Robust stabilization of a chemical reactor

Robust static output feedback control was applied to a continuous stirred tank reactor with parametric uncertainty and multiple steady states in which exothermic reaction takes place. The problem of robust controller design was converted to a solution of linear matrix inequalities and a computationally simple non-iterative algorithm is presented. The possibility of using robust static output feedback for stabilization of reactors with uncertainty and comparison of robust P and PI controllers with an optimal controller is demonstrated by simulation results.     

Robust model-based predictive control of exothermic chemical reactor

A case study of the robust model-based predictive control (MPC) of an exothermic continuous stirred tank reactor (CSTR) with uncertain parameters is presented. Three robust MPC approaches are considered and the simulation results are compared in terms of quality of control performance and total consumption of coolant. The results reveal the main benefits of the considered approaches and confirm that the robust MPC can bring about a reduction in consumption of the coolant.     

Anion exchange kinetics of nanodimensional layered metal hydroxides: use of isoconversional analysis

Anion exchange reactions of nanodimensional layered metal hydroxide compounds are utilized to create materials with targeted physical and chemical properties and also as a means for controlled release of intercalated anions. The kinetics of this important class of reaction are generally characterized by model-based approaches. In this work, a different approach based on isothermal, isoconversional analysis was utilized to determine effective activation energies with respect to extent of reaction. Two different layered metal hydroxide materials were chosen for reaction with chloride anions, using a temperature range of 30-60 °C. The concentrations of anions released into solution and the changes in polycrystalline solid phases were evaluated using model-based (Avrami-Erofe'ev nucleation-growth model) and model-free (integral isoconversional) methods. The results demonstrate the utility of the isoconversional approach for identifying when fitting to a single model is not appropriate, particularly for characterizing the temperature dependence of the reaction kinetics.     

Mathematical Modelling Method Application for Optimisation of Catalytic Reforming process

The application of mathematical modelling method monitoring of catalytic reforming unit of Komsomolsk oil-refinery is proposed. The mathematical model-based system “Catalyst's Control” which takes into account both the physical and chemical mechanisms of hydrocarbon mixture conversion reaction as well as the catalyst deactivation was used for catalytic reforming installation monitoring. The models created can be used for optimization and prediction of operating parameters (octane number, reactors outlet temperature and yield) of the reforming process. It is shown, that the work on the optimal activity allows increasing product output with a constant level of production costs, and get the information about Pt-Re catalyst work efficiency.     

A sensitivity analysis of the smith predictor controller

The sensitivity of the Smith predictor controller to variations in system parameters is analyzed. The parameters considered are system gain, time constant, and delay or dead time. Both simulated and experimental results are discussed. First- and second-order models are studied. For the first-order model, a proportional plus integral control is used with the Smith predictor. A proportional plus integral plus derivative control is used with the Smith predictor for the second-order system. The controller is implemented digitally. An application of the Smith predictor with a model of the system obtained by a nonlinear least-squares parameter identification method is demonstrated on an experimental system.     

Configurable 3D-Printed millifluidic and microfluidic 'lab on a chip' reactionware devices

We utilise 3D design and 3D printing techniques to fabricate a number of miniaturised fluidic 'reactionware' devices for chemical syntheses in just a few hours, using inexpensive materials producing reliable and robust reactors. Both two and three inlet reactors could be assembled, as well as one-inlet devices with reactant 'silos' allowing the introduction of reactants during the fabrication process of the device. To demonstrate the utility and versatility of these devices organic (reductive amination and alkylation reactions), inorganic (large polyoxometalate synthesis) and materials (gold nanoparticle synthesis) processes were efficiently carried out in the printed devices.     

Behavior of thorium,zirconium, and vanadium as chemical modifiers in the determination of arsenic by electrothermal atomization atomic absorption spectrometry

The comparative effect of thorium, zirconium and vanadium used as chemical modifiers in wall and platform atomization of arsenic using two sample introduction modes (aerosol vs. liquid drop) was studied. The effect of proton concentration (as hydrochloric acid and nitric acid) on the behavior of these modifiers was also tested. A beneficial effect on the stabilization of arsenic from all the chemical modifiers was essentially derived in the presence of nitric acid mainly for the aerosol introduction mode. Nonetheless, the highest sensitivity and the best stabilization of arsenic were obtained using zirconium and thorium as a chemical modifier, because pyrolysis temperatures as high as ∼1500°C can be used. The mechanistic action of the chemical modifiers used is also studied, resulting in the formation of a mixture of oxides stabilized at high temperatures.     

Data Reconciliation and Control in Styrene-Butadiene Emulsion Polymerizations

Summary: A nonlinear model-based predictive control (NLMPC) method was developed using a First Principles model of an emulsion copolymerization of carboxylated styrene butadiene rubber (XSBR). Copolymer composition, conversion and average molecular weights of the copolymer were chosen as the controlled variables due to their influence on the final product properties and quality. These properties, however, are rarely measured in-line due to the operational difficulties associated with their measurement. For this reason a soft-sensor using reaction calorimetry techniques was developed and used to infer reaction conditions, rates, species concentrations and polymer properties in a industrial scale emulsion polymerization reactor.     

Neural network model predictive control of a styrene polymerization plant: online testing using an electronic worksheet

The batch styrene polymerization process presents transient and nonlinear temperature behavior. In this work, manual control and open loop experiments were carried out in order to build a process knowledge database. Initially, a cascade feedback control loop was implemented by manipulating the thyristor unit of the electrical heater in the thermal fluid tank. Aiming at the MPC development, algebraic equations of a neural network and its adjusted parameters were implemented in an electronic worksheet. Every five seconds, the worksheet was updated with measurements (reactor temperature, thermal fluid temperature and thyristor position) by means of the OLE for the Process Control protocol (OPC). The one-step-ahead temperature prediction was then employed in the objective function of the worksheet solver which used Visual Basic Applications programming. The manipulated variable action was then calculated and sent to the process. A hybrid controller (cascade feedback and MPC) outperformed the pure strategies since the time-integral performance indexes, IAE and ITAE, were reduced by around 22 % and 32 %, respectively. Methodology for the Model Predictive Control presented in this study was considered feasible because the solver of Microsoft Office Excel (2007) is very friendly, easy to understand and ready to implement using VBA.     

Cadmium concentration stabilization in a continuous sulfate reducing bioreactor via sulfide concentration control

Cadmium concentration stabilization in a single input-single output continuous bioreactor via sulfide concentration, as the controlled and measured output state variable, was assumed. For the above process, a novel kinetic model of the sulfate-reducing process for cadmium removal was proposed and experimentally confirmed. This model has been extended to continuous operation, which is employed as a virtual plant to enable the implementation of the proposed controller. The considered nonlinear control law contains a sigmoid feedback of the given control error in order to regulate the sulfide concentration at the maximum value indirectly leading to cadmium concentrations meeting the environmental regulations. A theoretical frame of the closed-loop stability of the bioreactor is provided under the assumption that bounded trajectories occur in the bioreactor. Finally, numerical experiments proved satisfactory performance of the proposed methodology in comparison with the standard sliding-mode and linear PI controllers.     

Model based robustness analysis of an ion-exchange chromatography step

Process development, optimization and robustness analysis for chromatographic separation are often entirely based on experimental work and generic knowledge. This paper describes a model-based approach that can be used to gain process knowledge and assist in the robustness analysis of an ion-exchange chromatography step using a model-based approach. A kinetic dispersive model, where the steric mass action model accounts for the adsorption is used to describe column performance. Model calibration is based solely on gradient elution experiments at different gradients, flow rates, pH and column loads. The position and shape of the peaks provide enough information to calibrate the model and thus single-component experiments can be avoided. The model is calibrated to the experiments and the confidence intervals for the estimated parameters are used to account for the model error throughout the analysis. The model is used to predict the result of a robustness analysis conducted as a factorial experiment and to design a robust pooling approach. The confidence intervals are used in a "worst case" approach where the parameters for the components are set at the edge of their confidence intervals to create a worst case for the removal of impurities at each point in the factorial experiment. The pooling limit was changed to ensure product quality at every point in the factorial analysis. The predicted purities and yields were compared to the experimental results to ensure that the prediction intervals cover the experimental results.     

Valence stabilization of polyvalent ions during gamma irradiation of their aqueous solutions by sacrificial protection. III-Valence stabilization of Fe(II) ions by organic additives

Valence stabilization of polyvalent ions in gamma irradiated aqueous solutions is sometimes necessary in some chemical operations. In previous publications, valence stabilization of some polyvalent ions in solution upon gamma irradiation was achieved by using inorganic additives capable of interacting with the oxidizing or reducing species formed during water radiolysis. The results showed that the nature and duration of valence stabilization of Fe(II) depend on the concentration of the inorganic additives used. In the present work, a series of some organic additives has been used to investigate their capability in inducing valence stabilization of polyvalent iron ions, taken as an indicator, in aqueous acidic solutions when subjected to extended gamma irradiation. The results showed that the efficiency of valence stabilization depends on the amount and chemical structure of the organic additive used.     

An improved visual tracking method in scanning electron microscope

Since their invention, nanomanipulation systems in scanning electron microscopes (SEMs) have provided researchers with an increasing ability to interact with objects at the nanoscale. However, most nanomanipulators that are capable of generating nanometer displacement operate in an open-loop without suitable feedback mechanisms. In this article, a robust and effective tracking framework for visual servoing applications is presented inside an SEM to achieve more precise tracking manipulation and measurement. A subpixel template matching tracking algorithm based on contour models in the SEM has been developed to improve the tracking accuracy. A feed-forward controller is integrated into the control system to improve the response time. Experimental results demonstrate that a subpixel tracking accuracy is realized. Furthermore, the robustness against clutter can be achieved even in a challenging tracking environment.     

Optimizing control of simulated moving bed separations of mixtures subject to the generalized Langmuir isotherm

Simulated moving bed (SMB) is a cost-efficient separation technique that offers high productivity and low solvent consumption. SMB has gained importance in the pharmaceutical and fine chemical industry to perform complex separation tasks. However, an open and challenging problem is the optimal, robust operation of the SMB process. We have developed a control scheme that integrates the optimization and control of the SMB unit. A significant feature of the controller is that only minimal information of the system has to be provided, i.e. the linear adsorption behavior of the mixture to be separated and the average void fraction of the columns. Therefore, a full characterization of the adsorption behavior of the mixture and the columns is no longer required. In this ‘cycle to cycle’ control scheme, the measurements, optimization and control actions are performed once in every cycle. This paper presents simulation results of the control scheme applied to the separation of binary mixtures characterized by generalized Langmuir isotherms. The results are presented and analyzed in the frame of the triangle theory that has been recently extended to encompass these types of isotherms. Besides, online optimum performance of the SMB unit is compared with off-line optimization carried out using genetic algorithm. The results show that the controller fulfills the product and process specifications while operating the SMB unit optimally, regardless of the different types of Langmuir isotherms that the systems exhibit.     

Enzyme immobilization strategies for the design of robust and efficient biocatalysts

Different strategies for the preparation of efficient and robust immobilized biocatalysts are here reviewed. Different physico-chemical approaches are discussed.i.- The stabilization of enzyme by any kind of immobilization on pre-existing porous supports.ii.- The stabilization of enzymes by multipoint covalent attachment on support surfaces.iii.- Additional stabilization of immobilized-stabilized enzyme by physical or chemical modification with polymers.These three strategies can be easily developed when enzymes are immobilized in pre-existing porous supports. In addition to that, these immobilized-stabilized derivatives are optimal to develop enzyme reaction engineering and reactor engineering. Stabilizations ranging between 1000 and 100,000 folds regarding diluted soluble enzymes are here reported.     

非线性化学反应动力学*

本文从实验和理论的角度综述非线性化学反应动力学。介绍了若干非线性化学反应动力学现象如时钟反应、反馈、混合振荡、化学混沌及反应扩散图案等; 对时空序列、功率谱、Lyapunov 指数、吸引子及其维数、Poincare 截面及分叉理论等常用于分析非线性动力学特征的手段作了介绍; 探讨了对非线性化学反应的实验装置、测试方法、机理和模型研究的方法; 简要回顾了非线性化学反应动力学的发展历史, 并展望了其发展趋势。     

The preparation of a series of nitrostilbene ester compounds using micro reactor technology

The synthesis of stilbene esters using Wittig chemistry has been used to illustrate the generic diversity micro reactors offer in terms of chemical control and rapid method development. The micro reactor consisted of a 'T' design based on channel geometries 200 microns wide and 100 microns deep, etched into borosilicate glass and sealed with a borosilicate top plate using a thermal bonding technique. The movement of the reagent and products was achieved using electroosmotic flow (EOF), assisted by the incorporation of micro porous silica frits within the micro-channels to allow accurate solution control. To optimise the operating conditions methyl 4-formylbenzoate, premixed with sodium methoxide, was reacted with 2-nitrobenzyl-triphenylphosphonium bromide in dry degassed MeOH using flow conditions for both reagents of 0.40 microL min-1 for 20 min. A product yield of 70% (2:1 reaction stoichiometry with the aldehyde in excess) was obtained representing a 10% increase compared with the traditional batch synthesis. To demonstrate the capability of micro reactors to perform atom efficient synthesis a series of experiments based on an injection methodology (optimised to 30 s) were performed in the micro reactor at 1:1 stoichiometry resulting in a yield of 59%. Finally, the capability of micro reactors to perform a series of analogue reactions was investigated. The yields for a further three aldehydes indicated that the technology will be suitable for the development of automated device to support the generation of combinatorial libraries and rapid high throughput synthetic methods.     

Two-step upflow anaerobic sludge bed system for sewage treatment under subtropical conditions with posttreatment in waste stabilization ponds

A pilot-scale sewage treatment system consisting of two upflow anaerobic sludge bed (UASB) reactors followed by five waste stabilization ponds (WSPs) in series was studied under subtropical conditions. The first UASB reactor started up in only 1 mo (stable operation, high chemical oxygen demand [COD] removal efficiency, low volatile fatty acids concentration in the effluent, alkalinity ratio above 0.7, biogas production above 0.1 Nm3/kg of CODremoved). Removal efficiencies up to 90% were obtained in the anaerobic steps at a hydraulic retention time of 6 + 4 h (80% removal in the first step). Fecal coliform removal in the whole system was 99.9999% (99.94% in anaerobic steps and 99.98% in WSPs). COD balances over UASB reactors are provided. A minimum set of data necessary to build COD balances is proposed. Intermittent sludge washout was detected in the reactors with the COD balances. Sludge washout from single-step UASB reactors should be monitored and minimized in order to ensure constant compliance with discharge standards, especially when no posttreatment is provided. The system combined high COD and fecal coliform removal efficiency with an extremely low effluent concentration, complying with discharge standards, and making it an attractive option for sewage treatment in subtropical regions.     

Electrochemical properties of interface formed by interlaced layers of DNA- and lysozyme-coated single-walled carbon nanotubes

Multifunctional coatings were produced by the layer by layer assembly of single-walled carbon nanotubes (SWNT) dispersed in DNA and lysozyme (LSZ) on an insulating glass substrate. The electrochemical properties of these mechanically robust biocoatings were characterized for the first time using scanning electrochemical microscopy (SECM) and impedance spectroscopy (IS). SECM surface analysis demonstrated an increase in tip current with a corresponding increase in the number of oppositely polarized interlaced layers, indicating that subsequent layers were not electrically insulated from each other and a direct correlation exists between SECM feedback response and the number of layers. The rate of charge transport was also dependent on the chemical composition/polarity of the outermost surface layer. Coatings terminating in SWNT-DNA resulted in more positive feedback than those terminating in SWNT-LSZ. IS analysis demonstrated that the SWNT-DNA had a low charge transfer resistance in comparison with SWNT-LSZ, which is consistent with the results obtained by SECM. These results enable enhanced fundamental understanding and prediction of the electrical properties of SWNT-biopolymer layers with controlled interlaced polarities and orientation. Furthermore, these finding highlight the potential for SWNT-biopolymers in electronic and sensing applications.