Continuous‐Flow Di‐N‐Alkylation of 1H‐Benzimidazole in a Fixed‐Bed Reactor

A new process for a continuous‐flow di‐N‐alkylation of 1H‐benzimidazole to 1H‐benzimidazole‐3‐ium iodide by methylene iodide in the presence of potassium carbonate in a fixed‐bed reactor is presented. The synthesis was transferred from batch to continuous operation with similar yields and conversion rates. Moreover, the influence of temperature and residence time in the continuous flow setup was characterized; optimized conditions led to a doubling of yield. In addition, the continuous flow allowed for a better control of the two‐step reaction by adding an additional tube reactor after the fixed bed that further enhanced the overall performance. With this, the continuous‐flow system presented itself as superior due to higher available temperatures and a better controllability.     

Continuous‐Flow Surface Aeration Systems

An aeration process in an activated sludge plant is a continuous‐flow system. In this system, there is a steady input flow (flow from the primary clarifier or settling tank with some part from the secondary clarifier or secondary settling tank) and output flow connection to the secondary clarifier or settling tank. The experimental and numerical results obtained through batch systems can not be relied on and applied for the designing of a continuous aeration tank. In order to scale up laboratory results for field application, it is imperative to know the geometric parameters of a continuous system. Geometric parameters have a greater influence on the mass transfer process of surface aeration systems. The present work establishes the optimal geometric configuration of a continuous‐flow surface aeration system. It is found that the maintenance of these optimal geometric parameters systems result in maximum aeration efficiency. By maintaining the obtained optimal geometric parameters, further experiments are conducted in continuous‐flow surface aerators with three different sizes in order to develop design curves correlating the oxygen transfer coefficient and power number with the rotor speed. The design methodology to implement the presently developed optimal geometric parameters and correlation equations for field application is discussed.     

Optimization of Sugarcane Bagasse Hydrolysis by Microwave‐Assisted Pretreatment for Bioethanol Production

Sugarcane bagasse hydrolysis was optimized by dilute‐acid pretreatment and subsequent enzymatic treatment. The studied parameters were microwave heating temperature, residence time, and enzyme dosage as the main factors in a central composite design. The amount of released total reducing sugars, glucose, pentose, phenolic compounds, and furfural were measured after each stage. The optimum conditions with suitable concentrations of inhibitors and reducing sugars were applied for bioethanol production. As an example, ethanol was obtained from reducing sugars by Pichia stipitis without detoxification.     

Practical Continuous‐Flow Controlled/Living Anionic Polymerization

A continuous‐flow reaction system was developed, allowing flow conditions of the entire system to be maintained at a predetermined constant level, which is one of the most significant factors for successful industrial application. Controlled/living anionic polymerization was selected as a model reaction since the characteristics of its polymer products, molecular weights, and molecular weight distributions are highly susceptible to changes in the relative flow rates of a monomer and initiator solutions. In flow microreactors, controlled/living anionic polymerization of styrene in tetrahydrofuran (THF)/hexane initiated by THF‐diluted n‐butyllithium (n‐BuLi) was examined. Poly(styrenes) of larger molecule sizes such as Mn > 15 000 were successfully synthesized. After continuous operation for four hours, ca. 0.5 kg of the polymer was readily produced with narrow molecular weight distribution, demonstrating the applicability of this continuous‐flow system for controlled/living anionic polymerization on considerably large scale with a view to its industrial usage in the future.     

Microwave‐Assisted Synthesis of Magnetic Hydroxyapatite for Removal of Heavy Metals from Groundwater

A simple, fast, and economic methodology to fabricate a highly efficient superparamagnetic Fe₃O₄/hydroxyapatite nanocomposite (MHAP) was successfully developed. Hydroxyapatite was functionalized with magnetite nanoparticles through coprecipitation‐assisted microwave processes to improve the magnetic properties. The synthesized magnetic hybrid adsorbent matrix was investigated by different methods. Transmission electron microscopy demonstrated a good impregnation of Fe₃O₄ on the hydroxyapatite matrix with uniform morphology. Magnetic hysteresis measurement revealed that MHAP nanocomposites exhibit excellent strong, soft‐magnetic properties. The synergistic effect was an evidence for iron and manganese ion removal, enlightening their potentialities in treatment of polluted ground water.     

Efficient and General Continuous‐Flow Hydroarylation and Hydroalkylation of Styrenes

A simple and efficient continuous‐flow hydroarylation of arenes and heteroarenes using various styrenes in conjunction with a heterogeneous catalyst has been developed. Additionally, this method has been successfully extended to the hydroalkylation of styrenes by employing 1,3‐dicarbonyl compounds as the nucleophile. Multigram quantities of diarylmethanes have been prepared using this new flow method.     

高硫焦用强混反应器流动特性

根据炼油工业近年来流态化技术的发展及相关新技术的应用,设计了一套适合高硫焦燃烧特点的新型强混反应器冷态实验装置. 强混反应器主要由混合段和提升段两部分构成,两部分的设备结构尺寸分别为f240 mm′3000 mm和f70 mm ′9000 mm. 选取了适合工业应用的实验操作条件：提升段操作表观线速度6~20 m/s,颗粒循环速率20~230 kg/(m2.s). 系统考察了高硫焦模拟颗粒在混合段的流动特性. 通过对强混反应器轴、径向颗粒浓度和速度分布的实验测定,将强混反应器的混合段沿轴向分为两个区,沿径向分为两个或三个区,并提出用径向分布指数来表征颗粒浓度和速度的径向不均匀性.     

Characteristics‐Based Model Predictive Control of a Catalytic Flow Reversal Reactor

This paper describes the formulation and tuning of a model‐based controller for a catalytic flow reversal reactor (CFRR). A plug flow non‐linear pseudo‐homogeneous mathematical representation of the process is used to model the mass and energy transport phenomena for the model‐based controller. A combination of the method of characteristics and model predictive control (MPC) technology is used to formulate the controller (Shang et al., Ind. Eng. Chem. Res. 43 (9) 2140–2149 (2004)). Mass extraction from the midsection of the reactor is used as the manipulated variable. Numerical simulations are used to show the performance of the formulated controller. The performance of the controller is evaluated on a simulated catalytic flow reversal reactor unit for combustion of lean methane streams for reduction of greenhouse gases emissions.     

Industrial Xylene/Ethylbenzene Isomerization Unit Using a Radial‐Flow Reactor and EUO‐Type Zeolite

A mathematical model based on 34 days continuous operation of an industrial isomerization unit was developed. The unit involves a radial‐flow reactor with a catalyst capable of converting xylenes and ethylbenzene to mixed xylenes. The catalyst contains EU‐1 zeolite, platinum, and alumina as binder. Two reactions are considered, i.e., ethylbenzene isomerization and xylene isomerization. The rates are based on the Hougen‐Watson model according to the literature. An optimization procedure based on the trust‐region‐reflective algorithm was carried out in order to obtain new kinetic constants that minimize the difference between the actual and the calculated values. The standard error of the parameters estimated was calculated through the deleted‐one Jackknife method.     

Toward a Continuous‐Flow Synthesis of Boscalid®

A two‐step continuous‐flow protocol for the synthesis of 2‐amino‐4′‐chlorobiphenyl, a key intermediate for the industrial preparation of the fungicide Boscalid^® is described. Initial tetrakis(triphenylphosphine)palladium‐catalyzed high‐temperature Suzuki–Miyaura cross‐coupling of 1‐chloro‐2‐nitrobenzene with 4‐chlorophenylboronic acid in a microtubular flow reactor at 160 °C using the tert‐butanol/water/potassium tert‐butoxide solvent/base system provides 4′‐chloro‐2‐nitrobiphenyl in high yield. After in‐line scavenging of palladium metal with the aid of a thiourea‐based resin, subsequent heterogeneous catalytic hydrogenation is performed over platinum‐on‐charcoal in a dedicated continuous‐flow hydrogenation device. The overall two‐step homogeneous/heterogeneous catalytic process can be performed in a single operation providing the desired 2‐amino‐4′‐chlorobiphenyl in good overall yield and high selectivity.     

Simulation and Experimental Validation of Two‐Phase Flow in an Aerosol Counter‐Flow Reactor using Computational Fluid Dynamics

A simulation of the hydrodynamic behavior of an aerosol‐counter flow reactor was conducted using an Euler‐Lagrange method. The simulation results were then verified with experiments. The process simulated was a separation process required during the production of biodiesel (fatty acid methyl ester). In this process, the liquid ester/glycerol phases are continuously injected through a hollow cone nozzle with an overpressure of 10⁶ Pa into the reactor, operated at 15000 Pa. The liquid is atomized because of the pressure drop and a liquid particle spray is generated with an inlet velocity of 44.72 m/s. Water vapor of temperature 333 K is injected tangentially through two side, gas inlets with an inlet velocity of 1.2 m/s. Excess methanol is subjected to a mass transfer from the liquid phase into the gas phase, which is withdrawn through the head of the reactor and condensed in an external condenser unit. The stripping of the methanol off the liquid leads to a sharp interface between the glycerol and the ester phase, which can then be easily separated by gravity or pumping. The gas velocity field, pressure field and the liquid particle trajectories were calculated successfully. Simulated dwell time distribution curves were derived and analyzed with the open‐open vessel dispersion model. Experimental dwell time distribution curves were measured, analyzed with the open‐open vessel dispersion model, and compared with the simulated curves. A good consistency between simulated and measured Bodenstein numbers was achieved, but 25 % of the simulated particles exited at the reactor's head, contrary to experimental observations. The difference between simulated and measured dwell times was within one order of magnitude.     

管式振荡流反应器的流动模式研究(Ⅰ)PIV和RTD实验研究

采用粒子成像可视化（PIV）技术研究了管式振荡流反应器（OFR）内的流场形态和混合特点,并采用脉冲进样法测定了OFR在不同振荡条件下的停留时间分布函数。实验结果表明,OFR的混合特性十分复杂,并随振荡强度的变化呈现出不同的特征。振荡强度较低时,振荡使得OFR径向混合加强,减少了滞留区,流体的流动趋于平推流;振荡强度较高时,腔室内布满数目、尺寸和位置不断变化的漩涡,使每个腔室趋向于全混,腔室问的返混增大。实验数据与多级串联全混釜模型的比较结果显示,OFR的混合特性远非简单流动模式模型所能表征。     

Flow Regime Transitions in an Internal‐Loop Airlift Reactor

The flow regime transitions of the riser and downcomer in an internal‐loop airlift reactor are investigated. Analysis of the effects of mean value, standard deviation and chaotic time series on pressure fluctuation signals is recorded to determine the transition of the hydrodynamics in the riser and downcomer of the internal‐loop airlift reactor. Two major chaotic invariants, the correlation dimension and the largest Lyapunov exponent, are employed to indicate the regime transitions. The regime transitions are determined by the sudden increase and decrease of the chaotic invariants, which are computed by the pressure fluctuation signals obtained by varying the gas flow velocity. The determination of chaotic invariants predicts that there is no heterogeneous phase existing in the downcomer of the internal‐loop airlift reactor. The experimental observations agree well with the predicted results.     

Characterization of Residence Time Distribution in a Plug Flow Reactor

One of the biggest advantages of plug flow reactors lies in their narrow residence time distribution. The pulse experiment, as a common method on acquiring that distribution, relies on the tracer injection being a perfect pulse. A deviation from a perfect pulse leads to erroneous results if not taken into account. With a numerical analysis of experimental data, this effect is quantified in turbulent and laminar flow regime and the results are compared to an analytical method. Significant deviations occur mostly in the turbulent regime, which has the greatest technical relevance.     

径向流动反应器流体力学特性研究进展

论述了流体在多孔流道中的变质量流动特性，建立了基于机械能全能量守恒方程和动量交换方程的径向反应器流体力学模型，分析了动量交换系数对流道静压分布计算的影响。结果表明，模型计算在小型或模拟设备中得到了证实，但在大型工业设备中是否适用尚待检验；建模理论分析中忽略了位能或重力的影响，均假设流体纯径向穿过催化床，此假设所隐含的模型适用条件尚待阐明。     

Ultra‐Fast Continuous‐Flow Photo Degradation of Organic Peroxide Explosives for Their Efficient Conversion into Hydrogen Peroxide and Possible Application

Fast, quantitative, and efficient direct photo degradation of organic peroxide explosives (HMTD, MEKP, TATP) using characteristic continuous‐flow UV radiation was investigated in aqueous solutions and achieved in less than 30 s.     

Study of Ethylene Polymerization Under Single Liquid Phase and Vapor‐Liquid Phase Conditions in a Continuous‐Flow Tubular Reactor

The feasibility of using continuous‐flow tubular reactors (CFTR) as an efficient research tool for polymerization reactions is investigated. This is a continuation of the extensive effort that had been made at Dow in recent years to set up and employ an electro‐thermal microreactor (an ohmically‐heated CFTR), which resulted in several internal and external publications and a US Patent. The main focus of this work is to investigate the effect of operating conditions and flow composition, mainly the number of existing phases, on the molecular weight of the polymer. A series of polymerization experiments were performed in single‐phase (liquid) and two‐phase (vapor‐liquid) flow regimes. In single‐phase polymerization, the ethylene concentration falls continuously along the length of the reactor. This will have a significant effect on the kinetics of polymerization, particularly the molecular weight of the produced polymer. A key advantage of operating in the two‐phase region is that an almost constant ethylene concentration is maintained along the length of the reactor. In effect, the vapor phase serves as a reservoir that replenishes the ethylene consumed in the liquid phase by polymerization. The molecular weight data show that this assumption is valid provided that the rate of mass transfer is significantly higher than the rate of the polymerization reaction.     

Simulation of Propane Dehydrogenation to Propylene in a Radial‐Flow Reactor over Pt‐Sn/Al2O3 as the Catalyst

Catalytic paraffin dehydrogenation for manufacturing olefins is considered to be one of the most significant production routes in the petrochemical industries. A reactor kinetic model for the dehydrogenation of propane to propylene in a radial‐flow reactor over Pt‐Sn/Al₂O₃ as the catalyst was investigated here. The model showed that the catalyst activity was highly time dependent. In addition, the component concentrations and the temperature varied along the reactor radius owing to the occurring endothermic reaction. Moreover, a similar trend was noticed for the propane conversion as for the propylene selectivity, with both of them decreasing over the time period studied. Furthermore, a reversal of this trend was also revealed when the feed temperature was enhanced or when argon was added into the feed as an inert gas.     

Model‐Based Optimization of a Photocatalytic Reactor with Light‐Emitting Diodes

The complicated interplay between mass and photon transfer within a photocatalytic reactor calls for an integrated design approach. A model‐based optimization approach for LED‐based photocatalytic reactors is presented. First, a model that describes the distribution of reactants and photons within a photocatalytic reactor is developed. Then, several design variables related to the reactor dimensions and light sources are optimized simultaneously using the photocatalytic degradation of toluene as a model system. The results demonstrate how different formulations of the problem can be used to either minimize the reactor cost or to obtain a specified concentration profile within the reactor.     

管式振荡流反应器的流动模式研究 (II)高振荡强度下的流动模型和模拟

根据高振荡强度下的粒子成像流场可视化实验结果,在分析振荡流场中漩涡结构特征的基础上,提出用带有二次流区的全混腔室和室间返混的多釜串联模型来表征高振荡强度下的管式振荡流反应器流动特性。根据停留时间分布实验结果,运用小生境遗传算法优化求解模型参数与振荡参数之间的定量关系。模拟计算表明,优化后的模型给出的停留时间分布曲线与实验结果吻合良好。