Efficient simulation of periodically forced reactors with radial gradients

The aim of this paper is to present a limited memory iterative method, called the Broyden Rank Reduction method, to simulate periodically forced processes in plug-flow reactors with radial gradients taken into account. The simulation of periodically forced processes in plug-flow reactors leads to the development of partial differential equations that are normally solved in time using dynamical simulation. Depending on the convergence properties of the system at hand, the number of cycles that needs to be computed up to a cyclic steady state is reached can be large. Therefore direct iterative methods are essential in order to capture the long time dynamics of such systems. In order to overcome severe memory constraints many authors have reverted to pseudo-homogeneous 1D models and to coarse grid discretization, which renders such models inadequate or inaccurate. The results that we present show that the long time dynamics actually depends on the radius of the reactor and, hence, the full 2D model is essential in order to simulate periodically forced processes in plug-flow reactors accurately.     

Temperature wave‐trains of periodically forced networks of catalytic reactors

Networks of N identical catalytic reactors with periodically switched inlet and outlet sections are studied for first‐order irreversible exothermic reactions. Switching strategies with inlet and outlet sections periodically jumping a fixed number n_s of reactors are considered and the mechanisms governing the formation of traveling temperature wave‐trains are analyzed as n_s and N are varied. To this aim, a geometric approach to the analysis of the network energy balance is developed. Based on this approach, infinite domains of traveling temperature wave‐trains are predicted for any n_s and N. Analytical approximations are derived for the stability limits and the spatiotemporal patterns of these regimes. Stability boundaries predicted analytically include for any solution the largest part of the stability region computed by numerical simulation. Moreover, good agreement is found between the structure of the spatiotemporal patterns computed numerically and that predicted based on the proposed approach. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

Energy shaping plus damping injection control for a class of chemical reactors

Traditionally, stabilization of chemical reacting systems has been achieved with linear P or PD compensation schemes. Practical and numerical results have showed that classical linear compensation can yield acceptable performance. On the other hand, recent years have witnessed the emergence of systematic feedback control strategies based on energy and port-interconnected systems. These approaches exploit the physical structure of the chemical reactor to construct compensation schemes with physical appealing. The aim of this work is to show that traditional PD compensation for CSTRs can be interpreted in terms of mechanical system analogies. In the line of energy shaping plus damping injection for robotic systems, it is shown that proportional feedback is a type of potential energy shaping to accommodate a unique equilibrium point. On the other hand, derivative control acts as a damping injector for the energy balance within the chemical reactor. The stability proof uses a novel approach to convert the temperature dynamics into a second-order systems where the mechanical analogies become more evident. In this way, the stability analysis can be performed with singular perturbation methods with a Lyapunov function for the energy balance derived from a “potential plus kinetics” energy construction.     

微波化学反应器介质耦合窗应力计算分析与设计

微波能量耦合窗口是微波化学反应器的关键部件,它应该尽可能小地反射微波能量以避免烧毁功率源,同时密闭反应腔体以分隔反应物与微波装置。根据多物理场耦合模型,利用有限元方法对耦合窗进行了结构应力计算和设计,分析了微波加热过程中介质耦合窗的受热和热应力特点,得到了对工业应用具有参考价值的结果。提出可以通过设计适宜的介质垫片来降低窗体应力,提高可靠性。     

Combined effects of internal heat generation and higher order chemical reaction on the non‐darcian forced convective flow of a viscous incompressible fluid with variable viscosity and thermal conductivity over a stretching surface embedded in a porous medium

In this paper, we study the combined effects of internal heat generation and higher order chemical reaction on a steady two‐dimensional non‐Darcian forced convective flow of a viscous incompressible fluid with variable dynamic viscosity and thermal conductivity in a fluid saturated porous medium passing over a linear stretching sheet. Using similarity transformations, the governing nonlinear‐coupled partial differential equations are made dimensionless and solved numerically for similarity solutions using very robust computer algebra software Maple 8. The non‐dimensional velocity, temperature and concentration distributions are presented graphically for various pertinent parameters such as relative temperature difference parameter, Darcy number, porosity parameter, reaction rate parameter and the order of the chemical reaction. The variations of Prandtl number and Schmidt number within the boundary layer are also displayed graphically when the fluid dynamic viscosity and thermal conductivity are temperature dependent. From the present numerical computations it is found that Prandtl number as well as Schmidt number must be taken as variables within the flow domain when the fluid's dynamic viscosity and thermal conductivity are variable. In the presence of internal heat generation, dynamic viscosity and thermal conductivity of the fluid are found to be higher than when it is absent. Increasing Darcy number reduces dynamic viscosity as well as thermal conductivity whereas increasing pore size reduces the Schmidt number and increases the Prandtl number within the boundary layer. For higher order reaction the rate of increase in mass transfer function is less compared to the rate of increase for the lower order reaction. © 2011 Canadian Society for Chemical Engineering     

新型化学防砂剂的合成及性能评价

以DMDAAC、AM、水玻璃、OP-10为原料,合成了一种新型的含硅高分子防砂剂,对粒径0.074 mm以上的砂子具有良好的阻挡作用.并考察了防砂剂与地层流体的配伍性.     

Estimation of time-varying time delay and parameters of a class of jump Markov nonlinear stochastic systems

It is a challenging problem to estimate time-varying time delay and parameters, especially for systems subject to disturbances with unknown statistics in measurements. The desirable filter should be sensitive to unmodeled dynamics caused by random changes in time delay and parameters, and also be robust to disturbances. Recently, we proposed a finite-horizon robust Kalman filter (RKF) through designing and simultaneously minimizing the upper bounds of unknown covariances of prediction errors, filtering residuals and estimation errors. Unfortunately, unmodeled dynamics and disturbances must be hypothesized to be zero-mean white noises in the RKF. To cope with more general unmodeled dynamics and/or disturbances, a class of jump Markov stochastic systems (JMSS) subject to unmodeled dynamics and disturbances is considered in this article so that a priori system information, such as the value range of unknown and/or randomly changing parameters, can be introduced. Through combining the RKF with the interacting multiple model (IMM) estimation technique, a RKF/IMM algorithm is proposed for such JMSS. Then it is applied to estimate time-varying time delay and parameters of a continuous stirred tank reactor (CSTR) with sensors subject to Gaussian disturbances with unknown means and/or covariances. The RKF/IMM algorithm is compared with the extended Kalman filter (EKF), the strong tracking filter (STF) and the RKF through computer simulations. The results show that, in the case that measurement disturbances are zero-mean noise with unknown covariances, the RKF/IMM and RKF achieve almost the same accurate estimates, which are superior to those of the STF and EKF; in the case that such disturbances have unknown covariances and time-varying means, only the RKF/IMM remains the ability to estimate time-varying time delay and parameters. Furthermore the RKF/IMM has unique ability to identify the disturbance mean no matter whether it is constant or time-varying. Moreover, the RKF/IMM algorithm is shown having strong robustness against the a priori filter parameters, this may be attractive in practical applications.     

Glass formation, chemical properties and surface analysis of cu-based bulk metallic glasses

This paper reviews the influence of alloying elements Mo, Nb, Ta and Ni on glass formation and corrosion resistance of Cu-based bulk metallic glasses (BMGs). In order to obtain basic knowledge for application to the industry, corrosion resistance of the Cu-Hf-Ti-(Mo, Nb, Ta, Ni) and Cu-Zr-Ag-Al-(Nb) bulk glassy alloy systems in various solutions are reported in this work. Moreover, X-ray photoelectron spectroscopy (XPS) analysis is performed to clarify the surface-related chemical characteristics of the alloy before and after immersion in the solutions; this has lead to a better understanding of the correlation between the surface composition and the corrosion resistance.     

不同堆存时间电解锰渣的理化特性分析

渣场堆存的电解锰渣中含有大量易迁移的锰和氨氮,极易污染周边环境。本文系统研究了不同堆存时间（3个月~10年）电解锰渣的pH、含水率、电导率、金属总量、浸出毒性和化学形态等理化特性,采用X射线衍射（XRD）、扫描电子显微镜（SEM）、能谱仪（EDS）以及X射线光电子能谱（XPS）等分析手段,探察电解锰渣在不同堆存时间下的物相组成、微观形貌、表面电子价态等变化规律。研究结果表明,随着堆存时间增加,锰渣的pH、含水率和电导率下降,可溶性Mn²⁺、Ca²⁺、Mg²⁺、Se⁴⁺和NH{}_{\mathrm{4}}^{+}-N浓度降低,其中可交换态和碳酸盐结合态的Mn是Mn元素流失的主要形态。同时,堆存10年的电解锰渣仍存在较大的环境污染风险,其中电解锰渣中的Cu、Cr、Cd、Pb、Zn等金属总量远超广西土壤背景值,Se⁴⁺的浸出浓度是《危险废物鉴别标准 浸出毒性鉴别》（GB 5085.3—2007）中浓度限值的11倍,Mn²⁺和NH{}_{\mathrm{4}}^{+}-N的浸出浓度是《污水综合排放标准》（GB/T 8978—1996）一级标准限值的102倍和45倍。不同堆存时间的电解锰渣中锰和氨氮主要以(NH₄)(Mn,Ca,Mg)PO₄·H₂O、(NH₄)₂SO₄、MnSO₄·H₂O、MnCO₃、Mn₂O₃、MnO₂等物相存在,含铁物相主要包括FeS₂、FeOOH、Fe₃O₄和Fe₂O₃等,且电解锰渣中还含有Al₄(OH)₈(Si₄O₁₀)、Al₂Mg₄(OH)₁₂(CO₃)·3H₂O和KAl(SO₄)₂·12H₂O等黏土矿物。此外,随着堆存时间的增加,电解锰渣的平均孔径减小,块状、柱状和绒球形的电解锰渣颗粒交错包裹现象增加,同时Fe(OH)₃胶体颗粒也逐渐转变成FeOOH、Fe₂O₃等含铁物相。本研究成果为电解锰渣无害化处理与资源化利用提供了基础理论支持。     

Enhanced mechanical and thermal properties of AlN ceramics via a chemical precipitation process

A uniform dispersion of sintering additives is crucial to improve the thermal and mechanical properties of AlN ceramics. In this study, the Y₂O₃-coated AlN composite powder was successfully prepared by the chemical precipitation (CP) process, thereby improving the homogenization of Y₂O₃ in AlN green compacts. The precipitation coating behavior of Y₂O₃ precursor was investigated by FTIR and TG-DSC, and the corresponding reaction equation was proposed. The results of TEM, XRD, and XPS for the CP processed AlN powder indicated that a uniform amorphous Y₂O₃ layer was fully wrapped on the surface of AlN powder. The microstructures and phases of the sintered AlN samples prepared via the CP and conventional ball-milling (BM) processes, respectively, were compared. The CP process can result in decreasing oxygen content in AlN grains, facilitating the formation of the desirable isolated second phases, and strengthening the grain and grain boundary of AlN ceramic. As a result, the thermal conductivity, bending strength and fracture toughness of the CP processed AlN ceramic are 9.43%, 10.56%, and 18.50% higher than those of the BM processed sample, respectively, illustrating the CP process is a pretty effective way to simultaneously improve the thermal and mechanical properties of AlN ceramics.     

某电厂基建锅炉化学清洗质量事故调查与分析

某电厂基建锅炉化学清洗后,对水冷壁及省煤器割管检查发现,未形成均匀、致密的钝化膜,并且有铁锈生成。监视管段中试片的腐蚀速率为10.16g/(m2.h),腐蚀总量为99.89g/m2,均未达到相关标准规定。通过对此次化学清洗过程中工艺控制参数分析,找出了影响化学清洗效果的原因。     

Fast and robust fault diagnosis for a class of nonlinear systems: detectability analysis

In recent years, robust fault diagnosis of nonlinear systems has received much more attention due to the universal existence of nonlinearities and model uncertainties in practice. By introducing a new adaptive law and sliding mode observers with boundary layer control into Polycarpou's online approximator, we propose a fast and robust fault diagnosis strategy for a class of nonlinear systems in this article. The robustness and stability are proved theoretically by the Lyapunov method and the detectability conditions as well as the upper bound of detection time are given, which demonstrate that the detection time of our strategy is much shorter than that of Polycarpou's approach. Simulation results on the three-tank system “DTS200” show the effectiveness and fastness of the proposed strategy.     

Hydrogen production via chemical looping dry reforming of methane: Process modeling and systems analysis

The present study presents and analyses a family of “chemical looping dry reforming” (CLDR) processes that produce inherently separated syngas (H₂ and CO) streams via a combination of methane cracking in a “cracker reactor” and the Boudouard reaction (i.e., conversion of the formed carbon with CO₂ to CO) in a “CO₂ reactor,” and then further maximize the H₂ yield via conversion of the produced CO via water-gas-shift. Remaining CO₂ emissions are minimized via CO₂ capture and sequestration. Four different configurations are evaluated which differ in how the heat required for the highly endothermic dry reforming reaction is supplied: (i) combustion of additional CH₄ feed (CLDR-CH₄); (ii) combustion of some of the CO produced in the CO₂ reactor (CLDR-CO); and combustion of some of the carbon produced in the cracker reactor with (iii) pure oxygen (CLDR-C-oxy); or (iv) with air (CLDR-C-air). Process models are developed to comparatively analyze the mass and energy balances of these configurations, and benchmark them against H₂-production via conventional dry reforming and steam reforming of methane. Our results show that CLDR-C-oxy is the most promising H₂-production pathway among the chemical looping and conventional technologies both in terms of chemical energy efficiency and in terms CO₂ emissions. Thus, the unique flexibility offered by the production of inherently separated syngas streams in CLDR enables overcoming the disadvantage of the strongly endothermic dry reforming reaction by combusting carbon internally in the reactor and thus achieving highly effective heat integration. Overall, the results support the technical viability and demonstrate the promise for strong process intensification of CLDR compared to conventional dry reforming and even steam reforming, the most widely used H₂-production pathway to-date.     

Surface chemical and morphological properties of a blend containing semi-crystalline and amorphous polymers studied with ToF-SIMS, XPS and AFM

The polymers BA-C8 and 6FBA-C8 were obtained by condensation polymerization of 1,8-dibromo-octane with bisphenol A and 4,4′-(hexafluoroisopropylidene)diphenol, respectively. A blend (BA-C8/6FBA-C8 (80/20)) containing 80 wt% of BA-C8 and 20 wt% 6FBA-C8 was prepared. Only one glass transition temperature was detected using a differential scanning calorimeter, suggesting that the blend is miscible. The surface chemical and morphological properties of the blend were studied as BA-C8 crystallized using atomic force microscopy, X-ray photoelectron spectroscopy, time-of-flight secondary ion mass spectrometry and contact angle measurements. The results of the surface analyses showed that the surface of the blend was found to be enriched in the 6FBA-C8 polymer, especially at the crystalline regions. The crystalline regions were found to be raised above the amorphous regions. Surface segregation and crystallization were the two main factors that contributed to the changes in the chemical composition and morphology of the surface.     

The effects of Ni-addition on the crystal structure,thermal properties and morphology of Mg-based hydroxyapatites synthesized by a wet chemical method

Four Mg-based hydroxyapatites (HAps) doped with Ni at various amounts of 0, 0.6, 1.2 and 1.8?at% were prepared at the temperature of 870?°C by a wet chemical synthesis. The crystallite size, lattice parameters and crystallinity percent dramatically decreased with adding of Ni. The amount of HAp phase for all the Ni-containing samples is smaller than that of the Ni-free MgHAp. Furthermore, the lattice strain, stress and anisotropic energy density values were affected by the amount of Ni. The differential thermal analysis (DTA) measurements taken in the temperature range from 25 to 1000?°C showed that all the samples are thermally stable. No significant change in the morphology was observed. It was observed that the gradual introduction of Ni caused the Ca-deficiency.     

Homotopy analysis of heat and mass transfer boundary layer flow through a non‐porous channel with chemical reaction and heat generation

This paper describes the two‐dimensional flow of an incompressible viscous fluid through a non‐porous channel with heat generation and a chemical reaction. Employing similarity transformations the governing non‐linear partial differential equations are solved both analytically and numerically. Analytically, we used the homotopy analysis method and numerically, we used the Matlab in‐built boundary value solver bvp4c. The effects of the Reynolds number Re, the Eckert number Ec, heat generation parameter δ, chemical reaction parameter γ, and the local Grashof number Gc on the velocity, temperature, and concentration fields are shown through tables and graphs and discussed.     

Towards a methodology for the systematic analysis and design of efficient chemical processes: Part 1. From unit operations to elementary process functions

A successful intensification of a chemical process requires a holistic view of the process and a systematic debottlenecking, which is obtained by identifying and eliminating the main transport resistances that limit the overall process performance and thus can be considered as rate determining steps on the process level. In this paper, we will suggest a new approach that is not based on the classical unit operation concept, but on the analysis of the basic functional principles that are encountered in chemical processes.A review on the history of chemical engineering in general and more specifically on the development of the unit operation concept underlines the outstanding significance of this concept in chemical and process engineering. The unit operation concept is strongly linked with the idea of thinking in terms of apparatuses, using technology off the shelf. The use of such “ready solutions” is of course convenient in the analysis and design of chemical processes; however, it can also be a problem since it inherently reduces the possibilities of process intensification measures.Therefore, we break with the tradition of thinking in terms of “unit apparatuses” and suggest a new, more rigorous function-based approach that focuses on the underlying fundamental physical and chemical processes and fluxes.For this purpose, we decompose the chemical process into so-called functional modules that fulfill specific tasks in the course of the process. The functional modules itself can be further decomposed and represented by a linear combination of elementary process functions. These are basis vectors in thermodynamic state space. Within this theoretical framework we can individually examine possible process routes and identify resistances in individual process steps. This allows us to analyze and propose possible options for the intensification of the considered chemical process.