Kinetic modeling studies of heterogeneously catalyzed biodiesel synthesis reactions

The heterogeneously catalyzed transesterification reaction for the production of biodiesel from triglycerides was investigated for reaction mechanism and kinetic constants. Three elementary reaction mechanisms Eley-Rideal (ER), Langmuir-Hinshelwood-Hougen-Watson (LHHW), and Hattori with assumptions, such as quasi-steady-state conditions for the surface species and methanol adsorption, and surface reactions as the rate-determining steps were applied to predict the catalyst surface coverage and the bulk concentration using a multiscale simulation framework. The rate expression based on methanol adsorption as the rate limiting in LHHW elementary mechanism has been found to be statistically the most reliable representation of the experimental data using hydrotalcite catalyst with different formulations. © 2011 American Chemical Society.

Implications of Recent Trends in Telecommunications on Modeling and Simulation for the Telecommunication Industry

With this paper we would like to trigger a discussion on future needs of modeling and simulation techniques and tools for the telecommunication industry. We claim that the telecommunication market has undergone severe changes that affect the need for and type of simulations in industrial research. We suggest some approaches how to address these new challenges. We believe that there is need for intensive research in the area.

Frontline employees' collaboration in industrial service innovation:routes of co-creation's effects on new service performance

From a Service-Dominant Logic (S-DL) perspective, employees constitute operant resources that firms can draw to enhance the outcomes of innovation efforts. While research acknowledges that frontline employees (FLEs) constitute, through service encounters, a key interface for the transfer of valuable external knowledge into the firm, the range of potential benefits derived from FLE-driven innovation deserves more investigation. Using a sample of knowledge intensive business services firms (KIBS), this study examines how the collaboration with FLEs along the new service development (NSD) process, namely FLE co-creation, impacts on service innovation performance following two routes of different effects. Partial least squares structural equation modeling (PLS-SEM) results indicate that FLE co-creation benefits the NS success among FLEs and firm’s customers, the constituents of the resources route. FLE co-creation also has a positive effect on the NSD speed, which in turn enhances the NS quality. NSD speed and NS quality integrate the operational route, which proves to be the most effective path to impact the NS market performance. Accordingly, KIBS managers must value their FLEs as essential partners to achieve successful innovation from an internal and external perspective, and develop the appropriate mechanisms to guarantee their effective involvement along the NSD process.

A framework for transforming, analyzing, and realizing software designs in unified modeling language

Unified Modeling Language (UML) is the most comprehensive and widely accepted object-oriented modeling language due to its multi-paradigm modeling capabilities and easy to use graphical notations, with strong international organizational support and industrial production quality tool support. However, there is a lack of precise definition of the semantics of individual UML notations as well as the relationships among multiple UML models, which often introduces incomplete and inconsistent problems for software designs in UML, especially for complex systems. Furthermore, there is a lack of methodologies to ensure a correct implementation from a given UML design. The purpose of this investigation is to verify and validate software designs in UML, and to provide dependability assurance for the realization of a UML design.^ In my research, an approach is proposed to transform UML diagrams into a semantic domain, which is a formal component-based framework. The framework I proposed consists of components and interactions through message passing, which are modeled by two-layer algebraic high-level nets and transformation rules respectively. In the transformation approach, class diagrams, state machine diagrams and activity diagrams are transformed into component models, and transformation rules are extracted from interaction diagrams. By applying transformation rules to component models, a (sub)system model of one or more scenarios can be constructed. Various techniques such as model checking, Petri net analysis techniques can be adopted to check if UML designs are complete or consistent. A new component called property parser was developed and merged into the tool SAM Parser, which realize (sub)system models automatically. The property parser generates and weaves runtime monitoring code into system implementations automatically for dependability assurance. The framework in the investigation is creative and flexible since it not only can be explored to verify and validate UML designs, but also provides an approach to build models for various scenarios. As a result of my research, several kinds of previous ignored behavioral inconsistencies can be detected.^

Integrated surface-ground water modeling in wetlands with improved methods to simulate vegetative resistance to flow

In topographically flat wetlands, where shallow water table and conductive soil may develop as a result of wet and dry seasons, the connection between surface water and groundwater is not only present, but perhaps the key factor dominating the magnitude and direction of water flux. Due to their complex characteristics, modeling waterflow through wetlands using more realistic process formulations (integrated surface-ground water and vegetative resistance) is an actual necessity. This dissertation focused on developing an integrated surface – subsurface hydrologic simulation numerical model by programming and testing the coupling of the USGS MODFLOW-2005 Groundwater Flow Process (GWF) package (USGS, 2005) with the 2D surface water routing model: FLO-2D (O’Brien et al., 1993). The coupling included the necessary procedures to numerically integrate and verify both models as a single computational software system that will heretofore be referred to as WHIMFLO-2D (Wetlands Hydrology Integrated Model). An improved physical formulation of flow resistance through vegetation in shallow waters based on the concept of drag force was also implemented for the simulations of floodplains, while the use of the classical methods (e.g., Manning, Chezy, Darcy-Weisbach) to calculate flow resistance has been maintained for the canals and deeper waters. A preliminary demonstration exercise WHIMFLO-2D in an existing field site was developed for the Loxahatchee Impoundment Landscape Assessment (LILA), an 80 acre area, located at the Arthur R. Marshall Loxahatchee National Wild Life Refuge in Boynton Beach, Florida. After applying a number of simplifying assumptions, results have illustrated the ability of the model to simulate the hydrology of a wetland. In this illustrative case, a comparison between measured and simulated stages level showed an average error of 0.31% with a maximum error of 2.8%. Comparison of measured and simulated groundwater head levels showed an average error of 0.18% with a maximum of 2.9%. The coupling of FLO-2D model with MODFLOW-2005 model and the incorporation of the dynamic effect of flow resistance due to vegetation performed in the new modeling tool WHIMFLO-2D is an important contribution to the field of numerical modeling of hydrologic flow in wetlands.

Flat-top supercontinuum and tunable femtosecond fiber laser sources at 1.9-2.5 μm

We report the high-energy flat-top supercontinuum covering the mid-infrared wavelength range of 1.9-2.5 μm as well as electronically tunable femtosecond pulses between 1.98-2.22 μm directly from the thulium-doped fiber laser amplifier. Comparison of experimental results with numerical simulations confirms that both sources employ the same nonlinear optical mechanism - Raman soliton frequency shift occurring inside the Tm-fiber amplifier. To illustrate that, we investigate two versions of the compact diode-pumped SESAM mode-locked femtosecond thulium-doped all-silica-fiber-based laser system providing either broadband supercontinuum or tunable Raman soliton output, depending on the parameters of the system. The first system operates in the Raman soliton regime providing femtosecond pulses tunable between 1.98-2.22 μm. Wide and continuous spectral tunability over 240 nm was realized by changing only the amplifier pump diode current. The second system generates high-energy supercontinuum with the superior spectral flatness of better than 1 dB covering the wavelength range of 1.9-2.5 μm, with the total output energy as high as 0.284 μJ, the average power of 2.1 W at 7.5 MHz repetition rate. We simulate the amplifier operation in the Raman soliton self-frequency shift regime and discuss the role of induced Raman scattering in supercontinuum formation inside the fiber amplifier. We compare this system with a more traditional 1.85-2.53 μm supercontinuum source in the external highly-nonlinear commercial chalcogenide fiber using the Raman soliton MOPA as an excitation source. The reported systems1 can be readily applied to a number of industrial applications in the mid-IR, including sensing, stand-off detection, medical surgery and fine material processing.

Enhancing non-refractory aerosol apportionment from an urban industrial site through receptor modelling of complete high time-resolution aerosol mass spectra

Receptor modelling was performed on quadrupole unit mass resolution aerosol mass spectrometer (Q-AMS) sub-micron particulate matter (PM) chemical speciation measurements from Windsor, Ontario, an industrial city situated across the Detroit River from Detroit, Michigan. Aerosol and trace gas measurements were collected on board Environment Canada’s CRUISER mobile laboratory. Positive matrix factorization (PMF) was performed on the AMS full particle-phase mass spectrum (PMFFull MS) encompassing both organic and inorganic components. This approach was compared to the more common method of analysing only the organic mass spectra (PMFOrg MS). PMF of the full mass spectrum revealed that variability in the non-refractory sub-micron aerosol concentration and composition was best explained by six factors: an amine-containing factor (Amine); an ammonium sulphate and oxygenated organic aerosol containing factor (Sulphate-OA); an ammonium nitrate and oxygenated organic aerosol containing factor (Nitrate-OA); an ammonium chloride containing factor (Chloride); a hydrocarbon like organic aerosol (HOA) factor; and a moderately oxygenated organic aerosol factor (OOA). PMF of the organic mass spectrum revealed three factors of similar composition to some of those revealed through PMFFull MS: Amine, HOA and OOA. Including both the inorganic and organic mass proved to be a beneficial approach to analysing the unit mass resolution AMS data for several reasons. First, it provided a method for potentially calculating more accurate sub-micron PM mass concentrations, particularly when unusual factors are present, in this case, an Amine factor. As this method does not rely on a priori knowledge of chemical species, it circumvents the need for any adjustments to the traditional AMS species fragmentation patterns to account for atypical species, and can thus lead to more complete factor profiles. It is expected that this method would be even more useful for HR-ToF-AMS data, due to the ability to better understand the chemical nature of atypical factors from high resolution mass spectra. Second, utilizing PMF to extract factors containing inorganic species allowed for the determination of extent of neutralization, which could have implications for aerosol parameterization. Third, subtler differences in organic aerosol components were resolved through the incorporation of inorganic mass into the PMF matrix. The additional temporal features provided by the inorganic aerosol components allowed for the resolution of more types of oxygenated organic aerosol than could be reliably re-solved from PMF of organics alone. Comparison of findings from the PMFFull MS and PMFOrg MS methods showed that for the Windsor airshed, the PMFFull MS method enabled additional conclusions to be drawn in terms of aerosol sources and chemical processes. While performing PMFOrg MS can provide important distinctions between types of organic aerosol, it is shown that including inorganic species in the PMF analysis can permit further apportionment of organics for unit mass resolution AMS mass spectra.

Dynamic Life Cycle Assessment Modeling Approaches for Transboundary Energy Feedstocks

The rise of the twenty-first century has seen the further increase in the industrialization of Earth’s resources, as society aims to meet the needs of a growing population while still protecting our environmental and natural resources. The advent of the industrial bioeconomy – which encompasses the production of renewable biological resources and their conversion into food, feed, and bio-based products – is seen as an important step in transition towards sustainable development and away from fossil fuels. One sector of the industrial bioeconomy which is rapidly being expanded is the use of biobased feedstocks in electricity production as an alternative to coal, especially in the European Union.

As bioeconomy policies and objectives increasingly appear on political agendas, there is a growing need to quantify the impacts of transitioning from fossil fuel-based feedstocks to renewable biological feedstocks. Specifically, there is a growing need to conduct a systems analysis and potential risks of increasing the industrial bioeconomy, given that the flows within it are inextricably linked. Furthermore, greater analysis is needed into the consequences of shifting from fossil fuels to renewable feedstocks, in part through the use of life cycle assessment modeling to analyze impacts along the entire value chain.

To assess the emerging nature of the industrial bioeconomy, three objectives are addressed: (1) quantify the global industrial bioeconomy, linking the use of primary resources with the ultimate end product; (2) quantify the impacts of the expaning wood pellet energy export market of the Southeastern United States; (3) conduct a comparative life cycle assessment, incorporating the use of dynamic life cycle assessment, of replacing coal-fired electricity generation in the United Kingdom with wood pellets that are produced in the Southeastern United States.

To quantify the emergent industrial bioeconomy, an empirical analysis was undertaken. Existing databases from multiple domestic and international agencies was aggregated and analyzed in Microsoft Excel to produce a harmonized dataset of the bioeconomy. First-person interviews, existing academic literature, and industry reports were then utilized to delineate the various intermediate and end use flows within the bioeconomy. The results indicate that within a decade, the industrial use of agriculture has risen ten percent, given increases in the production of bioenergy and bioproducts. The underlying resources supporting the emergent bioeconomy (i.e., land, water, and fertilizer use) were also quantified and included in the database.

Following the quantification of the existing bioeconomy, an in-depth analysis of the bioenergy sector was conducted. Specifically, the focus was on quantifying the impacts of the emergent wood pellet export sector that has rapidly developed in recent years in the Southeastern United States. A cradle-to-gate life cycle assessment was conducted in order to quantify supply chain impacts from two wood pellet production scenarios: roundwood and sawmill residues. For reach of the nine impact categories assessed, wood pellet production from sawmill residues resulted in higher values, ranging from 10-31% higher.

The analysis of the wood pellet sector was then expanded to include the full life cycle (i.e., cradle-to-grave). In doing to, the combustion of biogenic carbon and the subsequent timing of emissions were assessed by incorporating dynamic life cycle assessment modeling. Assuming immediate carbon neutrality of the biomass, the results indicated an 86% reduction in global warming potential when utilizing wood pellets as compared to coal for electricity production in the United Kingdom. When incorporating the timing of emissions, wood pellets equated to a 75% or 96% reduction in carbon dioxide emissions, depending upon whether the forestry feedstock was considered to be harvested or planted in year one, respectively.

Finally, a policy analysis of renewable energy in the United States was conducted. Existing coal-fired power plants in the Southeastern United States were assessed in terms of incorporating the co-firing of wood pellets. Co-firing wood pellets with coal in existing Southeastern United States power stations would result in a nine percent reduction in global warming potential.

Essays on Energy Economics and Industrial Organization

The dissertation consists of three chapters related to the low-price guarantee marketing strategy and energy efficiency analysis. The low-price guarantee is a marketing strategy in which firms promise to charge consumers the lowest price among their competitors. Chapter 1 addresses the research question "Does a Low-Price Guarantee Induce Lower Prices'' by looking into the retail gasoline industry in Quebec where there was a major branded firm which started a low-price guarantee back in 1996. Chapter 2 does a consumer welfare analysis of low-price guarantees to drive police indications and offers a new explanation of the firms' incentives to adopt a low-price guarantee. Chapter 3 develops the energy performance indicators (EPIs) to measure energy efficiency of the manufacturing plants in pulp, paper and paperboard industry.

Chapter 1 revisits the traditional view that a low-price guarantee results in higher prices by facilitating collusion. Using accurate market definitions and station-level data from the retail gasoline industry in Quebec, I conducted a descriptive analysis based on stations and price zones to compare the price and sales movement before and after the guarantee was adopted. I find that, contrary to the traditional view, the stores that offered the guarantee significantly decreased their prices and increased their sales. I also build a difference-in-difference model to quantify the decrease in posted price of the stores that offered the guarantee to be 0.7 cents per liter. While this change is significant, I do not find the response in comeptitors' prices to be significant. The sales of the stores that offered the guarantee increased significantly while the competitors' sales decreased significantly. However, the significance vanishes if I use the station clustered standard errors. Comparing my observations and the predictions of different theories of modeling low-price guarantees, I conclude the empirical evidence here supports that the low-price guarantee is a simple commitment device and induces lower prices.

Chapter 2 conducts a consumer welfare analysis of low-price guarantees to address the antitrust concerns and potential regulations from the government; explains the firms' potential incentives to adopt a low-price guarantee. Using station-level data from the retail gasoline industry in Quebec, I estimated consumers' demand of gasoline by a structural model with spatial competition incorporating the low-price guarantee as a commitment device, which allows firms to pre-commit to charge the lowest price among their competitors. The counterfactual analysis under the Bertrand competition setting shows that the stores that offered the guarantee attracted a lot more consumers and decreased their posted price by 0.6 cents per liter. Although the matching stores suffered a decrease in profits from gasoline sales, they are incentivized to adopt the low-price guarantee to attract more consumers to visit the store likely increasing profits at attached convenience stores. Firms have strong incentives to adopt a low-price guarantee on the product that their consumers are most price-sensitive about, while earning a profit from the products that are not covered in the guarantee. I estimate that consumers earn about 0.3% more surplus when the low-price guarantee is in place, which suggests that the authorities should not be concerned and regulate low-price guarantees. In Appendix B, I also propose an empirical model to look into how low-price guarantees would change consumer search behavior and whether consumer search plays an important role in estimating consumer surplus accurately.

Chapter 3, joint with Gale Boyd, describes work with the pulp, paper, and paperboard (PP&PB) industry to provide a plant-level indicator of energy efficiency for facilities that produce various types of paper products in the United States. Organizations that implement strategic energy management programs undertake a set of activities that, if carried out properly, have the potential to deliver sustained energy savings. Energy performance benchmarking is a key activity of strategic energy management and one way to enable companies to set energy efficiency targets for manufacturing facilities. The opportunity to assess plant energy performance through a comparison with similar plants in its industry is a highly desirable and strategic method of benchmarking for industrial energy managers. However, access to energy performance data for conducting industry benchmarking is usually unavailable to most industrial energy managers. The U.S. Environmental Protection Agency (EPA), through its ENERGY STAR program, seeks to overcome this barrier through the development of manufacturing sector-based plant energy performance indicators (EPIs) that encourage U.S. industries to use energy more efficiently. In the development of the energy performance indicator tools, consideration is given to the role that performance-based indicators play in motivating change; the steps necessary for indicator development, from interacting with an industry in securing adequate data for the indicator; and actual application and use of an indicator when complete. How indicators are employed in EPA’s efforts to encourage industries to voluntarily improve their use of energy is discussed as well. The chapter describes the data and statistical methods used to construct the EPI for plants within selected segments of the pulp, paper, and paperboard industry: specifically pulp mills and integrated paper & paperboard mills. The individual equations are presented, as are the instructions for using those equations as implemented in an associated Microsoft Excel-based spreadsheet tool.

Modeling of a Heat-Induced Buckling of Plates Using the Mesh-free Method

In the process of engineering design of structural shapes, the flat plate analysis results can be generalized to predict behaviors of complete structural shapes. In this case, the purpose of this project is to analyze a thin flat plate under conductive heat transfer and to simulate the temperature distribution, thermal stresses, total displacements, and buckling deformations. The current approach in these cases has been using the Finite Element Method (FEM), whose basis is the construction of a conforming mesh. In contrast, this project uses the mesh-free Scan Solve Method. This method eliminates the meshing limitation using a non-conforming mesh. I implemented this modeling process developing numerical algorithms and software tools to model thermally induced buckling. In addition, convergence analysis was achieved, and the results were compared with FEM. In conclusion, the results demonstrate that the method gives similar solutions to FEM in quality, but it is computationally less time consuming.

Computational approaches and tools for modeling biomass pyrolysis

Thesis (Ph.D.)--University of Washington, 2016-08

Systems Modeling of Lung Cancer Screening Programs to Improve Quality

Thesis (Master's)--University of Washington, 2016-08

Dimensionamento de uma ponte metálica de suporte de uma tela transportadora de inertes a utilizar numa instalação industrial

Trabalho de Projeto para obtenção do grau de Mestre em Engenharia Civil na Área de Especialização em Estruturas

Sequestering of Fe and Pb ions from Wastewater by Canarium schweinfurthii after carbonization and chemical treatment: Isothermal and Kinetic Modeling

In this paper agricultural waste; Canarium schweinfurthii was explored for the sequestering of Fe and Pb ions from wastewater solution after carbonization and chemical treatment at 400oC. Optimum time of 30 and 150 min with percentage removal of 95 and 98% at optimum pH of 2 and 6 was obtained for Fe and Pb ions. Kinetics model followed pseudofirst order as sum of absolute error (EABS) between Qe and Qc greater than that of pseudo second order. Parameters evaluated from isothermal equation (Freundlich and Langmuir) showed that KL and QO for Fe > Pb and R2 for Langmuir> Freundlich. The study reveals the suitability of the adsorbent for sequestering of Fe and Pb ions from industrial wastewater.

Planar solid oxide fuel cell modeling and optimization targeting the stack's temperature gradient minimization

Minimization of undesirable temperature gradients in all dimensions of a planar solid oxide fuel cell (SOFC) is central to the thermal management and commercialization of this electrochemical reactor. This article explores the effective operating variables on the temperature gradient in a multilayer SOFC stack and presents a trade-off optimization. Three promising approaches are numerically tested via a model-based sensitivity analysis. The numerically efficient thermo-chemical model that had already been developed by the authors for the cell scale investigations (Tang et al. Chem. Eng. J. 2016, 290, 252-262) is integrated and extended in this work to allow further thermal studies at commercial scales. Initially, the most common approach for the minimization of stack's thermal inhomogeneity, i.e., usage of the excess air, is critically assessed. Subsequently, the adjustment of inlet gas temperatures is introduced as a complementary methodology to reduce the efficiency loss due to application of excess air. As another practical approach, regulation of the oxygen fraction in the cathode coolant stream is examined from both technical and economic viewpoints. Finally, a multiobjective optimization calculation is conducted to find an operating condition in which stack's efficiency and temperature gradient are maximum and minimum, respectively.