heat release peak but the effect decreased rapidly afterwards. Copyright © 2012 John Wiley & Sons, Ltd.     

Measuring enthalpy of fast exothermal reaction with micro‐reactor‐based capillary calorimeter

This work presents a new micro‐reactor‐based capillary calorimeter for the enthalpy measurement of fast exothermal reactions. The new calorimeter was operated in the continuous way and the reaction enthalpy can be easily measured with the online temperatures from detached sensor chips. A standard reaction system and an industrial reaction system were selected to test this new calorimeter with homogeneous and heterogeneous reaction processes. The measurement was taken place at nearly adiabatic situations and the reaction enthalpy was calculated from the rising of temperature. High accuracy and good repeatability were obtained from this new calorimeter with relative experimental errors less than 3.5% and 2.4%, respectively. The temperature response was quick in this new calorimeter too, which was benefit to the low cost of reactive component. The fast and accurate measurement was contributed to the nice mixing performance and strict plug flowing in the calorimeter. © 2009 American Institute of Chemical Engineers AIChE J, 2010     

Precipitation polymerization of acrylic acid: Kinetics,viscosity and heat transfer

The free-radical precipitation polymerization of acrylic acid in toluene was studied in an isothermal reaction calorimeter. The polymerization shows an autocatalytic behaviour of the rate of polymerization typical for precipitation polymerizations. The rate of polymerization with respect to conversion can be modeled by taking the volume fraction of the precipitated polymer into consideration. The viscosity of the reaction mixture increases with increasing volume fraction of precipitated polymer. The viscosity runs through a maximum at high conversion. The final viscosity decrease is probably due to shear stress caused aggregation phenomena of the polymer particles. A model is discussed which can describe the increase and decrease of viscosity of the system. By means of reaction calorimetry it is possible to determine the reaction-sided heat transfer coefficient during polymerization. The comparison of the experimentally determined temperature course of the reaction mixture and the temperature course calculated with a coupled model of the polymerization and the calorimeter shows that the heat-transfer characteristic changes instantaneously during a small conversion interval at the very beginning of the polymerization.     

Study of the Heat and Kinetics of Nitration of 1,2,4‐Triazol‐5‐one (TO)

The heat effects of the nitration and dissolution processes of 1,2,4‐triazol‐5‐one (TO) in acidic environments were measured by differential reaction calorimetry. The kinetics of nitration of TO in a 200‐mL reactor were investigated by UV/Vis spectroscopy. Temperature changes were measured in a 10‐L batch reactor during the TO nitration. A model of kinetics for the synthesis of 3‐nitro‐1,2,4‐triazol‐5‐one (NTO) was proposed and it was used to simulate the phenomena occurring in the calorimeter and in the reactors. The experimental data were compared with modeling results and parameters of the Arrhenius equation for synthesis of NTO with selected nitration mixtures were determined.     

融合C80数据的绝热加速量热法热惯量因子修正

受限于仪器原理,绝热加速量热法数据分析需进行热惯量因子修正。然而,现有的修正方法均违背由反应物比热及炉体温度动态追踪效果变化等引起热惯量因子动态变化的事实,导致动力学参数求取存在偏差。针对上述不足,提出一种基于C80与绝热加速量热数据联用的绝热加速量热热惯量因子修正及动力学计算方法。具体步骤如下：基于Friedman法分析C80数据获取无模型动力学参数,将其代入绝热数据求解反应体系比热容与等效热惯量因子乘积,并在绝热平衡方程中由上述乘积替代恒定热惯量因子及比热实现动力学计算。以过氧化二叔丁基(DTBP)和过氧化氢异丙苯(CHP)为实验对象进行实验验证。结果表明,基于两种量热模式联用的热惯量因子修正方法避免了热惯量动态变化对动力学分析的影响,从而获得更加准确的动力学参数。     

Isothermal reaction calorimeters—I. A literature review

Most chemical and physical processes are accompanied by heat effects. These heat effects may contain significant information concerning the mechanism of the process, and a safe scale up of the process often requires a quantitative knowledge of the heat generated or consumed. In the present review one particular laboratory equipment for measurement of heat effects—the isothermal reaction calorimeter—will be described. Part I is a literature study of the available calorimeter equipment. Isothermal reaction calorimeters are described and classified according to the measurement principle of the particular design. Part II describes different techniques for numerical treatment of calorimeter data. It is argued that modern filtering methods and careful mathematical modeling can be used to obtain a significant improvement in the determination of physical and chemical parameters from calorimeter experiments. Finally, as an example a new data treatment system for a commercial bench scale isothermal calorimeter will be discussed.     

Is heat transfer governing chemical reactions in supercritical fluids?

A high pressure reactor calorimeter has been developed to study chemical reactions in supercritical fluids. Non-dimensional analysis of the heat transfer mechanism in the calorimeter verifies the application of the Nusselt correlation in scCO₂. The reactor's cover and flange have been modified to be fully temperature controlled and their contribution to the dynamic response of the calorimeter is investigated. Finally, the esterification of methanol with acetic anhydride was chosen as a model reaction and the role of heat transfer in chemical reactions in supercritical fluids is discussed.