O uso do biodiesel está em expansão no mercado mundial. A presença de metais alcalinos é um dos parâmetros de qualidade que mais se destaca devido aos prejuízos que pode causar ao automóvel. Neste trabalho propôs-se um método alternativo para determinar íon sódio usando um sensor eletroquímico baseado em eletrodo quimicamente modificado (EQM) com filme de octafenilciclotetrasiloxano (OFCTS), o qual possui estrutura molecular sugestiva para uma coordenação com Na+. A caracterização do sensor foi realizada por Espectroscopia de Infravermelho com Transformada de Fourier (FT-IR) e Difração de Raios X (DRX). A interação metal:ligante foi estuda por cálculos teóricos, Espectrofotometria UV-Vis, Espectroscopia de Impedância Eletroquímica (EIE) e Voltametria Cíclica (VC). A imobilização do OFCTS no eletrodo de carbono vítreo foi alcançada por adsorção usando a técnica drop coating. O par redox [Ru(NH 3)5 Cl] 2+/3+foi empregado como íon sonda e a corrente de pico (Ip) foi monitorada por voltametria de pulso diferencial com varredura anódica. Adições sucessivas de Na+ à célula eletroquímica causaram a diminuição da Ip do íon sonda, devido à interação do íon sódio com o ligante imobilizado no eletrodo e consequente repulsão com o íon sonda. Empregando este efeito, a concentração de íons sódio pode ser indiretamente medida. Após a otimização dos principais parâmetros da eletroanálise, a curva analítica foi construída através da relação entre diferença de Ip (δIp) do [Ru(NH 3) 5Cl]2+/3+e a quantidade de íons sódio adicionada, obtendo um coeficiente de correlação (r) de 0,998, LD e LQ iguais a 0,38 mg kg -1 e 1,29 mg kg-1 , respectivamente. As amostras de biodiesel foram preparadas por digestão ácida por via úmida com radiação de micro-ondas. As recuperações foram obtidas e os percentuais para a fortificação foi biodiesel 105% e para água mineral foi 81%. O método alternativo foi aplicado para amostra real e detectou 4,1 mg Kg-1 de sódio em biodiesel. / The use of biodiesel is expanding in the world market. The presence of alkali metals is one of its quality parameters that stand out, due to the damage that they can cause to vehicles. This study aimed to propose an alternative method to determine sodium ions using an electrochemical sensor based on chemically modified electrode (CME) with octaphenylcyclotetrasiloxane (OFCTS), which has suggestive molecular structure for coordination with Na+ ion. The characterization of the sensor was carried out by Fourier Transform Infrared Spectroscopy (FT-IR) and X-Ray Diffraction (XRD). The metal:ligand interaction was studied by theoretical calculations, UV-Visible Spectroscopy, Electrochemical Impedance Spectroscopy (EIS) and Cyclic Voltammetry (CV). Immobilization of OPCTS on glassy carbon electrode was achieved by adsorption through drop coating technique. The [Ru(NH 3) 5Cl]2+/3+e redox couple was used as ion probe, and its peak current (Ip) was monitored by stripping anodic stripping differential pulse voltammetry . Successive additions of Na+ to the electrochemical cell promote the Ip decrease of the ion probe, due to interaction between the sodium ion and the immobilized ligand on the electrode and the subsequent repulsion with the ion probe. Using this effect, the sodium ions concentration could be indirectly measured. After the main parameters optimization of the electroanalysis, the analytical curve was constructed by plotting the Ip difference (δIp) of [Ru(NH 3) 5Cl]2+/3+e against the amount of sodium ions added, obtaining a coefficient of correlation (r 2) of 0.99 and LOD and LOQ equal to 0,38 and 1,29 mg Kg-1, respectively. The biodiesel samples were pretreated by microwave assisted acid digestion. Recoveries were obtained and the percentages for the fortification for biodiesel was 105,5% and for mineral water was 81%. The alternative method was applied for real sample and detected 4 mg Kg -1 of the sodium in biodiesel.

I have used the Embedded Atom Method (EAM) to investigate the vibrational behaviors of a large number of metallic systems. The systems examined are the bulk bcc metals Li, Na, K, Rb, Cs, Nb, Ta, Mo, W, and Fe, the bulk fcc metals Ni, Cu, and Al, the (100), (110), (111), and (211) surfaces of the Li, Na, K, Rb, and Cs, and the (100), (110), and (111) surfaces of Ni and Cu. I have conducted a more detailed and extensive review of existing EAM models and their ability to characterize bulk vibrational behavior than has ever previously been reported. I show the ability of an EAM model to quantitatively predict the vibrational properties of the bulk alkali metals in excellent agreement with experiment. The present work remedies a lack of computational investigation into bcc metallic surfaces by performing lattice dynamics calculations of the (110), (100), (111), and (211) alkali metal surfaces. Additionally, I present lattice dynamics calculations on the (111), (100), and (110) surfaces of Cu and Ni. An accurate set of surface Debye temperatures for these metal surfaces has been calculated. The extensive number of metals and planar geometries studied has enabled the identification and clarification of general relationships between surface phonons, surface coordination, and atomic density. The changes in vibrational behavior due to the truncation of the bulk near a surface can be understood by the consideration of three things: the vibrational behavior of a 1-D chain of harmonic oscillators, the bulk dispersion relation in the direction perpendicular to a surface, and the atomic coordination of near surface atoms. In general, relaxation causes force constants between atoms to stiffen, resulting in higher vibrational frequencies. The impact of stiffening on the vibrational characteristics depends largely on the surface geometry, as well as the particular properties of the metal. It can cause new surface modes and resonances, or cause surface vibrations to be more strongly coupled to the vibrations of bulk atoms.

Vaal University of Technology / ii Abstract The use of biosorption to complement conventional water treatment techniques has gained widespread appeal partly due to the abundance of waste materials that can be used as low cost biosorbents. However, some materials have not yet been exploited in this regard. This research was aimed at evaluating the biosorption potential of Mangifera indica (mango) seed shells that are readily available in several farming areas of the Limpopo and Mpumalanga Provinces of South Africa. In this work, powdered ethylenediaminetetraacetic acid (EDTA) functionalized biosorbent was prepared from alkali treated biomass of waste mango seed shells. The influence of alkali treatment and EDTA functionalization on the physicochemical properties of the biomass was characterized using Fourier transform infra-red spectroscopy, X-ray diffraction and thermogravimetric analysis. Results confirmed removal of hemicelluloses, conversion of crystalline to amorphous cellulose and the introduction of carboxyl, ester and tertiary amine groups from EDTA. Furthermore, the powdered biosorbent was immobilized using calcium alginate for adaptation to column sorption. The powdered biosorbents were tested for sorption of lead(II) ions using batch sorption experiment. Through EDTA functionalization, improvement in sorption capacity for lead(II) ions from 59.25 mg.g-1 to 306.33 mg.g-1 was realized. The Langmuir and Pseudo-nth order models most suitably simulated the equilibrium and kinetics of sorption by both functionalized and non-functionalized biomaterials. The calcium alginate immobilized biosorbent was evaluated for non-specific sorption of ionic species of copper, chromium, nickel and iron from electroplating wastewater through discontinuous column sorption experiments. Highest copper, chromium, nickel and iron removal was 12.3%, 14.8%, 4.4% and 13.8% from nonacidified samples at an initial pH of 3.4, and 15.5%, 18.7%, 13.7% and 17.3% from samples acidified to an initial pH of 1.8. Repeated sorption-desorption cycles involving acidified wastewater resulted in successive improvement in metal uptake against declining recovery indicating irreversible binding on –COOH groups formed from –CH2OH groups through a redox reaction involving reduction of chromium(VI) to chromium(III). Keywords: Mangifera indica; biosorption; alkali treatment; carboxyl functionalization; calcium alginate

by J.K. Galt. / "September 17, 1947." / Bibliography: p. 24. / Army Signal Corps Contract No. W-39-039 sc-32037

No description available.

The effects of using alkali-silica reaction (ASR) affected recycled concrete aggregate (ASR-RCA) in hot mix asphalt (HMA) were investigated in this study. Dilatometer and modified beam tests were performed to determine the possibility of new ASR occurring in reactive aggregates within the HMA or re-expansion of existing gel. The Lottman test and micro-calorimeter were used to determine the moisture susceptibility of HMA made with ASR-RCA. A differential scanning calorimeter (DSC) with thermogravimetric analysis (TGA) was used to evaluate the drying of an artificial gel and x-ray diffraction (XRD) was used to check for the potential presence of gel in the filler fraction of the ASR-RCAs. Micro-deval and freeze-thaw tests were evaluated for their potential to indicate the presence of excess micro-cracks or ASR gel. Expansion testing indicated that both ASR-RCAs were still reactive with 0.5 N NaOH solution saturated with calcium hydroxide (CH) at 60 degrees C. Dilatometer testing of HMA specimens in NaOH CH solution at 60 degrees C indicated a reaction between the asphalt binder and the solution, but little, if any, ASR. The lack of expansion in the modified beam test supports the binder-solution interaction. However, dilatometer testing in deicer solution at the same temperature indicated that some ASR may have occurred along with the primary binder-solution interaction. The volume change characteristics associated with the binder-solution interaction with and without ASR was supported by the change in pH and alkali concentration of the test solution. DSC/TGA testing indicated that the artificial gel dehydrated at approximately 100 degrees C. XRD analysis of the filler indicated that some gel may have accumulated in this fraction. Moisture damage testing indicated good resistance to moisture damage by HMA mixtures made with ASR-RCA especially compared to a virgin siliceous aggregate. Micro-deval and freeze-thaw tests can detect the presence of micro-cracks due to ASR in ASR-RCAs as higher mass loss than the virgin aggregate. The potential distress mechanisms that may occur when using ASR-RCA in an HMA pavement were identified. Results obtained using accelerated laboratory conditions were extrapolated based on anticipated field conditions. Guidelines for the mitigation of potential distresses in HMA made with ASR-RCA are presented.

Thesis (Ph. D.)--Institute of Paper Chemistry, 1976. / Includes bibliographical references (p. 129-133).

Power generation through decentralized small scale CHP would facilitate the use of biomass as an energy source, with the externally fired gas turbine (EFGT) being a promising technology due to its high electrical efficiency. In an EFGT hot flue gases are heat-exchanged with an air cycle, driving the turbine. The operation requires higher flue gas temperatures than other technologies, for example steam turbines, to achieve optimal performance.  The operating conditions subjects the high temperature heat exchanger (HT-HE) to both physical and chemical stress, with the corrosion related issues yet to be solved. Problems concerning deposit formation and corrosion, on for example super heaters and heat exchangers, when firing biomass are important issues even in commercially available technologies, where the choice of fuel and fuel additives together with component design and choice of material plays important roles in order to minimize the problems. The significantly higher temperatures of the heat transferring surfaces for an EFGT entails combustion deposit related problems less studied. The evaluation of turbine control, deposit formation and corrosion as well as design of the HT-HE and system integration will enable the development of the EFGT technology for applications with small- and medium-size biomass combustion. In this work four potential HT-HE alloys of various grades have been evaluated with respect to corrosion resistance, when exposed to alkali salts and salt mixtures in the KCl-K2CO3-K2SO4 system. The exposures were done in a tube furnace during 24 h for each experiment at four temperature levels between 700–1000oC. Morphological and elemental analysis of the alloy surface and corrosion layers was performed with SEM-EDS. The presence of KCl in the salt caused the most severe corrosion attacks while the corrosion attacks of the pure sulfate and carbonate were more modest. Significant differences between the four materials were observed. X20 experienced severe corrosion, with corrosion scale formation in most cases. The KCl-containing salts caused 253MA to form corrosion scales at all temperatures, while the corrosion resistance to other salts was fairly good. Inconel 600 had the second best overall corrosion resistance. However, it should be pointed out that in some cases the alloy was surpassed by 253MA. Kanthal showed the best overall performance, with limited corrosion scale formation and surprisingly high corrosion resistance to the KCl-containing ternary salt mixture at 900°C and 1000°C.

Surfactant-polymer (SP) and alkali-surfactant-polymer (ASP) flooding has gained little traction among different tertiary recovery strategies such as thermal and miscible gas flooding; however, many mature onshore reservoirs could be potential candidates. More than four decades of research has detailed technical challenges and successes through laboratory experimentation, chemical flood simulation, and some pilot projects, which have provided technical screening procedures to efficiently filter unfeasible projects. Therefore, technical understanding seems sufficient to advance projects through early development stages; however, a project value identification and realization process ultimately dictates project implementation in the oil and gas industry, with technical feasibility merely supporting overall valuation and project feasibility. A quick early screening methodology integrating important project valuation criteria can efficiently assess large numbers of projects. The relatively few studies detailing chemical flooding valuation from just an economic standpoint reflects the need for an integrated process-oriented framework for quick early screening valuation of chemical flooding opportunities. This study develops an integrated process-oriented framework for early screening and valuation, with an overall objective to quickly filter unfeasible projects based on valuation criteria, rather than technical feasibility alone. A reservoir-to-market model was developed, integrating information from laboratory experiments (phase behavior, core flood), field analogues (well performance and layout), facilities, rigs, costs, scheduling, and economics. Recently published ASP flood data of the central Xing2 area in Daqing, China was used for model inputs. A reservoir-to-market benchmark model for a typical mature onshore field was successfully built and tested, and could value projects using standard economic metrics (net present value, internal rate of return, value investment ratio, unit technical cost, and payback period). Model simplification was achieved through global sensitivity analysis. Using a mean-reversion oil price model, the oil price accounted for 98% of the total sensitivity. . Model efficiency was achieved through discretization of input parameter uncertainties, which sped the screening process. Decision-making between model alternatives given information and different states of nature was performed through decision-tree techniques based on overall project valuation. Overall, this study was novel and provided benefit as a robust, integrated process-oriented framework for chemical EOR project screening, valuation, and decision-making. / text

It is estimated that the shallow reservoirs of Ugnu, West Sak and Shraeder Bluff in the North Slope of Alaska hold about 20 billion barrels of heavy oil. The proximity of these reservoirs to the permafrost makes the application of thermal methods for the oil recovery very unattractive. It is feared that the heat from the thermal methods may melt this permafrost leading to subsidence of the unconsolidated sand (Marques 2009; Peyton 1970; Wilson 1972). Thus it is necessary to consider the development of cheap non-thermal methods for the recovery of these heavy oils. This study investigates non-thermal techniques for the recovery of heavy oils. Chemicals such as alkali, surfactant and polymer are used to demonstrate improved recovery over waterflooding for two oils (A:10,000cp and B:330 cp). Chemical screening studies showed that appropriate concentrations of chemicals, such as alkali and surfactant, could generate emulsions with oil A. At low brine salinity oil-in-water (O/W) emulsions were generated whereas water-in-oil (W/O) emulsions were generated at higher salinities. 1D and 2D sand pack floods conducted with alkali surfactant (AS) at different salinities demonstrated an improvement of oil recovery over waterflooding. Low salinity AS flood generated lower pressure drop, but also resulted in lower oil recovery rates. High salinity AS flood generated higher pressure drop, high viscosity emulsions in the system, but resulted in a greater improvement in oil recovery over waterfloods. Polymers can also be used to improve the sweep efficiency over waterflooding. A 100 cp polymer flood improved the oil recovery over waterflood both in 1D and 2D geometry. In 1D geometry 1PV of polymer injection increased the oil recovery from 30% after waterflood to 50% OOIP. The tertiary polymer injection was found to be equally beneficial as the secondary polymer injection. It was also found that the combined application of AS and polymer did not give any major advantage over polymer flood or AS flood alone. Chemical EOR technique was considered for the 330cp oil B. Chemical screening studies showed that microemulsions could be generated in the system when appropriate concentrations of alkali and surfactant were added. Solubilization ratio measurement indicted that the interfacial tension in the system approached ultra-low values of about 10-3 dynes/cm. The selected alkali surfactant system was tested in a sand pack flood. Additionally a partially hydrolyzed polymer was used to provide mobility control to the process. The tertiary injection of ASP (Alkali-Surfactant-Polymer) was able to improve the oil recovery from 60% OOIP after the waterflood to almost 98% OOIP. A simple mathematical model was built around viscous fingering phenomenon to match the experimental oil recoveries and pressure drops during the waterflood. Pseudo oil and water relative permeabilities were calculated from the model, which were then used directly in a reservoir simulator in place of the intrinsic oil-water relative permeabilities. Good agreement with the experimental values was obtained. For history matching the polymer flood of heavy oil, intrinsic oil-water relative permeabilities were found to be adequate. Laboratory data showed that polymer viscosity is dependent on the polymer concentration and the effective brine salinity. Both these effects were taken into account when simulating the polymer flood or the ASP flood. The filtration theory developed by Soo and Radke (1984) was used to simulate the dilute oil-in-water emulsion flow in the porous media when alkali-surfactant flood of the heavy oil was conducted. The generation of emulsion in the porous media is simulated via a reaction between alkali, surfactant, water and heavy oil. The theory developed by Soo and Radke (1984) states that the flowing emulsified oil droplets clog in pore constrictions and on the pore walls, thereby restricting flow. Once captured, there is a negligible particle re-entrainment. The simulator modeled the capture of the emulsion droplets via chemical reaction. Next, the local water relative permeability was reduced as the trapping of the oil droplets will reduce the mobility of the water phase. This entrapment mechanism is responsible for the increase in the pressure drop and improvement in oil recovery. The model is very sensitive to the reaction rate constants and the oil-water relative permeabilities. ASP process for lower viscosity 330 cp oil was modeled using the UTCHEM multiphase-multicomponent simulator developed at the University of Texas at Austin. The simulator can handle the flow of three liquid phases; oil, water and microemulsion. The generation of microemulsion is modeled by the reaction of the crude oil with the chemical species present in the aqueous phase. The experimental phase behavior of alkali and surfactant with the crude oil was modeled using the phase behavior mixing model of the simulator. Oil and water relative permeabilities were enhanced where microemulsion is generated and interfacial tension gets reduced. Experimental oil recovery and pressure drop data were successfully history matched using UTCHEM simulator. / text