水相酶促酯化法拆分dl－薄荷醇的连续操作

对影响脂肪酶活性、稳定性和对映选择性的因素，如有机溶剂和反应温度等首先进行了优化。其次，使用悬浮于环已烷的粉末状游离脂肪酶（ＣａｎｄｉｄａｃｙｌｉｎｄｒａｃｅａｌｉｐａｓｅＯＦ３６０）作生物催化剂，成功地构建了一个高效的非水相游离酶连续搅拌釜反应器。当使用高度反应性的丙酸酐作为薄荷醇的酰基给体，进行连续的酶促对映选择性酯化反应时，醇的转化率在两周内可保持４０％以上，所生成酯的光学纯度超过９５％ｅ．ｅ。但是，当使用相应的游离丙酸（而不是酸酐）作酰基给体时，薄荷醇的转化率在连续操作开始后迅速下降，表明使用酸酐时的生产力要比使用游离酸时高。最后，对底物溶液的浓度和流速进行了进一步优化；同时对反应器系统的含水量进行了监测，并通过对酸酐料液的浓度或流速进行微调的方法，有效地将有机溶液相的水分浓度控制在一定的范围（２～４ｍｍｏｌ／Ｌ）之内，结果，ｄｌ－薄荷醇对映选择性连续酯化反应非常稳定地运行了两个月之久（转化率４７～３５％，光学纯度９５～９８％ｅ．ｅ．），酶反应器的半衰期超过２００天。     

Input Multiplicity Analysis in a Non‐Isothermal CSTR for Acid‐Catalyzed Hydrolysis of Acetic Anhydride

Multiplicity analysis gives practical guidance for process design to eliminate difficult operating regions associated with input and output multiplicities. Continuous stirred tank reactors (CSTRs) present challenging operational problems due to complex behavior such as input and output multiplicities, ignition/extinction, parametric sensitivity, and nonlinear oscillations. In the absence of a unified mathematical theory for representing various nonlinear system characteristics, the present study was aimed at understanding the dynamic behavior of CSTRs by means of experiments and to link the experimental data to theoretical considerations for further detection and elimination of operating problems. Theoretical modeling and analysis of a non‐isothermal CSTR with acid‐catalyzed hydrolysis of an acetic anhydride system for input multiplicity are discussed. Theoretical modeling of a non‐isothermal CSTR using a root‐finding technique was carried out for predicting steady‐state temperatures. Alternatively, a mathematical model for a non‐isothermal CSTR using unsteady‐state mass and energy balance equations is proposed. Computer‐based simulation was carried out using a program developed in MATLAB for final transient temperature and time‐temperature data of the CSTR system under investigation. The results of a theoretical analysis conducted for confirming the existence of input multiplicity in non‐isothermal CSTRs with acid‐catalyzed hydrolysis of acetic anhydride were compared with experimental investigations for validation.     

ENHANCED IMC-PID CONTROLLER DESIGN WITH LEAD-LAG FILTER FOR UNSTABLE AND INTEGRATING PROCESSES WITH TIME DELAY

In this article, a design method for a PID controller is proposed based on IMC principles for control of open loop integrating and unstable first-order processes with time delay. The design is based on H₂ optimal closed-loop transfer function for set point changes and step input disturbances. The method has one tuning parameter, and systematic guidelines are provided for the selection of this tuning parameter based on peak value of the sensitivity function. The performance of the designed controller is verified on various integrating and unstable processes, and it is observed that nominal and robust control performance is achieved with the proposed design method. Improved closed-loop performance was obtained when compared to other methods recently reported in the literature. Further, the proposed method provides good closed-loop performance even when there are large uncertainties in the process parameters.     

APPLICATION OF ADAPTIVE PID CONTROL WITH GENETIC ALGORITHM TO A POLYMERIZATION REACTOR

This article describes the application of adaptive PID control with genetic algorithm (GA) to a jacketed batch polymerization reactor. This method was used to keep the polymerization reactor temperature at the desired optimal path, which was determined by the Hamiltonian maximum principle method. The reactor was simulated and the model equations of this jacketed polymerization reactor were solved by means of Runge-Kutta-Felthberg methods. A genetic algorithm can be a good solution for finding the optimum PID parameters because unlike other techniques it does not impose many limitations and it is simple. In this research, suitability of these parameters was checked by the integral absolute error (IAE) criterion. The control parameters in the PID algorithm were changed with time during the control of a polymerization reactor. It was seen that the genetic algorithm was able to tune the PID controller used in this system in terms of higher robustness and reliability by changing the parameters continuously.     

Dynamic behavior and sensitivity of skeleton thermokinetic model for acetaldehyde oxidation

This work elucidated the dynamic behavior of the Wang-Mou model, a three-variable, skeleton model for acetaldehyde oxidation, in a continuously stirred tank reactor. The characteristics of the five dynamic regimes reported in the literature were numerically explored herein, specifically: (I) low-temperature steady state, (II) oscillatory two-stage ignitions, (III) complex oscillations, (IV) oscillatory cool flames, and (V) high-temperature steady state. Regimes were noted with new dynamic characteristics, which had not previously been reported. Additionally, bifurcations around the bistable and the birhythmic regimes were examined in detail.The sensitivity analysis polynomial approximation method revealed the significance of the kinetic parameters on the system's dynamics. Furthermore, the sequences of the sensitivity coefficients for the five dynamic regimes were reported. The step which initiates oxidation controls the ignition oscillation's dynamics, while the low-temperature branching and high-temperature termination steps control the cool flame.     

基于神经网络和多模型的非线性自适应PID控制及应用

针对一类未知的单输入单输出离散非线性系统,提出了基于神经网络和多模型的非线性自适应PID控制方法。该方法由线性自适应PID控制器、神经网络非线性自适应PID控制器以及切换机构组成。采用线性自适应PID控制器可保证闭环系统所有信号有界;采用神经网络非线性自适应PID控制器可改善系统性能;通过引入合理的切换机制,能够在保证闭环系统稳定的同时,提高系统性能。理论分析表明,该方法能够保证闭环系统所有信号有界,如果适当地选择神经网络的结构和参数,系统的跟踪误差将收敛于任意给定的紧集。将所提出的方法应用于连续搅拌反应釜,仿真结果验证了所提出方法的有效性。由于该方法基于增量式数字PID控制器,在工业过程中有着广阔的应用前景。     

Experimental and theoretical investigation of parametric sensitivity and dynamics of a continuous stirred tank reactor for acid catalyzed hydrolysis of acetic anhydride

The continuous stirred tank reactor is a dynamic system exhibiting nonlinear behavior such as multiplicity and oscillations and, in certain range of operating conditions, may exhibit a parametric sensitivity where small changes in one or more of the input parameters lead to large changes in the output variable. In the present work, hydrolysis of acetic anhydride reaction system was used to demonstrate the existence of parametric sensitivity with respect to the input parameter, the cooling water flow rate. The applications of parametric sensitivity analysis were used for detection of parametric sensitivity in a continuous stirred tank reactor using catalyses hydrolysis of acetic anhydride reaction system. Also, theoretical investigation revealed that the effect of wall capacitance has definite influence on the dynamics of continuous stirred tank reactor. The continuous stirred tank reactor showed parametric sensitivity both in the regions of uniqueness and multiplicity, and a mathematical model was developed for the reactor. The numerically simulated results are in satisfactory agreement with the experimental data.     

An Approach for Achieving Unstable Convergence for Non‐Isothermal CSTRs

The nonlinearity introduced by the temperature variation in the non‐isothermal continuous stirred tank reactor (CSTR) exhibits concentration multiplicity for certain parameter ranges. The dynamics of reactor temperature under these conditions would be very difficult to observe and maintain. In this work, a novel algorithm is proposed to stabilize the system by designing a cascade of CSTRs that are capable of achieving this inaccessible steady state. Optimization of reactors parameters is performed in an iterative manner to achieve this solution. For a first‐order reaction rate, this method was successful in achieving the inaccessible steady state temperature of 312.5 K using three CSTRs cascades. The suggested algorithm is presented both graphically as well as using computational optimization techniques. The transient simulation studies using the above three CSTRs showed that the unstable steady state is achieved. The newly designed cascade meets the design criteria and achieves the locally unstable steady state temperature to a high degree of accuracy.     

Modeling the continuous melt transesterification of bisphenol-A and diphenyl carbonate in a continuous stirred tank reactor

A model of continuous melt transesterification of bisphenol-A and diphenyl carbonate in a continuous stirred tank reactor is developed using phase equilibria assumption and the method of molecular weight moments. The model equations can be simplified into a polynomial system that has 17 equations and 17 unknowns. Solution of the polynomial system gives out almost every aspects of the continuous transesterification process. Molecular weight and polydispersity index, end group ratio of hydroxyl to phenyl carbonate, contents of molecular species, and lost diphenyl carbonate fractions are studied in different operation parameters.     

Removal of oxytetracycline (OTC) in a synthetic pharmaceutical wastewater by sequential anaerobic multichamber bed reactor (AMCBR)/completely stirred tank reactor (CSTR) system: biodegradation and inhibition kinetics

BACKGROUND: The antibiotics in industrial and munipical wastewaters could not be removed effectively in conventional anaerobic and aerobic biological treatment plants. Few studies have been performed to investigate the biodegradation and inhibition kinetics of oxytetracycline (OTC) on methanogens and total volatile fatty acids (TVFA). RESULTS: A high rate anaerobic multichamber bed reactor (AMCBR) was effective in removing the molasses‐chemical oxygen demand (COD), and the OTC antibiotic with yields as high as 96% at an influent OTC loading rate of 133.33 gOTC m^?3 day^?1 at a hydraulic retention time (HRT) of 2.25 days. Increasing the OTC loading rates from 22.22 gOTC m^?3 day^?1 to 133.33 gOTC m^?3 day^?1 improved both hydrolysis and specific utilization of molasses‐COD. The inhibition constants of TVFA (K_I?TVFA?meth) and OTC (K_I?OTC?meth) on methanogens decreased at OTC loadings > 133.33 gOTC m^?3 day^?1. The direct effect of OTC loadings > 133.3 gOTC m^?3 day^?1 on acidogens and methanogens was evaluated using the Haldane inhibition kinetic. CONCLUSION: OTC antibiotic was effectively removed in a sequential AMCBR/completely stirred tank reactor (CSTR). The Haldane inhibition constant (K_ID) decreased significantly at high OTC loads indicating the increase in toxicity. Copyright © 2012 Society of Chemical Industry     

Identification of LPV Models with Non-uniformly Spaced Operating Points by Using Asymmetric Gaussian Weights

In this paper, asymmetric Gaussian weighting functions are introduced for the identification of linear parameter varying systems by utilizing an input-output multi-model structure. It is not required to select operating points with uniform spacing andmore flexibility is achieved. To verify the effectiveness of the proposed approach, severalweighting functions, including linear, Gaussian and asymmetric Gaussianweighting functions, are evaluated and compared. It is demonstrated through simulations with a continuous stirred tank reactor model that the proposed approach provides more satisfactory approximation.     

Design and testing of continuous acid-catalyzed esterification reactor for high free fatty acid mixed crude palm oil

Using acid-catalyzed esterification, a continuous reactor, containing four separate continuous stirred tank reactors (CSTR's), was designed and used to reduce the free fatty acid (FFA) content of mixed crude palm oil (MCPO). A six-blade disk turbine and four baffles were installed in each of the four reactors to enhance mixing. The complete reactor was tested using response surface methodology (RSM). A 5-level, 4-factor, central composite design (CCD) was employed to optimize the four important reaction variables (methanol/oil ratio; sulfuric acid/oil ratio; speed of the stirrer; and residence time) to reduce the FFA content of the MCPO to less than 1 wt.% of oil. Multiple regression analysis was used to derive a polynomial equation to predict the FFA content of the product. This was then used to indicate optimal conditions for reducing the FFA in mixed crude palm oil to less than 1 wt.%.     

Multi-objective nonlinear model predictive control through switching cost functions and its applications to chemical processes

This paper proposes a switching multi-objective model predictive control (MOMPC) algorithm for constrained nonlinear continuous-time process systems. Different cost functions to be minimized inMPC are switched to satisfy different performance criteria imposed at different sampling times. In order to ensure recursive feasibility of the switching MOMPC and stability of the resulted closed-loop system, the dual-mode control method is used to design the switching MOMPC controller. In this method, a local control law with some free-parameters is constructed using the control Lyapunov function technique to enlarge the terminal state set of MOMPC. The correction termis computed if the states are out of the terminal set and the free-parameters of the local control laware computed if the states are in the terminal set. The recursive feasibility of the MOMPC and stability of the resulted closed-loop system are established in the presence of constraints and arbitrary switches between cost functions. Finally, implementation of the switching MOMPC controller is demonstrated with a chemical process example for the continuous stirred tank reactor.     

Experimentelle und theoretische Betrachtungen der Methanol- und direkten DME-Synthese im Labor- und Technikums-Maßstab

Engineering of strongly exothermic heterogeneously catalyzed reactions to industrial size is challenging. Synthesis of methanol and direct dimethyl ether synthesis serve as example for such type of reactions and related experimental results are described. Results from laboratory as well as technical scale are provided. The experiments show the variation of two main operational parameters: reaction temperature and CO₂ content at reactor inlet.     

Balanced multiple weighted linear discriminant analysis and its application to visual process monitoring

Visual process monitoring is important in complex chemical processes. To address the high state separation of industrial data, we propose a new criterion for feature extraction called balanced multiple weighted linear discriminant analysis(BMWLDA). Then, we combine BMWLDA with self-organizing map(SOM) for visual monitoring of industrial operation processes. BMWLDA can extract the discriminative feature vectors from the original industrial data and maximally separate industrial operation states in the space spanned by these discriminative feature vectors. When the discriminative feature vectors are used as the input to SOM, the training result of SOM can differentiate industrial operation states clearly.This function improves the performance of visual monitoring. Continuous stirred tank reactor is used to verify that the class separation performance of BMWLDA is more effective than that of traditional linear discriminant analysis, approximate pairwise accuracy criterion, max–min distance analysis, maximum margin criterion, and local Fisher discriminant analysis. In addition, the method that combines BMWLDA with SOM can effectively perform visual process monitoring in real time.     

CFD simulations of two stirred tank reactors with stationary catalytic basket

Among the different systems used for laboratory kinetic investigation, stationary catalytic basket stirred tank reactors (SCBSTRs) allow one to study triphasic reactions involving shaped catalyst with large size. The hydrodynamics of these complex reactors is not well known and has been studied experimentally in only a few cases. Despite the difference in the design of two commercial SCBSTRs reported in these works, the local measurements of the liquid-solid mass transfer coefficient inside the catalytic basket revealed the same velocity profile. The aim of the present work is therefore to investigate more accurately the hydrodynamics of the two reactors by means of CFD in order to compare the effect of the blade/baffle hydrodynamic interaction on the flow pattern. Owing to the geometrical complexity of the reactors, the hydrodynamic investigation is based on the k-ε model and the Brinkman-Forsheimer equations. The agreement at the local level with the experimental data (PIV and mass transfer measurements) validates this preliminary work performed with the standard values of the parameters present in the turbulent model and the Brinkman-Forsheimer equations. The simulations reveal in both reactors a ring-shaped vortex around the impeller in the agitation region. The high axial location of its centre induces a reverse flow at the tips of the basket. Owing to the fluid friction in the porous medium, the azimuthal flow in the core region is transformed into a radial flow in the basket where the flow decreases abruptly. Vertical vortices are located at the blade tips and at the downstream face of the baffles or they are located in the basket on both sides of the baffles, depending on the design and the location of the baffles. At the inner radius interface of the basket, the vertical blade impeller induces a rather homogeneous velocity profile, but the pitched blade impeller imposes a high velocity at the plane of symmetry. Therefore the simulations demonstrate that two different local velocity patterns and two different porous media may induce the same mass transfer properties.     

MODELING AND OPTIMIZATION OF MEMBRANE CHEMICAL CLEANING BY ARTIFICIAL NEURAL NETWORK,FUZZY LOGIC,AND GENETIC ALGORITHM

Robust artificial neural network (ANN) and fuzzy logic (FL) models were derived for chemical cleaning of microfiltration membranes fouled by milk under a wide range of operating conditions. The accuracies of the models were compared with multiple linear regressions (MLR). The developed models are useful tools for predicting the performance of chemical cleaning. The effects of different operating conditions on cleaning performance were elucidated using the ANN developed model. Moreover, optimum cleaning condition was determined by genetic algorithm and ANN model. The current research demonstrated that fuzzy logic and an artificial neural network can quantitatively capture cumulative effects of a range of operating conditions on flux recovery and resistance removal during a cleaning process.     

Evaluation of the potential of periodically operated reactors based on the second order frequency response function

A new, fast and easy method for analysing the potential for improving reactor performance by replacing steady state by forced periodic operation is presented. The method is based on Volterra series, generalized Fourier transform and the concept of higher-order frequency response functions (FRFs). The second order frequency response function, which corresponds to the dominant term of the non-periodic (DC) component, G₂(ω, −ω), is mainly responsible for the average performance of the periodically operated processes. Based on that, in order to evaluate the potential of periodic reactor operation, it is enough to derive and analyze G₂(ω, −ω). The sign of this function defines the sign of the DC component and reveals whether a performance improvement by cycling is possible compared to optimal steady state process. The method is used to analyze the periodic performance of a continuous stirred tank reactor (CSTR), a plug flow tubular reactor (PFTR) and a dispersive flow tubular reactor (DFTR), after introducing periodic changes of the input concentrations. A homogeneous, n-th order reaction is studied under isothermal conditions.     

Einfluss der Reaktorkonfiguration auf die Enantioselektivität einer kinetischen Racematspaltung

The optical purity of a product at the reactor outlet depends not only on the enantioselectivity of the catalyst, but also on the reactor configuration. Different reactor configurations are compared with respect to the enantiomeric excess (ee) at a respective conversion that can be achieved in a kinetic resolution of a racemate. For batch, fed‐batch and plug flow reactors enantioselectivities (E value) of 35 are sufficient to achieve high enantiomeric excess. For a continuously operated stirred tank reactor high ee values are only obtained for E values higher than 190.