Control of integrated unit operations

As a thermal separation method, distillation is one of the most important technologies in the chemical industry. Given its importance, it is no surprise that increasing efforts have been made in reducing its energy inefficiencies. A great deal of research is focused in the design and optimization of the Divided-Wall Column. Its applications are still reduced due to distrust of its controllability. Previous references studied the decentralized control of DWC but still few papers deal about Model Predictive Control. In this work we present a decentralized control of both a DWC column along with its equivalent MPC schema.

Optimal synthesis of thermally coupled distillation sequences using a novel MILP approach

This paper introduces a novel MILP approach for the design of distillation columns sequences of zeotropic mixtures that explicitly include from conventional to fully thermally coupled sequences and divided wall columns with a single wall. The model is based on the use of two superstructure levels. In the upper level a superstructure that includes all the basic sequences of separation tasks is postulated. The lower level is an extended tree that explicitly includes different thermal states and compositions of the feed to a given separation task. In that way, it is possible to a priori optimize all the possible separation tasks involved in the superstructure. A set of logical relationships relates the feasible sequences with the optimized tasks in the extended tree resulting in a MILP to select the optimal sequence. The performance of the model in terms of robustness and computational time is illustrated with several examples.

Estudo do processo de absorção e dessorção de CO2 na solução aquosa de metildietanolamina e piperazina.

Estudou-se o processo de absorção e dessorção de CO2 em solução aquosa da mistura de metildietanolamina (MDEA) e piperazina (PZ). Os ensaios de absorção foram realizados numa coluna de parede molhada com promotor de película, e, os ensaios de dessorção num sistema de semibatelada, ambos em escala de laboratório. Os testes experimentais de absorção foram realizados a 298 K e pressão atmosférica, com vazão de gás (CO2 e ar atmosférico) de 2,2.10-4 m3 s-1 e as seguintes vazões de líquido: 1,0.10-6; 1,3.10-6 e 1,7.10-6 m3 s-1. O sistema de absorção foi caracterizado através da determinação da área interfacial, a, o coeficiente volumétrico de transferência de massa, kGa, e o coeficiente volumétrico global médio de transferência de massa, KGa. No caso dos ensaios de dessorção, estes foram realizados nas temperaturas de 353, 363 e 368 K, onde empregou-se uma solução carbonatada de 10% PZ-20% MDEA e uma corrente de ar atmosférico nas vazões de 1,1.10-5 m3 s-1 e 2,7.10-5 m3 s-1. Este sistema foi caracterizado através da determinação do coeficiente volumétrico global de transferência de massa, KLa. Os resultados experimentais da área interfacial mostram que este é função da vazão do líquido, sugerindo uma maior área de irrigação como o aumento desta, onde teve-se uma maior área de transferência de massa. O resultado do parâmetro, KGa, indica uma dependência da vazão de líquido, a qual está associada à variação da área interfacial e à dependência do parâmetro KG com o perfil das concentrações da MDEA e PZ ao longo da coluna. A partir da teoria do duplo filme e pelo conhecimento dos parâmetros KGa, a e kGa, estimou-se um parâmetro cinético-difusivo associado à fase líquida, (( ) ) . Os resultados experimentais mostram que esse parâmetro varia pouco com a vazão de líquido, indicando tratar-se de um processo independente da hidrodinâmica do líquido, característico de sistemas com reação rápida. A concentração das aminas e carbamatos, nos ensaios de absorção e dessorção, foi determinada através dos modelos de calibração obtidas pela técnica de espectroscopia no infravermelho. Nos ensaios de absorção, foram observados que a concentração de PZ teve uma variação considerável (4 a 5% massa massa-1), entanto que a de MDEA variou pouco (0,3 a 0,5% massa massa-1), sugerindo que o processo de absorção de CO2 na mistura MDEA-PZ é controlado principalmente pela PZ, e supõe-se que a MDEA tem um papel de receptor de prótons procedentes da reação entre a PZ e o CO2. Nos ensaios de dessorção, observou-se que esse processo é afetado pela temperatura, sendo que, em temperaturas perto da ebulição (372 K), a taxa de dessorção de CO2 é maior do que em temperaturas menores, em certa forma é devido à dependência da velocidade de reação química com a temperatura. Os resultados do parâmetro KLa indicam que este diminui em função da concentração de carbamato de PZ (por exemplo, na temperatura de 368 K, de 7,5.10-4 a 1,0.10-4 s-1), devido a que este componente é decomposto em altas temperaturas gerando o CO2 e as aminas, sugerindo uma diminuição na velocidade de dessorção de CO2. Assim também, os resultados experimentais do parâmetro KLa indicam que este aumenta ligeiramente com a vazão do gás.

A Sequential Algorithm for the Rigorous Design of Thermally Coupled Distillation Sequences

A sequential design method is presented for the design of thermally coupled distillation sequences. The algorithm starts by selecting a set of sequences in the space of basic configurations in which the internal structure of condensers and reboilers is explicitly taken into account and extended with the possibility of including divided wall columns (DWC). This first stage is based on separation tasks (except by the DWCs) and therefore it does not provide an actual sequence of columns. In the second stage the best arrangement in N-1 actual columns is performed taking into account operability and mechanical constraints. Finally, for a set of candidate sequences the algorithm try to reduce the number of total columns by considering Kaibel columns, elimination of transfer blocks or columns with vertical partitions. An example illustrate the different steps of the sequential algorithm.

CO2 absorption into aqueous amine blended solutions containing monoethanolamine (MEA), N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) for post-combustion capture processes

Presently monoethanolamine (MEA) remains the industrial standard solvent for CO2 capture processes. Operating issues relating to corrosion and degradation of MEA at high temperatures and concentrations, and in the presence of oxygen, in a traditional PCC process, have introduced the requisite for higher quality and costly stainless steels in the construction of capture equipment and the use of oxygen scavengers and corrosion inhibitors. While capture processes employing MEA have improved significantly in recent times there is a continued attraction towards alternative solvents systems which offer even more improvements. This movement includes aqueous amine blends which are gaining momentum as new generation solvents for CO2 capture processes. Given the exhaustive array of amines available to date endless opportunities exist to tune and tailor a solvent to deliver specific performance and physical properties in line with a desired capture process. The current work is focussed on the rationalisation of CO2 absorption behaviour in a series of aqueous amine blends incorporating monoethanolamine, N,N-dimethylethanolamine (DMEA), N,N-diethylethanolamine (DEEA) and 2-amino-2-methyl-1-propanol (AMP) as solvent components. Mass transfer/kinetic measurements have been performed using a wetted wall column (WWC) contactor at 40°C for a series of blends in which the blend properties including amine concentration, blend ratio, and CO2 loadings from 0.0-0.4 (moles CO2/total moles amine) were systematically varied and assessed. Equilibrium CO2 solubility in each of the blends has been estimated using a software tool developed in Matlab for the prediction of vapour liquid equilibrium using a combination of the known chemical equilibrium reactions and constants for the individual amine components which have been combined into a blend.From the CO2 mass transfer data the largest absorption rates were observed in blends containing 3M MEA/3M Am2 while the selection of the Am2 component had only a marginal impact on mass transfer rates. Overall, CO2 mass transfer in the fastest blends containing 3M MEA/3M Am2 was found to be only slightly lower than a 5M MEA solution at similar temperatures and CO2 loadings. In terms of equilibrium behaviour a slight decrease in the absorption capacity (moles CO2/mole amine) with increasing Am2 concentration in the blends with MEA was observed while cyclic capacity followed the opposite trend. Significant increases in cyclic capacity (26-111%) were observed in all blends when compared to MEA solutions at similar temperatures and total amine concentrations. In view of the reasonable compromise between CO2 absorption rate and capacity a blend containing 3M MEA and 3M AMP as blend components would represent a reasonable alternative in replacement of 5M MEA as a standalone solvent.

Structural behaviour and design of cold-formed steel wall systems under fire conditions

In recent times, light gauge steel framed (LSF) structures, such as cold-formed steel wall systems, are increasingly used, but without a full understanding of their fire performance. Traditionally the fire resistance rating of these load-bearing LSF wall systems is based on approximate prescriptive methods developed based on limited fire tests. Very often they are limited to standard wall configurations used by the industry. Increased fire rating is provided simply by adding more plasterboards to these walls. This is not an acceptable situation as it not only inhibits innovation and structural and cost efficiencies but also casts doubt over the fire safety of these wall systems. Hence a detailed fire research study into the performance of LSF wall systems was undertaken using full scale fire tests and extensive numerical studies. A new composite wall panel developed at QUT was also considered in this study, where the insulation was used externally between the plasterboards on both sides of the steel wall frame instead of locating it in the cavity. Three full scale fire tests of LSF wall systems built using the new composite panel system were undertaken at a higher load ratio using a gas furnace designed to deliver heat in accordance with the standard time temperature curve in AS 1530.4 (SA, 2005). Fire tests included the measurements of load-deformation characteristics of LSF walls until failure as well as associated time-temperature measurements across the thickness and along the length of all the specimens. Tests of LSF walls under axial compression load have shown the improvement to their fire performance and fire resistance rating when the new composite panel was used. Hence this research recommends the use of the new composite panel system for cold-formed LSF walls. The numerical study was undertaken using a finite element program ABAQUS. The finite element analyses were conducted under both steady state and transient state conditions using the measured hot and cold flange temperature distributions from the fire tests. The elevated temperature reduction factors for mechanical properties were based on the equations proposed by Dolamune Kankanamge and Mahendran (2011). These finite element models were first validated by comparing their results with experimental test results from this study and Kolarkar (2010). The developed finite element models were able to predict the failure times within 5 minutes. The validated model was then used in a detailed numerical study into the strength of cold-formed thin-walled steel channels used in both the conventional and the new composite panel systems to increase the understanding of their behaviour under nonuniform elevated temperature conditions and to develop fire design rules. The measured time-temperature distributions obtained from the fire tests were used. Since the fire tests showed that the plasterboards provided sufficient lateral restraint until the failure of LSF wall panels, this assumption was also used in the analyses and was further validated by comparison with experimental results. Hence in this study of LSF wall studs, only the flexural buckling about the major axis and local buckling were considered. A new fire design method was proposed using AS/NZS 4600 (SA, 2005), NAS (AISI, 2007) and Eurocode 3 Part 1.3 (ECS, 2006). The importance of considering thermal bowing, magnified thermal bowing and neutral axis shift in the fire design was also investigated. A spread sheet based design tool was developed based on the above design codes to predict the failure load ratio versus time and temperature for varying LSF wall configurations including insulations. Idealised time-temperature profiles were developed based on the measured temperature values of the studs. This was used in a detailed numerical study to fully understand the structural behaviour of LSF wall panels. Appropriate equations were proposed to find the critical temperatures for different composite panels, varying in steel thickness, steel grade and screw spacing for any load ratio. Hence useful and simple design rules were proposed based on the current cold-formed steel structures and fire design standards, and their accuracy and advantages were discussed. The results were also used to validate the fire design rules developed based on AS/NZS 4600 (SA, 2005) and Eurocode Part 1.3 (ECS, 2006). This demonstrated the significant improvements to the design method when compared to the currently used prescriptive design methods for LSF wall systems under fire conditions. In summary, this research has developed comprehensive experimental and numerical thermal and structural performance data for both the conventional and the proposed new load bearing LSF wall systems under standard fire conditions. Finite element models were developed to predict the failure times of LSF walls accurately. Idealized hot flange temperature profiles were developed for non-insulated, cavity and externally insulated load bearing wall systems. Suitable fire design rules and spread sheet based design tools were developed based on the existing standards to predict the ultimate failure load, failure times and failure temperatures of LSF wall studs. Simplified equations were proposed to find the critical temperatures for varying wall panel configurations and load ratios. The results from this research are useful to both structural and fire engineers and researchers. Most importantly, this research has significantly improved the knowledge and understanding of cold-formed LSF loadbearing walls under standard fire conditions.

Design of LSF wall studs under fire conditions

Cold-formed steel lipped channels are commonly used in LSF wall construction as load bearing studs with plasterboards on both sides. Under fire conditions, cold-formed thin-walled steel sections heat up quickly resulting in fast reduction in their strength and stiffness. Usually the LSF wall panels are subjected to fire from one side which will cause thermal bowing, neutral axis shift and magnification effects due to the development of non-uniform temperature distributions across the stud. This will induce an additional bending moment in the stud and hence the studs in LSF wall panels should be designed as a beam column considering both the applied axial compression load and the additional bending moment. Traditionally the fire resistance rating of these wall panels is based on approximate prescriptive methods. Very often they are limited to standard wall configurations used by the industry. Therefore a detailed research study is needed to develop fire design rules to predict the failure load and hence the failure time of LSF wall panels subject to non-uniform temperature distributions. This paper presents the details of an investigation to develop suitable fire design rules for LSF wall studs under non-uniform elevated temperature distributions. Applications of the previously developed fire design rules based on AISI design manual and Eurocode 3 Parts 1.2 and 1.3 to LSF wall studs were investigated in detail and new simplified fire design rules based on AS/NZS 4600 and Eurocode 3 Part 1.3 were proposed in the current study with suitable allowances for the interaction effects of compression and bending actions. The accuracy of the proposed fire design rules was verified by using the results from full scale fire tests and extensive numerical studies.

Matter and movement: Expression as topological continuity or a return to Butades' wall

This paper aims to address the ways in which drawing can be understood as the becoming-expressive of materials, site, and body, over time. The discussion pivots around a series of studies that replace linear or causal relationships – in history, drawing and expression – with topological movement. My approach is largely through a speculative case study. In a rereading of the familiar Butades myth, I examine how a shadow tracing can variously be taken as the first mimetic art with its origins in the urge to “capture”, and, antithetically, as the originary expressive folding of matter, site and body. The paper is divided into five sections. The first presents the Butades myth, identifying the representational problem that lies at the roots of its traditional telling. The next three sections outline a series of topologies that facilitate a discussion of the Butades myth from historical, disciplinary, and expressive perspectives. The final section aims to show the relevance of this discussion to a contemporary drawing practice, using my own drawing research as a case study. The field of inquiry is that of representational critique. The fold, an image associated with a topological geometry, replaces the relational or signifying disjuncture of representational structures, and suggests a becoming- expressive of subject and object, form and matter.

The stress in a slowly sheared granular column

We report measurements of the wall stress in a granular material sheared in a cylindrical Couette cell, as a function of the distance from the free surface. Our results shows that when the material is static, all components of the stress saturate to constant values within a short distance from the free surface, in conformity with earlier experiments and theoretical predictions. When the material is sheared by rotating the inner cylinder at a constant rate, the stresses are remarkably altered. The radial normal stress does not saturate, and increases even more rapidly with depth than the linear hydrostatic pressure profile. The axial shear stress changes sign on shearing, and its magnitude increases with depth. These results are discussed in the context of the predictions of the classical and Cosserat plasticity theories.

Virus-sized colloid transport in a single pore: Model development and sensitivity analysis

A mathematical model is developed to simulate the transport and deposition of virus-sized colloids in a cylindrical pore throat considering various processes such as advection, diffusion, colloid-collector surface interactions and hydrodynamic wall effects. The pore space is divided into three different regions, namely, bulk, diffusion and potential regions, based on the dominant processes acting in each of these regions. In the bulk region, colloid transport is governed by advection and diffusion whereas in the diffusion region, colloid mobility due to diffusion is retarded by hydrodynamic wall effects. Colloid-collector interaction forces dominate the transport in the potential region where colloid deposition occurs. The governing equations are non-dimensionalized and solved numerically. A sensitivity analysis indicates that the virus-sized colloid transport and deposition is significantly affected by various pore-scale parameters such as the surface potentials on colloid and collector, ionic strength of the solution, flow velocity, pore size and colloid size. The adsorbed concentration and hence, the favorability of the surface for adsorption increases with: (i) decreasing magnitude and ratio of surface potentials on colloid and collector, (ii) increasing ionic strength and (iii) increasing pore radius. The adsorbed concentration increases with increasing Pe, reaching a maximum value at Pe = 0.1 and then decreases thereafter. Also, the colloid size significantly affects particle deposition with the adsorbed concentration increasing with increasing particle radius, reaching a maximum value at a particle radius of 100 nm and then decreasing with increasing radius. System hydrodynamics is found to have a greater effect on larger particles than on smaller ones. The secondary minimum contribution to particle deposition has been found to increase as the favorability of the surface for adsorption decreases. The sensitivity of the model to a given parameter will be high if the conditions are favorable for adsorption. The results agree qualitatively with the column-scale experimental observations available in the literature. The current model forms the building block in upscaling colloid transport from pore scale to Darcy scale using Pore-Network Modeling. (C) 2014 Elsevier By. All rights reserved.

Theory of the positive column of a gas discharge

An attempt is made to provide a theoretical explanation of the effect of the positive column on the voltage-current characteristic of a glow or an arc discharge. Such theories have been developed before, and all are based on balancing the production and loss of charged particles and accounting for the energy supplied to the plasma by the applied electric field. Differences among the theories arise from the approximations and omissions made in selecting processes that affect the particle and energy balances. This work is primarily concerned with the deviation from the ambipolar description of the positive column caused by space charge, electron-ion volume recombination, and temperature inhomogeneities.

The presentation is divided into three parts, the first of which involved the derivation of the final macroscopic equations from kinetic theory. The final equations are obtained by taking the first three moments of the Boltzmann equation for each of the three species in the plasma. Although the method used and the equations obtained are not novel, the derivation is carried out in detail in order to appraise the validity of numerous approximations and to justify the use of data from other sources. The equations are applied to a molecular hydrogen discharge contained between parallel walls. The applied electric field is parallel to the walls, and the dependent variables—electron and ion flux to the walls, electron and ion densities, transverse electric field, and gas temperature—vary only in the direction perpendicular to the walls. The mathematical description is given by a sixth-order nonlinear two-point boundary value problem which contains the applied field as a parameter. The amount of neutral gas and its temperature at the walls are held fixed, and the relation between the applied field and the electron density at the center of the discharge is obtained in the process of solving the problem. This relation corresponds to that between current and voltage and is used to interpret the effect of space charge, recombination, and temperature inhomogeneities on the voltage-current characteristic of the discharge.

The complete solution of the equations is impractical both numerically and analytically, and in Part II the gas temperature is assumed uniform so as to focus on the combined effects of space charge and recombination. The terms representing these effects are treated as perturbations to equations that would otherwise describe the ambipolar situation. However, the term representing space charge is not negligible in a thin boundary layer or sheath near the walls, and consequently the perturbation problem is singular. Separate solutions must be obtained in the sheath and in the main region of the discharge, and the relation between the electron density and the applied field is not determined until these solutions are matched.

In Part III the electron and ion densities are assumed equal, and the complicated space-charge calculation is thereby replaced by the ambipolar description. Recombination and temperature inhomogeneities are both important at high values of the electron density. However, the formulation of the problem permits a comparison of the relative effects, and temperature inhomogeneities are shown to be important at lower values of the electron density than recombination. The equations are solved by a direct numerical integration and by treating the term representing temperature inhomogeneities as a perturbation.

The conclusions reached in the study are primarily concerned with the association of the relation between electron density and axial field with the voltage-current characteristic. It is known that the effect of space charge can account for the subnormal glow discharge and that the normal glow corresponds to a close approach to an ambipolar situation. The effect of temperature inhomogeneities helps explain the decreasing characteristic of the arc, and the effect of recombination is not expected to appear except at very high electron densities.

DIRECT-INJECTION OF URINE AND DETERMINATION OF ACETAMINOPHEN BY MICELLAR LIQUID-CHROMATOGRAPHY WITH A WALL-JET CELL CARBON-FIBER MICROELECTRODE

A wall-jet cell/carbon fibre microelectrode detector was designed and used for the micellar liquid chromatographic assay of acetaminophen. The separations were carried out in an analytical column packed with C-18 stationary phase and the mobile phase was

AMPEROMETRIC DETECTION AT A CARBON-FIBER ARRAY RING GLASSY-CARBON DISK ELECTRODE IN A WALL-JET CELL

A wall-jet cell incorporating a carbon fibre array ring/glassy-carbon disk electrode has been constructed, and characterized by the cyclic voltammetry and flow-injection techniques. The ring (composed of several microdisks) and glassy-carbon disk electrode, can be used separately for different purposes, e.g., detection in solution without a supporting electrolyte, collection/shielding detection with dual-electrode and voltammetric/amperometric detection with series dual-electrode. The electrode shows better collection and shielding effects than usual ring-disk electrode in quiescent solution and the series dual-electrode in a thin-layer flow-through cell. The detection limit at the ring electrode is comparable with that at a conventional-size electrode, and has been used in the mobile phase without a supporting electrolyte, proving to be a promising detector for normal-phase liquid chromatography.

Effects of Nd : YAG laser irradiation on root canal dentin wall: A scanning electron microscopic study

Objective: the purpose of this study was to evaluate, by scanning electron microscopy (SEM), the effects of Nd:YAG laser irradiation applied perpendicular or parallel to the root canal dentin wall. Methods: Thirty human teeth were divided into two groups: Group A (20 roots), laser application with circular movements, parallel to the dentin root surface; and Group B (10 roots), roots cut longitudinally and laser applied perpendicular to the root surface. Group A was subdivided into A1 (10 roots), laser application with 100 mJ, 15 Hz and 1.5 W; and A2 (10 roots) with 160 mJ, 15 Hz, and 2.4 W. Group B was subdivided into B1 (10 hemisections) and B2 (10 hemi-sections) with parameters similar to A I and A2. Four applications of 7-sec duration were performed, with a total exposure of 28 sec. SEM evaluations were made in the cervical, middle, and apical thirds, with 500X and 2000X magnifications. Morphological changes scores were attributed, and the results were submitted to Kruskal Wallis statistical test (5%). Results: Significant statistical differences were found between groups A and B (p = 0.001). In groups A1 and A2, few areas of dentin melting were observed. In groups B1 and B2, areas of melting dentin covering dentin surface were observed. Conclusions: It was concluded that intracanal laser application with circular movements (parallel to the surface) produces limited morphological changes in root canal dentin wall.

Effects of copper vapor laser radiation on the root canal wall of human teeth: A scanning electron microscope study

Objective: The aim of this study is to analyze the effects of copper vapor laser radiation on the radicular wall of human teeth. Materials and Methods: Immediately after the crowns of 10 human uniradicular teeth were cut along the cement-enamel junction, a chemical-surgical preparation of the radicular canals was completed. Then the roots were longitudinally sectioned to allow for irradiation of the surfaces of the dentin walls of the root canals. The hemi-roots were separated into two groups: one (control) with five hemi-roots that were not irradiated, and another (experimental) with 15 hemi-roots divided into three subgroups that were submitted to the following exposure times: 0.02,0.05, and 0.1 s. A copper vapor laser (510.6 nm) with a total average power of 6.5 W in green emission, frequency of 16.000 Hz, and pulse duration of 30 ns was used. Results: The results obtained by scanning electron microscope analysis showed the appearance of a cavity in the region of laser beam impact, with melting, recrystallization, and cracking on the edges of the dentin of the cavity due to heat diffusion. Conclusions: We determined that the copper vapor laser produces significant morphologic changes in the radicular wall of human teeth when using the parameters in this study. However, further research should be done to establish parameters that are compatible with dental structure in order to eliminate thermal damages. © Mary Ann Liebert, Inc.