Reactive distillation has enormous potential for the economical synthesis of tertiary ethers. Methyl tert-butyl ether (MTBE) has been commercially produced with this technology since the early 1980s and it appears that the process also has application for Ethyl tert-butyl ether (ETBE) and other ethers. However, the combination of reaction and distillation in a single unit operation produces a process complexity that inhibits expeditious design and tight control, and presents a technology risk for potential developers. This particularly applies to hybrid reactive distillation where both reactive and non-reactive column sections are employed.The steady state simulation of a series of reactive distillation columns and processes for the production of ETBE and MTBE illuminated a number of important issues related to the optimal design techniques. Many of these issues are peculiar to reactive distillation and would not reasonably be anticipated without a priori knowledge of the phenomena involved. For example, the addition of theoretical equilibrium stages and an increase in the reflux ratio do not always have a directionally equivalent effect. The trade-off between energy consumption and capital cost which is the basis for most distillation designs cannot always be applied to reactive distillation. Importantly, the use of standard modelling techniques for equilibrium processes was also validated for reactive distillation design.The use of residue curve diagrams and reactive residue curve diagrams for the design of reactive distillation processes was investigated and shown to provide useful information regarding the feasibility of reaction-separations. Combined with simulation tools (e.g. Pro/II and SpeedUp), these techniques form the basis of a proposed design strategy for hybrid reactive distillation. It is important to apply these design tools appropriately and to ++ / select the correct process for a given application. The optimal design must also consider economics and the relative values of products, reactants and energy. These issues were studied with respect to ETBE production for gasoline oxygenation.The complexity of hybrid reactive distillation not only presents design challenges but potentially makes the process more difficult to control. Dynamic simulations of ETBE and MTBE reactive distillation processes were used to explore some unusual dynamic phenomena and to elucidate the process non-linearity and bidirectionality of reactive distillation. The presence of multiple steady states for some reactive distillation columns has been documented previously but the analysis of this behaviour has been incomplete and somewhat flawed. It was shown that the distinction between molar inputs and physically realisable mass or volumetric inputs is crucial and that multiplicity could be present in one case and not in the other. Multiplicity that is only observed with molar inputs (relatively common) was termed pseudo-multiplicity. Pseudo-multiplicity has few implications for the operation and control of practical reactive distillation processes although most literature examples of multiple steady states fall into this category. Four distinct causes of output multiplicity were identified including one new cause, reaction hysteresis, which is only applicable to hybrid reactive distillation. It was shown, using dynamic simulations, that transitions between parallel steady states are possible for a range of physically realisable and practical disturbances. This contrasts with other work in the area, which examines only unrealisable events and control schemes.An extensive analysis of reactive distillation control was also undertaken with respect to ETBE and MTBE hybrid columns. Manual (open-loop) control was shown to be impractical due to ++ / the need to sustain the operating conditions at close to the optimal values in order to produce acceptable process performance. One-point composition control was found to be relatively easy to implement and effective with either an energy-balance or a material-balance control scheme provided only one steady state was present. Where multiple steady states exist, there are restrictions on the feasible control structures due to unavoidable instability in the inventory controllers. For example, if multiple steady states exist for the one value of the reboiler duty, only the bottoms product draw rate can be used to control the reboiler sump level. Thus, a material-balance control structure that uses the reboiler duty to control the sump level cannot be implemented in practice. Two-point control was also investigated and found to effectively prevent transitions between parallel steady states. Although more complex and difficult to implement than one-point control, a two-point scheme could be used successfully to control both the product composition and the reactant conversion and this could be desirable in some cases.A reactive distillation pilot plant was designed and operated for ETBE synthesis from ethanol and a locally available refinery hydrocarbon stream. The design of the pilot plant was based on simulation studies and the objective of operating in the industrially significant ranges of product purity and isobutene conversion. A fully automatic control system was designed and installed on the pilot plant to permit precise control of the manipulated variables and the framework to implement a range of control structures and schemes.Keywords: reactive distillation; process simulation; process design; process control; dynamic simulation; multiplicity; bidirectionality; distillation control; inferential control; pilot plant design and operation.

This dissertation presents an analysis of two aspects of the chromatographic separation process known as Simulated Moving Bed (SMB) chromatography. The first aspect is system design, and the second is improving computer simulations to generate heuristics for choosing operational modes. For the past 15-20 years, there has been a surge of interest in the use of Simulated Moving Bed systems for the chromatographic separation of chemicals¹. A wide variety of methods, nomenclatures, and conventions have been adopted over the years²⁻⁴, as teams from different backgrounds adopt and improve on the SMB technology. This work presents a unifying discussion of the two major design methods, Triangle Theory and Standing Wave Design, used in the SMB field. We provide the complete computer code required to execute both design methods. A sample problem is worked, which demonstrates the novelty and ease of use that such tools provide. Mathematica was chosen for the implementation of these design methods, because of its strong symbolic analysis capabilities, and simplicity of creating interfaces for new users. We present derivations of the classic Langmuir results in Mathematica, and proceed to extend those implementations. When analytic solutions are impossible, we use Mathematica's numerical methods. This work also develops a distributed computing tool known as ChromRunner which allows large numbers of detailed numerical simulations to be run simultaneously. The motivations and benefits of this approach are discussed alongside implementation details. We apply the distributed computing system to two separate SMB separations in order to optimize them, as well as determine heuristics governing their operational modes. We wrote ChromRunner in C#, and took advantage of Visual Studio's Entity Framework to create the database backend. The user interface for this software was created using Microsoft's "Windows Presentation Foundation" (WPF) technologies. / Ph. D.

This thesis details various techniques and considerations for the purification of complex biomacromolecules.   Initially an α-mannosidase from babaco fruit was purified using anion exchange-, lectin affinity- and size exclusion chromatography.  The enzyme was approximately 260-280 kDa in size with an apparent an unusual octagonal stoichiometry and displayed properties similar to other known plant α-mannosidases.   Mucins were fractionated by ion exchange and size exclusion chromatography to assess the properties that govern the mucin surface coating interactions in biomaterial research.  Commercially available mucins, of bovine and porcine origin, as wells as crude human mucin were tested. All showed to consist of a population of molecules which differ in size, charge and composition.   The third part of the thesis concerns different aspects of plasmid DNA purification processes. A two-step method for analysis of plasmid DNA consisting of size exclusion followed by thiophilic adsorption chromatography was evaluated. It allowed determination of the supercoiled plasmid DNA concentration in all process steps without requirement for extensive sample preparation. This method was shown to be fully comparable in terms of accuracy to capillary gel electrophoresis, considered as the industry standard. Purification of plasmid DNA generally involves bacterial cell alkaline lysis, which creates a solution with flocculate material which needs to be removed prior to further processing. The addition of ammonium hydrogen carbonate to the suspension was evaluated to clarify the solution. The released carbon dioxide and ammonium lifts the flocculate to the surface and allows draining of a clear solution. The method is fully scalable, does not affect the plasmid DNA quality and requires no special equipment. Thiophilic adsorption chromatography was evaluated for simplification of an existing commercial large scale purification process and was shown to increase both product purity and yields of several tested plasmids. Also, implementation of this step significantly reduced overall production process time.

Much research in the area of process integration has focused on steady-state processes. However, there are many process units that are inherently unsteady-state or perform best when operated in an unsteady-state manner. Unsteady-state units are vital to chemical processes but are unable to be included in current process optimization methods. Previous methods to optimize processes containing unsteady-state units place restrictions or constraints on their use. This optimization still does not give the best system design because the solution found will only be the best out of the available options which likely excludes the true optimal design. To remedy this, a methodology was created to incorporate unsteady-state process units into process optimization analysis. This methodology is as general as possible. Unlike many existing unsteadystate optimization methods, it determines all three main components of process design: the network configuration, sizes of units, and operation schedule. This generality ensures that the truly optimal process design will be found. Three problems were solved to illustrate the solution methodology. First, a general mass exchange network was optimized. The optimization formulation resulted in a mixed-integer nonlinear program, and linearization techniques were used to find the global solution. A property interception network was also optimized, the first work done using property integration for systems with unsteady-state behavior. Finally, an industrial semi-batch water purification system was optimized. This problem showed how process integration could be used to optimize a hybrid system and gain insights into the process under many different operating conditions.

Biodiesel has achieved worldwide recognition for many years due to its renewability, lubricating property, and environmental benefits. The abstract represents a summary of all the chapters of the thesis. The research chapters are defined as research phases in the abstract. The thesis starts with an introduction followed by literature review. In the literature review, all the necessary data were collected reviewing the literature. Then an artificial neural network model (ANN) was built based on the published research data to capture the general trends or to make predictions. Both catalyst properties and reaction conditions were trended and predicted using the network model. The review study revealed that esterification and transesterification required catalysts with slightly different properties. In the first phase of the study, biodiesel production using 12-Tungstophosphric acid (TPA) supported on SBA-15 as a solid acid catalyst was studied. In this phase of the study, a large number of 0-35% TPA on SBA-15 catalysts were synthesized by impregnation method and the effects of various operating conditions such as–catalyst wt.% and methanol to oil molar ratio on the transesterification of model feedstock Triolein were studied. A 25% TPA loading was found to be the optimum. A 4.15 wt.% catalysts (based on Triolein) and 39:1 methanol to Triolein molar ratio was found to be the optimum reaction parameter combination, when the reaction temperature was kept fixed at 200C, stirring speed of 600 rpm and 10 h reaction time. The biodiesel yield obtained using this condition was 97.2%. In the second phase of the study, a 12-Tungstophosphoric acid (TPA) was supported by using organic functional group (i.e. 3-aminopropyltriethoxysilane (APTES)) and was incorporated into the SBA-15 structure. A 45 wt.% TPA incorporated SBA-15 produced an ester with biodiesel yield of 97.3 wt.%, when 3 wt.% catalyst (based on the green seed canola (GSC) oil) and 25.8:1 methanol GSC oil molar ratio were used at 2000C for reaction time of 6.2 h. In the third phase, process sustainability (i.e. process economics, process safety, energy efficiency, environmental impact assessment) studies were conducted based on the results obtained in phase three. Based on the study, it was concluded that heterogeneous acid catalyzed process had higher profitability as compared to the homogeneous acid catalyzed process. Additionally, it was obtained that heterogeneous acid catalyzed process was safe, more energy efficient and more environment friendly than homogenous process. In the fourth phase, the catalytic activity of Tungsten oxide (WO3) and TPA supported (by impregnation) on H-Y, H-β and H-ZSM-5 zeolite catalysts were tested for biodiesel production from Green Seed Canola (GSC) oil. In this phase of the study, TPA/H-Y and TPA/H- zeolite were proved to be effective catalysts for esterification and transesterification, respectively. A 55% TPA/H- showed balanced catalytic activity for both esterification and transesterification. It yielded 99.3 wt.% ester, when 3.3 wt.% catalyst (based on GSC oil) and 21.3:1 methanol to GSC oil molar ratio were used at 200C, reaction pressure of 4.14 MPa and reaction time of 6.5 h. Additionally, this catalyst (55% TPA/H-) was experimented for etherification of pure glycerol, and maximum conversion of glycerol (100%) was achieved in 5 h at 120C, 1 MPa, 1:5 molar ratio (glycerol: (tert-butanol) TBA), 2.5% (w/v) catalyst loading. Later, these conditions were used to produce glycerol ether successfully from the glycerol derived after transesterification of green seed canola oil. A mixture of GSC derived biodiesel, and glycerol ether was defined as biofuels. In the fifth phase, catalytic activity of H-Y supported TPA (using different impregnation methods) was studied in details further for esterification of free fatty acid (FFA) of GSC oil. From the optimization study, 97.2% FFA (present in the GSC oil) conversion was achieved using 13.3 wt.% catalyst, 26:1 methanol to FFA molar ratio at 120°C reaction temperature and 7.5 h of reaction time.In the sixth- and final phase, techno-economic and ecological impacts were compared between biodiesel and combined biofuel production processes based on the results obtained in phase four. Based on the study, it was concluded that, biodiesel production process had higher profitability as compared to that for combined biofuel production process. Additionally, biodiesel production process was more energy efficient than combined biofuel production process. However, combined biofuel production process was more environment-friendly as compared to that for biodiesel production process.

This work introduces a systematic seawater reverse osmosis (SWRO) membrane network synthesis approach, based on the coordinated use of process superstructure representations and global optimization. The approach makes use of superstructure formulations that are capable of extracting a globally optimal design as a performance target, by taking into consideration desired process conditions and constraints that are typically associated with reverse osmosis systems. Thermodynamic insights are employed to develop lean network representations so that any underperforming solutions can be eliminated a priori. This essentially results in considerable improvement of the overall search speed, compared to previously reported attempts. In addition, the approach enables the extraction of structurally different design alternatives. In doing so, distinct membrane network design classes were established by partitioning the search space, based on network size and connectivity. As a result, corresponding lean superstructures were then systematically generated, which capture all structural and operational variants within each design class. The overall purpose is thus to enable the extraction of multiple distinct optimal designs, through global optimization. This mainly helps provide design engineers with a better understanding of the design space and trade-offs between performance and complexity. The approach is illustrated by means of a numerical example, and the results obtained were compared to previously related work. As anticipated, the proposed approach consistently delivered the globally optimal solutions, as well as alternative efficient design candidates attributed to different design classes, with reduced CPU times. This work further capitalizes on the developed representation, by accounting for detailed water quality information, within the SWRO desalination network optimization problem. The superstructures were modified to incorporate models that capture the performance of common membrane elements, as predicted by commercially available simulator tools, e.g. ROSA (Dow) and IMSDesign (Hydranautics). These models allow tracing of individual components throughout the system. Design decisions that are supported by superstructure optimization include network size and connectivity, flow rates, pressures, and post treatment requirements. Moreover, a detailed economic assessment capturing all the significant capital and operating costs associated in SWRO processes, including intake, pre and post treatment has also been accounted for. These modifications were then illustrated using a case study involving four seawater qualities, with salinities ranging from 35 to 45 ppt. The results highlight the dependency of optimal designs on the feed water quality involved, as well as on specified permeate requirements.

A gestão de projetos de design é uma ferramenta eficiente que pode auxiliar a geração e implantação de uma cultura empresarial afetando positivamente a imagem da organização. Porém, para a empresa poder gerir design, esta deve capacitar-se nesta área. Deve incorporar os sistemas de apoio especializados existentes no mercado e conseguir com que estes aportes maximizem seus rendimentos. Neste sentido, observa-se a relevância da Gestão de Design como diferencial para as organizações no cenário mundial. Porém, no âmbito regional não são encontrados muitos estudos desenvolvidos na área. Sob estas condições se faz necessário um estudo aprofundado sobre as características do processo de Gestão de Design realizada por prestadores de serviços em design de Porto Alegre/RS. Com isso, o estudo busca contribuir para que os processos da gestão de design de empresas gaúchas sejam identificados e aprimorados. Neste contexto, esta dissertação tem por objetivo caracterizar como os escritórios e prestadores de serviços em design de Porto Alegre/RS desenvolvem seu processo de Gestão de Design. Para esta caracterização, foi necessária uma revisão e fundamentação bibliográfica, além de entrevistas com especialistas da área. Optouse por utilizar para a realização da pesquisa, a verificação das práticas das áreas de conhecimento da gestão de projetos do PMBOK (2004). Através do estudo, conseguiu-se caracterizar como os escritórios e prestadores de serviços em design de Porto Alegre/RS desenvolvem seu processo de Gestão de Design. Como resultados, verificou-se que todos os escritórios estudados possuem e utilizam processos distintos, nem sempre formalizados, para a realização de sua Gestão de Design. Verificou-se a aplicação das etapas do plano de gerenciamento de projetos do PMBOK (2004), em todos os escritórios estudados. / Design Project Management is an efficient tool for creating and implementing an entrepreneurial culture. But for the company to manage design projects, there must be a training program to its employees in this area. The company must incorporate new systems available in the market in order to be able to maximize its revenues. Therefore, the importance of design management for organizations all over the world is remarkable. However, in the Southern Brazil regional scenario, there are not many studies developed in the Design Project Management area. This dissertation aims at analysing the characteristics of the design management process developed by design companies in Porto Alegre, Rio Grande do Sul, Brazil. Besides, the study also intends to offer theoretical support for the identification and improvement of local design companies’ design project management process. It was based on a background research in design management area and interview with experts. In addition, the areas of PMBOK (2004) were analyzed, in order to discuss the way local design companies develop their design management process. The study results point out how design companies in Porto Alegre/RS develop their design management process. All design companies studied have different management processes, but they were not always formally established.

A gestão de projetos de design é uma ferramenta eficiente que pode auxiliar a geração e implantação de uma cultura empresarial afetando positivamente a imagem da organização. Porém, para a empresa poder gerir design, esta deve capacitar-se nesta área. Deve incorporar os sistemas de apoio especializados existentes no mercado e conseguir com que estes aportes maximizem seus rendimentos. Neste sentido, observa-se a relevância da Gestão de Design como diferencial para as organizações no cenário mundial. Porém, no âmbito regional não são encontrados muitos estudos desenvolvidos na área. Sob estas condições se faz necessário um estudo aprofundado sobre as características do processo de Gestão de Design realizada por prestadores de serviços em design de Porto Alegre/RS. Com isso, o estudo busca contribuir para que os processos da gestão de design de empresas gaúchas sejam identificados e aprimorados. Neste contexto, esta dissertação tem por objetivo caracterizar como os escritórios e prestadores de serviços em design de Porto Alegre/RS desenvolvem seu processo de Gestão de Design. Para esta caracterização, foi necessária uma revisão e fundamentação bibliográfica, além de entrevistas com especialistas da área. Optouse por utilizar para a realização da pesquisa, a verificação das práticas das áreas de conhecimento da gestão de projetos do PMBOK (2004). Através do estudo, conseguiu-se caracterizar como os escritórios e prestadores de serviços em design de Porto Alegre/RS desenvolvem seu processo de Gestão de Design. Como resultados, verificou-se que todos os escritórios estudados possuem e utilizam processos distintos, nem sempre formalizados, para a realização de sua Gestão de Design. Verificou-se a aplicação das etapas do plano de gerenciamento de projetos do PMBOK (2004), em todos os escritórios estudados. / Design Project Management is an efficient tool for creating and implementing an entrepreneurial culture. But for the company to manage design projects, there must be a training program to its employees in this area. The company must incorporate new systems available in the market in order to be able to maximize its revenues. Therefore, the importance of design management for organizations all over the world is remarkable. However, in the Southern Brazil regional scenario, there are not many studies developed in the Design Project Management area. This dissertation aims at analysing the characteristics of the design management process developed by design companies in Porto Alegre, Rio Grande do Sul, Brazil. Besides, the study also intends to offer theoretical support for the identification and improvement of local design companies’ design project management process. It was based on a background research in design management area and interview with experts. In addition, the areas of PMBOK (2004) were analyzed, in order to discuss the way local design companies develop their design management process. The study results point out how design companies in Porto Alegre/RS develop their design management process. All design companies studied have different management processes, but they were not always formally established.

A gestão de projetos de design é uma ferramenta eficiente que pode auxiliar a geração e implantação de uma cultura empresarial afetando positivamente a imagem da organização. Porém, para a empresa poder gerir design, esta deve capacitar-se nesta área. Deve incorporar os sistemas de apoio especializados existentes no mercado e conseguir com que estes aportes maximizem seus rendimentos. Neste sentido, observa-se a relevância da Gestão de Design como diferencial para as organizações no cenário mundial. Porém, no âmbito regional não são encontrados muitos estudos desenvolvidos na área. Sob estas condições se faz necessário um estudo aprofundado sobre as características do processo de Gestão de Design realizada por prestadores de serviços em design de Porto Alegre/RS. Com isso, o estudo busca contribuir para que os processos da gestão de design de empresas gaúchas sejam identificados e aprimorados. Neste contexto, esta dissertação tem por objetivo caracterizar como os escritórios e prestadores de serviços em design de Porto Alegre/RS desenvolvem seu processo de Gestão de Design. Para esta caracterização, foi necessária uma revisão e fundamentação bibliográfica, além de entrevistas com especialistas da área. Optouse por utilizar para a realização da pesquisa, a verificação das práticas das áreas de conhecimento da gestão de projetos do PMBOK (2004). Através do estudo, conseguiu-se caracterizar como os escritórios e prestadores de serviços em design de Porto Alegre/RS desenvolvem seu processo de Gestão de Design. Como resultados, verificou-se que todos os escritórios estudados possuem e utilizam processos distintos, nem sempre formalizados, para a realização de sua Gestão de Design. Verificou-se a aplicação das etapas do plano de gerenciamento de projetos do PMBOK (2004), em todos os escritórios estudados. / Design Project Management is an efficient tool for creating and implementing an entrepreneurial culture. But for the company to manage design projects, there must be a training program to its employees in this area. The company must incorporate new systems available in the market in order to be able to maximize its revenues. Therefore, the importance of design management for organizations all over the world is remarkable. However, in the Southern Brazil regional scenario, there are not many studies developed in the Design Project Management area. This dissertation aims at analysing the characteristics of the design management process developed by design companies in Porto Alegre, Rio Grande do Sul, Brazil. Besides, the study also intends to offer theoretical support for the identification and improvement of local design companies’ design project management process. It was based on a background research in design management area and interview with experts. In addition, the areas of PMBOK (2004) were analyzed, in order to discuss the way local design companies develop their design management process. The study results point out how design companies in Porto Alegre/RS develop their design management process. All design companies studied have different management processes, but they were not always formally established.

BillerudKorsnäs is a manufacturer of fiber-based cartonboard and liquid packaging board. Microbial growth occurs at several steps in cartonboard production due to favourable environment and the good access to nutrients from the raw material, and additives such as starch. Vegetative bacteria are usually not harmful in the production and die in the hot drying end of the cartonboard machine. The most abundant microflora at paper- and cartonboard factories consists largely of sporeforming microorganisms from the genera Bacillus and Paenibacillus. The endospores are highly resistant and can stay in the final end product, which is undesirable. Levels of endospores from these species at BillerudKorsnäs production unit KM5 are usually low, but an occational increase can be seen when a new cartonboard product, KW1 is produced. Today, the method used for controlling the microbiology is by adding biocides to broke towers. This has shown to be both expensive and non-effective at KM5. A new method is needed for controlling the microbiology at KM5 that is more effective, costbeneficial and environmental friendly.The aim of this project was to test a hypothesis for spore formation at a paper board factory in lab-scale experiments. A suggestion of a technical change in the process would be made that could minimize spore formation and the use of biocides at KM5. A model organism Bacillus licheniformis (E-022052) was used to study effects of environmental conditions on spore formation. Experiments were also performed in controlled bioreactor trials, where methods to minimize spore formation were tested.The experiments showed that nutrient deficiency of a primary carbon source was the major reason for spore formation and should be avoided at KM5. Further, the experiments showed that oxygen limitation significantly decreases the endospore formation.The conclusion reached, was that spore formation could be minimized by a feed addition of glucose to Broke tower 1 during the few days production of KW1. A second alternative includes using a feed of concentrated pulp that could be used to minimize spore formation without the use of biocides and without the need for rebuilding of the mill.