Continuum approximation of large reaction mixtures in reactors with backmixing

The growing need to produce ultraclean fuels from hydrocarbon mixtures such as petroleum fractions and residues has put increasing pressure on refiners to achieve deep conversions. It is imperative to be able to predict the behavior of such mixtures at high conversions as functions of their properties and reactor type. To this end, treating the reaction mixture as a continuum greatly simplifies the analysis and modeling of the conversion process. However, the continuum approximation can become invalid at very high conversions. Previously, we examined the validity of the approximation for various reactions in plug flow reactors. The validity conditions for first‐order reaction mixtures in reactors with different mixing intensities are developed. In general, backmixing widens the range of validity. In certain cases, the continuum approximation is valid at arbitrarily high conversions. © 2014 American Institute of Chemical Engineers AIChE J, 61: 159–165, 2015     

甲醇蒸汽重整制氢反应动力学研究进展

甲醇蒸汽重整制氢技术对于解决汽车、船舶等交通工具上燃料电池的氢源问题具有重要意义,近年来已成为碳氢燃料重整制氢的研究热点。本文首先综述了甲醇蒸汽重整制氢的5种反应机理,该方面的研究仍处于定性和推理阶段,尚未达成统一的结论。然后分析了甲醇蒸汽重整反应动力学的研究进展,发现大多研究是基于Cu系催化剂提出,反应温度集中在160～350℃,反应压力多为1atm,研究表明反应物水醇比最优值为1.3～1.4。最后,整理了研究中所提出的动力学模型,指出相较于单速率和三速率模型,双速率模型可反映产物中CO的含量及其对反应速率的影响,且模型相对简单,动力学方程的求解过程也相对容易,但其适用性还有待进一步验证。本文可为甲醇蒸汽重整制氢系统的设计与优化提供理论依据。     

A composite reaction engineering approach to drying of aqueous droplets containing sucrose,maltodextrin (DE6) and their mixtures

Recently, several studies have been published on the spray drying of sucrose and other low‐molecular‐weight sugars which are typically sticky materials. Sticky materials can not be processed under normal drying conditions and may require addition of high‐molecular‐weight carbohydrates such as maltodextrin. Predicting appropriate drying conditions are however difficult due to the unavailability of drying kinetics. In this article, we have formulated the drying kinetics model using the reaction engineering approach (REA) for the drying of aqueous sucrose and aqueous maltodextrin (DE6) droplets. The relative activation energy was empirically obtained based on experimental measurements. To model the drying of droplets containing both solutes (sucrose and maltodextrin), a new “composite” REA has been established and presented here for the first time. Results demonstrated that the composite REA forms a reliable framework to model the drying of aqueous solutions of pure carbohydrates and their mixtures. © 2008 American Institute of Chemical Engineers AIChE J, 2009     

On mixing rules for the hydraulic permeability of fiber mixtures

We perform numerical simulations of Stokes flow through ordered arrays of fibers of square cross-section. The results for the permeability of single-size-fiber arrays are in very good agreement with the well-known correlation of Jackson and James, provided that an effective radius of equivalent cylindrical fibers is used with the same cross-sectional area. Then, we consider arrays of mixtures of different-sized fibers and test several mixing rules, proposed for estimating the composite permeability. The two most well-known, namely, the unweighted- and the volume-averaged resistivity rules give good predictions for not too large size-ratios, yet they systematically overestimate and underestimate the numerical results, respectively. Then, it appears almost self-evident that a combination of the above two mixing rules would provide a better prediction. Indeed, the geometric mean gives excellent agreement with the numerical results over an extended range of size ratios and relative volume fractions.     

液体乙烯基硅树脂的制备及固化反应动力学

合成了一种液体乙烯基硅树脂,并用FT-IR、GPC、¹H NMR和²⁹Si NMR等手段对其结构进行表征。采用非等温差示扫描量热法（DSC）研究了乙烯基硅树脂/苯基含氢硅油体系的固化反应动力学,用Kissinger方程和高级等转化率法（Vyazovkin方法）分别计算了该体系的表观活化能E_a,用Málek法进行模型拟合动力学分析,通过T-β外推法确定该体系的固化工艺参数。结果表明：Kissinger法和Vyazovkin法得到的活化能分别为85.3 kJ·mol^-1和84.0 kJ·mol^-1,二者所得结果的差别较小;乙烯基硅树脂体系固化动力学符合Šesták-Berggren（m,n）模型,m和n分别为0.092、1.440,拟合曲线与实验的DSC曲线吻合;该树脂体系的近似凝胶化温度为89.1℃,固化温度为127.8℃,后处理温度157.6℃。     

硅热法炼镁动力学的数学模型分析及数值模拟

硅热法是目前工业产镁的主要技术手段,但由于该过程涉及高温化学反应及复杂传热机理,鲜有报道对此技术进行详细动力学及数值计算研究。本工作采用实验的方法获得皮江法炼镁化学反应动力学数据,根据数据分析确定了分段动力学模型,并转化为精确的数学模型。然后建立了耦合数学模型、辐射模型和导热模型的三维非稳态数值计算模型,并通过数值模拟计算,获得工业产镁过程中球团反应转化率和温度随生产时间的分布规律。计算结果表明,生产时间2h后球团最低温度已达1203K,4h后物料平均还原率已达66%。该技术改进方向主要为增加外层球团数量并提高还原罐中心区域传热效率。本工作可以用于指导强化传热设备的设计,预测实际生产效果,节省大量试验投资。     

Power law models as descriptors of the kinetics of complex systems: Temperature effects

The effects of temperature on power law models for the kinetics of parallel first order systems are studied. The variation of the empirical power law parameters with temperature provides information on the relationship between the rate constant and activation energy distributions; in particular. if the power law exponent increases with temperature, there is a positive correlation between the rate constants and the activation energies; if the power law exponent decreases with temperature, there is a negative correlation between the rate constants and the activation energies; Arrhenius plots will always be concave unless the activation energies for all the reactions are equal. Application of the techniques described here to data from the catalytic cracking of gas oil over LaY zeolite reveals a compensation effect among the reacting hydrocarbon species.     

On the temperature control in a microstructured packed bed reactor for methanation of CO/CO2 mixtures

Microreactor technology is widely used for process intensification and is essential for fast and strongly exothermic reactions exhibiting mass and heat transfer limitations. In the scope of the MINERVE Power‐to‐Gas project, sponsored by KIC InnoEnergy from 2012 to 2015, a micro packed bed reactor was developed for conversion of syngas containing CO₂ into methane. This work focuses on heat removal and temperature control in a manufactured device using syngas throughputs less than 1.4 Nm³/h (10% CO, 7% CO₂, H₂/C = 4) while examining the cooling potential of different cooling fluids, e.g., air, steam and water. © 2016 American Institute of Chemical Engineers AIChE J, 63: 120–129, 2017     

Poly(ADP-ribose)-polymerase-catalyzed hydrolysis of NAD+: QM/MM simulation of the enzyme reaction

Poly(ADP-ribose) polymerase (PARP) is a nuclear enzyme which uses NAD+ as substrate and catalyzes the transfer of multiple units of ADP-ribose to target proteins. PARP is an attractive target for the discovery of novel therapeutic agents and PARP inhibitors are currently evaluated for the treatment of a variety of pathological conditions such as brain ischemia, inflammation, and cancer. Herein, we use the PARP-catalyzed reaction of NAD+ hydrolysis as a model for gaining insight into the molecular details of the catalytic mechanism of PARP. The reaction has been studied in both the gas-phase and in the enzyme environment through a QM/MM approach. Our results indicate that the cleavage reaction of the nicotinamide-ribosyl bond proceeds through an SN2 dissociative mechanism via an oxacarbenium transition structure. These results confirm the importance of the structural water molecule in the active site and may constitute the basis for the design of transition-state-based PARP inhibitors.     

On the use of the generalized autocatalytic models: The thermal decomposition of 3,5‐dinitro‐4‐methylbenzoic acid

The thermal decomposition of 3,5‐dinitro‐4‐methylbenzoic acid is studied by means of differential calorimetric techniques (DSC). Its autocatalytic behaviour has been highlighted and the decomposition process has been described considering the generalized expression of the ?esták–Berggren model. A new procedure for the optimization of the initiation parameter along with the other Arrhenius constants and kinetic exponents starting from the knowledge of the classic ?esták–Berggren model is illustrated. Encouraging results point out the validity of the approach which has been verified considering both a series of numerical and real experiments. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1300–1308, 2015