Some examples of modeling in chemical engineering: thermal treatment of polymers, phase equilibrium calculations and process design

Presentation submitted to PSE Seminar, Chemical Engineering Department, Center for Advanced Process Design-making (CAPD), Carnegie Mellon University, Pittsburgh (USA), October 2012.

Chemical and isotopic compositions of pore fluids from ODP Sites 169-1034 and 169-1037

We have analysed the concentrations of Li, K, Rb, Cs, and B, and the isotopic ratios of Li and B of a suite of pore fluids recovered from ODP Sites 1037 (Leg 169; Escanaba Trough) and 1034 (Leg 169S; Saanich Inlet). In addition, we have analysed dissolved K, Rb, and Cs concentrations for estuarine mixing of the Ganges-Brahmaputra river system. Together, these data sets have been used to assess the role of sediments in the marine geochemical cycles of the alkali elements and boron. Uptake onto clay minerals during estuarine mixing removes 20-30% of the riverine input of dissolved Cs and Rb to the oceans. Prior to this study, the only other recognised sink of Rb and Cs was uptake during low-temperature alteration of the oceanic crust. Even with this additional sink there is an excess of inputs over outputs in their modern oceanic mass balance. Pore fluid data show that Li and Rb are transferred into marine sediments during early diagenesis. However, modeling of the Li isotope systematics of the pore fluids from Site 1037 shows that seawater Li taken up during marine sedimentation can be readily returned to solution in the presence of less hydrated cations, such as NH4+. This process also appears to result in high concentrations of pore fluid Cs (relative to local seawater) due to expulsion of adsorbed Cs from cation exchange sites. Flux calculations based on pore fluid data for a series of ODP sites indicate that early diagenesis of clay sediments removes around 8% of the modern riverine input of dissolved Li. Although NH4+-rich fluids do result in a flux of Cs to the oceans, on the global scale this input only augments the modern riverine Cs flux by ~3%. Nevertheless, this may have implications for the fate of radioactive Cs in the natural environment and waste repositories.

PVT behaviour of fluids with potential models optimised for phase equilibria

NPT and NVT Monte Carlo simulations are applied to models for methane and water to predict the PVT behaviour of these fluids over a wide range of temperatures and pressures. The potential models examined in this paper have previously been presented in the literature with their specific parameters optimised to fit phase coexistence data. The exponential-6 potential for methane gives generally good prediction of PVT behaviour over the full range of temperature and pressures studied with the only significant deviation from experimental data seen at high temperatures and pressures. The NSPCE water model shows very poor prediction of PVT behaviour, particularly at dense conditions. To improve this. the charge separation in the NSPCE model is varied with density. Improvements for vapour and liquid phase PVT predictions are achieved with this variation. No improvement was found in the prediction of the oxygen-oxygen radial distribution by varying charge separation under dense phase conditions. (C) 2004 Elsevier B.V. All rights reserved.

Pattern competition in volumetricaly heated fluids

Finite element simulations have been performed along side Galerkin-type calculations that examined the development of volumetrically heated flow patterns in a horizontal layer controlled by the Prandtl number, Pr, and the Grashof number, Gr. The fluid was bounded by an isothermal plane above an adiabatic plane. In the simulations performed here, a number of convective polygonal planforms occurred, as Gr increased above the critical Grashof number, Grc at Pr = 7, while roll structures were observed for Pr < 1 at 2Grc.

Aggregation and caking processes of granular materials:continuum model and simulation with application to sugar

Aggregation and caking of particles are common severe problems in many operations and processing of granular materials, where granulated sugar is an important example. Prevention of aggregation and caking of granular materials requires a good understanding of moisture migration and caking mechanisms. In this paper, the modeling of solid bridge formation between particles is introduced, based on moisture migration of atmospheric moisture into containers packed with granular materials through vapor evaporation and condensation. A model for the caking process is then developed, based on the growth of liquid bridges (during condensation), and their hardening and subsequent creation of solid bridges (during evaporation). The predicted caking strengths agree well with some available experimental data on granulated sugar under storage conditions.

Geochemical determination of the fate and transport of injected fresh wastewater to a deep saline aquifer

Deep well injection into non-potable saline aquifers of treated domestic wastewater has been used in Florida for decades as a safe and effective alternative to ocean outfall disposal. The objectives of this study were to determine the fate and transport of injected wastewater at two deep well injection sites in Miami Dade County, Florida, USA. Detection of ammonium in the Middle Confining units of the Floridan aquifer above the injection zone at both sites has been interpreted as evidence of upward migration of injected wastewater, posing a risk to underground sources of drinking water. Historical water quality data, including ammonia, chloride, temperature, and pH from existing monitoring wells at both sites from 1983 to 2008, major ions collected monthly from 2006 and 2008, and a synoptic sampling event for stable isotopes, tritium, and dissolved gases in 2008, were used to determine the source of ammonium in groundwater and possible migration pathways. Geochemical modeling was used to determine possible effects of injected wastewater on native water and aquifer matrix geochemistry. Injected wastewater was determined to be the source of elevated ammonium concentrations above ambient water levels, based on the results of major ion concentrations, tritium, dissolved noble gases and 15N isotopes analyses. Various possible fluid migration pathways were identified at the sites. Data for the south site suggest buoyancy-driven vertical pathways to overlying aquifers bypassing the confining units, with little mixing of injected wastewater with native water as it migrated upward. Once it is introduced into an aquifer, the injectate appeared to migrate advectively with the regional groundwater flow. Geochemical modeling indicated that CO 2-enriched injected wastewater allowed for carbonate dissolution along the vertical pathways, enhancing permeability along these flowpaths. At the north site, diffusive upward flow through the confining units or offsite vertical pathways were determined to be possible, however no evidence was detected for any on-site confining unit bypass pathway. No evidence was observed at either site of injected wastewater migration to the Upper Floridan aquifer, which is used as a municipal water supply and for aquifer storage and recovery.

Methods of modelling people using discrete-event simulation

Discrete-event simulation (DES) is a developed technology used to model manufacturing and service systems. However, although the importance of modelling people in a DES has been recognised, there is little guidance on how this can be achieved in practice. The results from a literature review were used in order to identify examples of the use of DES to model people. Each article was examined in order to determine the method used to model people within the simulation study. It was found that there are no common methods but a diverse range of approaches used to model human behaviour in DES. This paper provides an outline of the approaches used to model people in terms of their decision making, availability for work, task performance and arrival rate. The outcome brings together the current knowledge in this area and will be of interest to researchers considering developing a methodology for modelling people in DES and to practitioners engaged with a simulation project involving the model ling of people’s behaviour.

An Alternative Goodness-of-fit Test for Normality with Unknown Parameters

Goodness-of-fit tests have been studied by many researchers. Among them, an alternative statistical test for uniformity was proposed by Chen and Ye (2009). The test was used by Xiong (2010) to test normality for the case that both location parameter and scale parameter of the normal distribution are known. The purpose of the present thesis is to extend the result to the case that the parameters are unknown. A table for the critical values of the test statistic is obtained using Monte Carlo simulation. The performance of the proposed test is compared with the Shapiro-Wilk test and the Kolmogorov-Smirnov test. Monte-Carlo simulation results show that proposed test performs better than the Kolmogorov-Smirnov test in many cases. The Shapiro Wilk test is still the most powerful test although in some cases the test proposed in the present research performs better.

Numerical Simulation Of Ultrasonic Wave Propagation In Elastically Anisotropic Media

The ultrasonic non-destructive testing of components may encounter considerable difficulties to interpret some inspections results mainly in anisotropic crystalline structures. A numerical method for the simulation of elastic wave propagation in homogeneous elastically anisotropic media, based on the general finite element approach, is used to help this interpretation. The successful modeling of elastic field associated with NDE is based on the generation of a realistic pulsed ultrasonic wave, which is launched from a piezoelectric transducer into the material under inspection. The values of elastic constants are great interest information that provide the application of equations analytical models, until small and medium complexity problems through programs of numerical analysis as finite elements and/or boundary elements. The aim of this work is the comparison between the results of numerical solution of an ultrasonic wave, which is obtained from transient excitation pulse that can be specified by either force or displacement variation across the aperture of the transducer, and the results obtained from a experiment that was realized in an aluminum block in the IEN Ultrasonic Laboratory. The wave propagation can be simulated using all the characteristics of the material used in the experiment evaluation associated to boundary conditions and from these results, the comparison can be made.

NUMERICAL SIMULATION STUDY OF VIBRATION MITIGATION EFFECTIVENESS OF TUNED MASS DAMPERS FOR TRAFFIC SIGNAL MAST ARM STRUCTURES

Fatigue damage in the connections of single mast arm signal support structures is one of the primary safety concerns because collapse could result from fatigue induced cracking. This type of cantilever signal support structures typically has very light damping and excessively large wind-induced vibration have been observed. Major changes related to fatigue design were made in the 2001 AASHTO LRFD Specification for Structural Supports for Highway Signs, Luminaries, and Traffic Signals and supplemental damping devices have been shown to be promising in reducing the vibration response and thus fatigue load demand on mast arm signal support structures. The primary objective of this study is to investigate the effectiveness and optimal use of one type of damping devices termed tuned mass damper (TMD) in vibration response mitigation. Three prototype single mast arm signal support structures with 50-ft, 60-ft, and 70-ft respectively are selected for this numerical simulation study. In order to validate the finite element models for subsequent simulation study, analytical modeling of static deflection response of mast arm of the signal support structures was performed and found to be close to the numerical simulation results from beam element based finite element model. A 3-DOF dynamic model was then built using analytically derived stiffness matrix for modal analysis and time history analysis. The free vibration response and forced (harmonic) vibration response of the mast arm structures from the finite element model are observed to be in good agreement with the finite element analysis results. Furthermore, experimental test result from recent free vibration test of a full-scale 50-ft mast arm specimen in the lab is used to verify the prototype structure’s fundamental frequency and viscous damping ratio. After validating the finite element models, a series of parametric study were conducted to examine the trend and determine optimal use of tuned mass damper on the prototype single mast arm signal support structures by varying the following parameters: mass, frequency, viscous damping ratio, and location of TMD. The numerical simulation study results reveal that two parameters that influence most the vibration mitigation effectiveness of TMD on the single mast arm signal pole structures are the TMD frequency and its viscous damping ratio.

Otimização e análise mecânica de pastas geopoliméricas para uso em poços sujeitos à injeção cíclica de vapor

Oil wells subjected to cyclic steam injection present important challenges for the development of well cementing systems, mainly due to tensile stresses caused by thermal gradients during its useful life. Cement sheath failures in wells using conventional high compressive strength systems lead to the use of cement systems that are more flexible and/or ductile, with emphasis on Portland cement systems with latex addition. Recent research efforts have presented geopolymeric systems as alternatives. These cementing systems are based on alkaline activation of amorphous aluminosilicates such as metakaolin or fly ash and display advantageous properties such as high compressive strength, fast setting and thermal stability. Basic geopolymeric formulations can be found in the literature, which meet basic oil industry specifications such as rheology, compressive strength and thickening time. In this work, new geopolymeric formulations were developed, based on metakaolin, potassium silicate, potassium hydroxide, silica fume and mineral fiber, using the state of the art in chemical composition, mixture modeling and additivation to optimize the most relevant properties for oil well cementing. Starting from molar ratios considered ideal in the literature (SiO2/Al2O3 = 3.8 e K2O/Al2O3 = 1.0), a study of dry mixtures was performed,based on the compressive packing model, resulting in an optimal volume of 6% for the added solid material. This material (silica fume and mineral fiber) works both as an additional silica source (in the case of silica fume) and as mechanical reinforcement, especially in the case of mineral fiber, which incremented the tensile strength. The first triaxial mechanical study of this class of materials was performed. For comparison, a mechanical study of conventional latex-based cementing systems was also carried out. Regardless of differences in the failure mode (brittle for geopolymers, ductile for latex-based systems), the superior uniaxial compressive strength (37 MPa for the geopolymeric slurry P5 versus 18 MPa for the conventional slurry P2), similar triaxial behavior (friction angle 21° for P5 and P2) and lower stifness (in the elastic region 5.1 GPa for P5 versus 6.8 GPa for P2) of the geopolymeric systems allowed them to withstand a similar amount of mechanical energy (155 kJ/m3 for P5 versus 208 kJ/m3 for P2), noting that geopolymers work in the elastic regime, without the microcracking present in the case of latex-based systems. Therefore, the geopolymers studied on this work must be designed for application in the elastic region to avoid brittle failure. Finally, the tensile strength of geopolymers is originally poor (1.3 MPa for the geopolymeric slurry P3) due to its brittle structure. However, after additivation with mineral fiber, the tensile strength became equivalent to that of latex-based systems (2.3 MPa for P5 and 2.1 MPa for P2). The technical viability of conventional and proposed formulations was evaluated for the whole well life, including stresses due to cyclic steam injection. This analysis was performed using finite element-based simulation software. It was verified that conventional slurries are viable up to 204ºF (400ºC) and geopolymeric slurries are viable above 500ºF (260ºC)

EXISTENCE OF UNUSED MANAGED CAPACITY ON DEDICATED LANES AND AN ALTERNATIVE ON HOW TO SELL IT VIA AUCTIONS

This dissertation verifies whether the following two hypotheses are true: (1) High-occupancy/toll lanes (and therefore other dedicated lanes) have capacity that could still be used; (2) such unused capacity (or more precisely, “unused managed capacity”) can be sold successfully through a real-time auction. To show that the second statement is true, this dissertation proposes an auction-based metering (ABM) system, that is, a mechanism that regulates traffic that enters the dedicated lanes. Participation in the auction is voluntary and can be skipped by paying the toll or by not registering to the new system. This dissertation comprises the following four components: a measurement of unused managed capacity on an existing HOT facility, a game-theoretic model of an ABM system, an operational description of the ABM system, and a simulation-based evaluation of the system. Some other and more specific contributions of this dissertation include the following: (1) It provides a definition and a methodology for measuring unused managed capacity and another important variable referred as “potential volume increase”. (2) It proves that the game-theoretic model has a unique Bayesian Nash equilibrium. (3) And it provides a specific road design that can be applied or extended to other facilities. The results provide evidence that the hypotheses are true and suggest that the ABM system would benefit a public operator interested in reducing traffic congestion significantly, would benefit drivers when making low-reliability trips (such as work-to-home trips), and would potentially benefit a private operator interested in raising revenue.

Estudo da segregação gravitacional do processo de injeção de vapor em reservátórios heterogêneos

Due to reservoirs complexity and significantly large reserves, heavy oil recovery has become one of the major oil industry challenges. Thus, thermal methods have been widely used as a strategic method to improve heavy oil recovery. These methods improve oil displacement through viscosity reduction, enabling oil production in fields which are not considered commercial by conventional recovery methods. Among the thermal processes, steam flooding is the most used today. One consequence in this process is gravity segregation, given by difference between reservoir and injected fluids density. This phenomenon may be influenced by the presence of reservoir heterogeneities. Since most of the studies are carried out in homogeneous reservoirs, more detailed studies of heterogeneities effects in the reservoirs during steam flooding are necessary, since most oil reservoirs are heterogeneous. This paper presents a study of reservoir heterogeneities and their influence in gravity segregation during steam flooding process. In this study some heterogeneous reservoirs with physical characteristics similar those found in the Brazilian Northeast Basin were analyzed. To carry out the simulations, it was used the commercial simulator STARS by CMG (Computer Modeling Group) - version 2007.11. Heterogeneities were modeled with lower permeability layers. Results showed that the presence of low permeability barriers can improve the oil recovery, and reduce the effects of gravity segregation, depending on the location of heterogeneities. The presence of these barriers have also increased the recovered fraction even with the reduction of injected steam rate

Influência da areia argilosa na recuperação de petróleo por injeção de vapor

Continuous steam injection is one of heavy oil thermal recovery methods used in the Brazilian Northeast because of high occurrence of heavy oil reservoir. In this process, the oil into the reservoir is heated while reduces, substantially, its viscosity and improves the production. This work analyzed how the shaly sand layers influenced in the recovery. The studied models were synthetics, but the used reservoir data can be extrapolated to real situations of Potiguar Basin. The modeling was executed using the STARS - Steam Thermal and Advanced Process Reservoir Simulator - whose version was 2007.10. STARS is a tool of CMG Computer Modeling Group. The study was conducted in two stages, the first we analyzed the influence of reservoir parameters in the thermal process, so some of these were studied, including: horizontal permeability of the reservoir and the layer of shaly sand, ratio of horizontal permeability to vertical permeability, the influence of capillary pressure layer of shaly sand and as the location and dimensions of this heterogeneity can affect the productivity of oil. Among the parameters studied the horizontal permeability of the reservoir showed the most significant influence on the process followed by diversity. In the second stage three models were selected and studied some operational parameters such as injection rate, distance between wells, production time and completion intervals. Among the operating parameters studied the low rate and intermediate distances between wells showed the best recoveries

Efeito da perda de carga e calor no poço injetor no processo de drenagem gravitacional assistido com vapor e solvente

Nowadays, most of the hydrocarbon reserves in the world are in the form of heavy oil, ultra - heavy or bitumen. For the extraction and production of this resource is required to implement new technologies. One of the promising processes for the recovery of this oil is the Expanding Solvent Steam Assisted Gravity Drainage (ES-SAGD) which uses two parallel horizontal wells, where the injection well is situated vertically above the production well. The completion of the process occurs upon injection of a hydrocarbon additive at low concentration in conjunction with steam. The steam adds heat to reduce the viscosity of the oil and solvent aids in reducing the interfacial tension between oil/ solvent. The main force acting in this process is the gravitational and the heat transfer takes place by conduction, convection and latent heat of steam. In this study was used the discretized wellbore model, where the well is discretized in the same way that the reservoir and each section of the well treated as a block of grid, with interblock connection with the reservoir. This study aims to analyze the influence of the pressure drop and heat along the injection well in the ES-SAGD process. The model used for the study is a homogeneous reservoir, semi synthetic with characteristics of the Brazilian Northeast and numerical simulations were performed using the STARS thermal simulator from CMG (Computer Modelling Group). The operational parameters analyzed were: percentage of solvent injected, the flow of steam injection, vertical distance between the wells and steam quality. All of them were significant in oil recovery factor positively influencing this. The results showed that, for all cases analyzed, the model considers the pressure drop has cumulative production of oil below its respective model that disregards such loss. This difference is more pronounced the lower the value of the flow of steam injection