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The demands for copper and rare earth elements (REEs) in the U.S. will keep rising due to their applications in green energy technologies. Meanwhile, copper production in the U.S. has been declining over the past five years due to the depletion of high-grade ore deposits. The situation for REEs is worse; there is no domestic supply chain of REEs in the U.S. since the demise of Molycorp, Inc. in 2016. Studies have shown that the rejected materials from copper and coal processing plants contain significant amounts of valuable metals. As such, this rejected material can be considered as potential secondary sources for extracting copper and REEs, which may help combat future supply risks for the supply of copper and REEs in the U.S. However, the valuable mineral particles in these resources are ultrafine in size, which poses considerable challenges to the most widely used fine particle beneficiation technique, i.e., froth flotation. A novel technology called the Hydrophobic-Hydrophilic Separation (HHS) process, developed at Virginia Tech, has been successfully applied to recover fine coal in previous research. The results of research into the HHS process showed that the process has no lower particle size limit, similar to solvent extraction. Therefore, the primary objective of this research is to explore the feasibility of using the new process to recover ultrafine particles of coal, copper minerals, and rare earth minerals (REMs) associated with coal byproducts. In the present work, a series of laboratory-scale oil agglomeration and HHS tests have been carried out on coal with the objectives of assisting the HHS tests in pilot-scale, and the scale-up of the process. The knowledge gained from this study was successfully applied to solving the problems encountered in the pilot-scale tests. Additionally, a new and more efficient equipment known as the Morganizer has been designed and constructed to break up the agglomerates in oil phase as a means to remove entrained gangue minerals and water. The effectiveness of the new Morganizers has been demonstrated in laboratory-scale HHS tests, which may potentially result in the reduction of capital costs in commercializing the HHS process. Furthermore, the prospect of using the HHS process for processing high-sulfur coals has been explored. The results of this study showed that the HHS process can be used to increase the production of cleaner coal from waste streams. Application of the HHS process was further extended to recover the micron-sized REMs from a thickener underflow sample from the LW coal preparation plant, Kentucky. The results showed that the HHS process was far superior to the forced-air flotation process. In one test conducted during the earlier stages of the present study, a concentrate assaying 17,590 ppm total REEs was obtained from a 300 ppm feed. In this test, the Morganizer was not used to upgrade the rougher concentrate due to the lack of proper understanding of the fundamental mechanisms involved in converting oil-in-water (o/w) Pickering emulsions to water-in-oil (w/o) Pickering emulsions. Many of the studies has, therefore, been focused on the studies of phase inversion mechanisms. The results showed that phase inversion requires that i) the oil contact angles (θo) of the particles be increased above 90o, ii) the phase volume of oil (ϕo) be increased, and iii) the o/w emulsion be subjected to a high-shear agitation. It has been found that the first criterion can be readily met by using a hydrophobicity-enhancing agent. These findings were applied to produce high-grade REM concentrates from an artificial mixture of micron-sized monazite and silica. Based on the improved understanding of phase inversion, a modified HHS process has been developed to recover ultrafine particles of copper minerals. After successfully demonstrating the efficacy and effectiveness of this process on a series of artificial copper ore samples, the modified HHS process was used to produce high-grade copper concentrates from a series of cleaner scavenger tails obtained from operating plants. / Doctor of Philosophy / Recovery and dewatering of ultrafine particles have been the major challenges in the minerals and coal industries. Based on the thermodynamic advantage that oil droplets form contact angles about twice as large as those obtainable with air bubbles, a novel separation technology called the hydrophobic-hydrophilic separation (HHS) process was developed at Virginia Tech to address this issues. The research into the HHS process previously was only conducted on the recovery of ultrafine coal particles; also, the fundamental aspects of the HHS process were not fully understood, particularly the mechanisms of phase inversion of oil-in-water emulsions to water-in-oil emulsions. As a follow-up to the previous studies, emulsification tests have been conducted using ultrafine silica and chalcopyrite particles as emulsifiers, and the results showed that phase inversion requires high contact angles, high phase volumes, and high-shear agitation. These findings were applied to improve the HHS process for the recovery of ultrafine particles of coal, copper minerals, and rare earth minerals (REMs). The results obtained in the present work show that the HHS process can be used to efficiently recover and dewater fine particles without no lower particle size limits.

A novel technique for selectively coagulating and separating coal from dispersed mineral matter has been developed at Virginia Tech. The process, which is known as Selective Hydrophobic Coagulation (SHC), differs from oil agglomeration, shear or polymer flocculation, and electrolytic coagulation processes in that it does not require reagents or additives to induce the formation of coagula. In most cases, simple pH control is all that is required to (i) induce the coagulation of coal particles and (ii) effectively disperse particles of mineral matter. If the coal is oxidized, a small dosage of reagents may be used to enhance the coagulation process. During the SHC development, it was discovered that the hydrophobic coagula were very difficult to separate from dispersed mineral matter due to their very small size and their susceptibility to breakage. Using the SHC technique, an evaluation of new methods for coagula recovery was conducted. In this effort, several methods for improving the separation of the coal coagula from dispersed mineral matter were examined. These included lamella thickening, centrifugal sedimentation, vacuum filtration, drum screening, and froth flotation. Each separation method was optimized using statistically-designed test matrices to determined the best separation method based on overall process performance. The thickener was found to be the best method for separating hydrophobic coagula from dispersed mineral matter based on overall process performance (e.g., recovery and grade), unit capacity, and engineering feasibility. Further testing of the thickener separation unit was conducted in an attempt to improve the process performance and the unit throughput. / Master of Science

Submitted by Rafael Santana (rafael.silvasantana@ufpe.br) on 2017-07-10T18:48:53Z No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Dissertação completa.pdf: 8076647 bytes, checksum: 5dc16e9ca5f10026afed3fda08fda16b (MD5) / Made available in DSpace on 2017-07-10T18:48:53Z (GMT). No. of bitstreams: 2 license_rdf: 811 bytes, checksum: e39d27027a6cc9cb039ad269a5db8e34 (MD5) Dissertação completa.pdf: 8076647 bytes, checksum: 5dc16e9ca5f10026afed3fda08fda16b (MD5) Previous issue date: 2016-05-12 / Minerais industriais em faixas ultrafinas (< 10 μm) têm suas propriedades potencializadas em relação ao mesmo mineral com maior granulometria. Os materiais ultrafinos são utilizados em diversos seguimentos industriais; por exemplo: materiais cerâmicos, papel e celulose, fármacos, polímeros e tintas. A produção de ultrafinos ocorre em moinhos de alta energia. Dentre estes, o moinho planetário de bolas destaca-se pelas altas taxas de redução de tamanho e pelo fato de poderem ser alimentados via seco ou via úmido em regime contínuo (escala industrial) ou por batelada. A produção de ultrafinos é limitada pelo consumo de energia e pela necessidade de controle das condições operacionais, tamanho, morfologia e composição das partículas. Para otimização das variáveis do processo, usam-se ferramentas computacionais embasadas em modelos matemáticos, tais como os modelos de balanço populacional (MBP), dada pela equação da moagem por batelada, e modelos energéticos. Este trabalho teve por objetivo estudar modelos cinético e energéticos, sendo o primeiro uma solução analítica da equação da moagem por batelada utilizado para descrever as distribuições de tamanhos de partículas, e o segundo dado pela relação energia-tamanho, que prevê uma taxa de redução de tamanho ilimitada, e pela relação tempo-tamanho, que está fundamentada na taxa de moagem () e no limite de moagem. Os modelos foram aplicados em duas centenas de curvas granulométricas resultantes de ensaios de moagem executados anteriormente em alíquotas de calcário e quartzo (duas procedências) com massa e granulometria controladas. Os tempos de moagem variaram de 2 a 960 minutos com velocidades de revolução de 100 a 300 rpm. Os ajustes dos modelos cinético e energéticos foram avaliados considerando os seguintes fatores: coeficiente de determinação (R2), erro padrão (EP), erro de ajuste () e índice de dependência (ID). O modelo cinético apresentou, para a maioria das condições de moagem testadas, grande incerteza associada a alguns de seus parâmetros ( > 10%), tornando os ajustes insatisfatórios segundo os critérios utilizados. Os fatores de avaliação para o modelo cinético só foram adequados para o quartzo de uma procedência, na faixa de 38x75 μm, satisfazendo a condição de compensação estabelecida. No caso dos modelos energéticos, os ajustes obtidos para a relação energiatamanho foram melhores para aquelas situações em que os diâmetros característicos não apresentaram uma estabilização em seu decrescimento. Por sua vez, a relação tempo-tamanho mostrou ajustes compatíveis com as situações em que foi observado um estado estático de decrescimento dos diâmetros característicos, atingindo o limite de moagem. A partir dos ajustes da relação tempo-tamanho foi possível determinar uma constante k’ que caracterizasse a resistência à fragmentação do material em função das condições de moagem estudadas. Os valores dessa constante mostraram que materiais mais resistentes à fragmentação possuem os menores valores de k’, que variaram entre 0,96 e 2,6 g/J para o calcário e entre 0,06 a 0,53 g/J para o quartzo. Concluiu-se, que o modelo cinético foi incompatível com a moagem ultrafina, devida a presença de eventos significativos de aglomeração e interações mecânicas multipartículas, confirmados pela variação do índice de uniformidade () com o tempo de moagem. Os modelos energéticos se complementam na descrição dos resultados experimentais. Logo um modelo intermediário que considere uma taxa de redução de tamanho como uma função potência, com um expoente e um parâmetro (l) que represente o limite de moagem, seja o mais recomendado para a representação dos processos de moagem ultrafina de minerais industriais. / Industrial minerals in ultrafine ranges (< 10 μm) have their properties potentiated compared to the same mineral with larger particle size. The ultrafine materials are used in several industries; for example, ceramics, paper and cellulose, pharmaceuticals, polymers and paints. The production of ultrafine occurs in high energy mills. Among these mills, the planetary ball mill stand out by high rates and can be fed dry or wet in continuous (industrial scale) or batch operation. The production of ultrafine is limited by the energy consumption and the need to control of the operating conditions, size, morphology and composition of the particles. Computational tools based on mathematical models are used in the optimization and control of process variables, such as the population balance models (MBP), given by equation milling batch, and energetic models. This work has as objective to study kinetic and energetic models, the first is a analytical solution for the batch grinding equation used to describe particle size distributions; the second given by the energy-size relations, which predict a size reduction rate unlimited, and by the time-size relations, which are based on the milling rate () and grinding limit. The models were applied to two hundred of particle sizes distributions curves resulting from grinding tests performed previously in aliquots of limestone and quartz (two origins) with control of mass and particle size. The milling times range 2 - 960 min with revolution speeds of 100 to 300 rpm. The fits of the kinetic and energetic models were evaluated considering the following factors: coefficient of determination (R2), standard error (SE), fit error (ε) and dependency index (ID). The kinetic model showed uncertainty associated with some of its parameters (ε > 10%) for most of the grinding conditions tested, resulting in unsatisfactory fits to the criteria used. The evaluation factors for the kinetic model were only suitable for one quartz, in the range of 38x75 μm satisfying the compensation condition. In the case of energetic models, the fits to the energy-size relation were better for those situations where the characteristic diameters did not show a stabilization in its decrease. On the other hand, the sizetime relation shown compatible fits with the situation where was observed a decrease static state of the characteristic diameters reaching the grinding limit. From the fits of the time-size relation was possible to determine a constant ′ that characterizes the resistance to fragmentation of the material depending on the grinding conditions studied. The values of this constant showed that materials more resistant to fragmentation have the smaller ′ values, ranging between 0.96 and 2.6 g/J for the limestone and from 0,06 to 0.53 g/J to quartz. It was concluded that the kinetic model was incompatible with ultrafine grinding, due to the presence of significant events of multi-particle interactions and agglomeration, which was confirmed by variation in the uniformity index (′) in milling time function. Energetic models complemented each other for description of the experimental results. Ready an intermediate model which consider a size reduction rate as a power function with an exponent η and a parameter (l) representing the grinding limit is the most recommended for the representation of the ultrafine grinding processes of industrial minerals.

<p>Ultrafine particles (UFP) emitted by traffic have been associated with health risks for people living and working near major roadways. Studies have shown that people living in near-roadway communities experience higher risk of aggravated asthma, respiratory diseases and even childhood leukemia. Sharp concentration gradients of UFP have been reported near major highways with the concentration decreasing rapidly away from the road. Dispersion of UFP downwind of a road depends on many parameters, such as the atmospheric stability and wind speed. Presence of different structures such as noise barriers and vegetation can greatly influence the dispersion and downwind concentrations of UFP. These structures can block the traffic emissions and increase vertical mixing. In addition, vegetation can reduce UFP by deposition processes. Two sets of experiments were conducted in this thesis to investigate the effect of barriers on UFP deposition and dispersion. </p><p>The first set of experiments was performed in a wind tunnel facility to address UFP deposition to vegetation barriers solely. Two analytical models were proposed to characterize UFP dry deposition to vegetation measured during the wind tunnel experiment. The first model was derived from the filtration theory to explain UFP dry deposition to pine and juniper branches. The model agrees well with the experimental data indicating that pine and juniper branches can be treated as fibrous filters. The fiber diameters of pine derived from the experimental data were also similar to the physical diameters of pine needles; thus, providing further evidence that vegetation can be regarded as fibers. The second model was derived from the continuity equation and can predict the branch-scale dry deposition of UFP using conventional canopy properties such as the drag coefficient and leaf area density. Both models agree with the measurement results to within 20%.</p><p>The second set of experiments was done in three near-roadway environments to investigate the effects of barriers on the dispersion and dry deposition of UFP. We used mobile and stationary measurements to obtain the spatial and temporal variability of UFP. Both mobile and stationary measurements indicated that vegetation and noise barriers can reduce downwind UFP concentrations through dispersion and dry deposition by 20-60 %. </p><p>In conclusion, the effect of barriers on UFP dispersion and deposition has been characterized in this thesis. Two analytical models were also proposed from the wind tunnel experiments to characterize dry deposition and agreed well with the measurement results. The analytical model could benefit future climate and air quality models.</p> / Dissertation

Ultrafine bubbles, often referred to as nanobubbles, have been used in various applications from environmental remediation to medicine. Even though the technology to generate ultrafine bubbles has been around for many years, the full potential of its applications has not been completely studied. This project seeks to study the use of ultrafine bubble technology for water treatment in combination with ozone gas. A factorial design experiment was chosen to test the effects of ultrafine bubbles on the concentration of an indicator organism, E. coli, in water as well as their effects on ozone gas being injected into water. Ozone gas or nitrogen gas was injected into water contaminated with E. coli as either ultrafine bubbles or fine bubbles as treatments for up to 60 minutes. Ultrafine bubbles were found to not have any significant effect on the concentration of E. coli in water. However, ultrafine bubbles did provide benefits when used in conjunction with ozone gas that regular, fine bubbles did not provide. The benefits included allowing the concentration of dissolved ozone in the water to decrease at a slower rate as well as allowing more ozone to dissolve into water at a higher rate than conventional methods of bubbling in ozone. While in this particular set of experiments the concentration of dissolved ozone in water didn't surpass 2 mg/L, which didn't allow for rapid disinfection and treatment of water, it is believed that with a more powerful ozone generator better results can be achieved. This project demonstrates the benefits and potential of injecting ozone gas as ultrafine bubbles into water as a way to effectively and efficiently disinfect and treat water.

Numerous studies have shown that respirable particles contribute to adverse human health outcomes including discomfort in irritated airways, increased asthma attacks, irregular heartbeat, non-fatal heart attacks, and even death. Particle emissions from diesel vehicles are a major source of airborne particles in urban areas. In response to energy security and global climate regulations, the use of biodiesel as an alternative fuel for petrodiesel has significantly increased in recent years. Particle emissions from diesel engines are highly dependent on fuel composition and, as such, the increased use of biodiesel in diesel vehicles may potentially change the concentration, size, and composition of particles in respirable air. One indicator used to evaluate the potential health risk of these particles to humans is particle diameter (Dp). Ultrafine particles (UFPs, Dp Current research in automotive emissions primarily focuses on particle emissions measured on a total particle mass (PM) basis from heavy-duty diesel vehicles. The nation's light-duty diesel fleet is, however, increasing; and because the mass of a UFP is much less than that of larger particles, the total PM metric is not sufficient for characterization of UFP emissions. As such, this research focuses on light-duty diesel engine transient UFP emissions, measured by particle number (PN), from petrodiesel, biodiesel, and blends thereof. The research objectives were to determine: 1) the difference in UFP emissions between petrodiesel and blends of waste vegetable oil-based biodiesel (WVO), 2) the differences between UFP emissions from blends of WVO and soybean oil-based biodiesel (SOY), and 3) the feasibility of using genetic programming (GP) to select the primary engine operating parameters needed to predict UFP emissions from different blends of biodiesel. The results of this research are significant in that: 1) Total UFP number emission rates (ERs) exhibited a non-monotonic increasing trend relative to biodiesel content of the fuel for both WVO and SOY that is contrary to the majority of prior studies and suggests that certain intermediate biodiesel bends may produce lower UFP emissions than lower and higher blends, 2) The data collected corroborate reports in the literature that fuel consumption of diesel engines equipped with pump-line-nozzle fuel injection systems can increase with biodiesel content of the fuel without operational changes, 3) WVO biodiesel blends reduced the overall mean diameter of the particle distribution relative to petrodiesel more so than SOY biodiesel blends, and 4) Feature selection using genetic programming (GP) suggests that the primary model inputs needed to predict total UFP emissions are exhaust manifold temperature, intake manifold air temperature, mass air flow, and the percentage of biodiesel in the fuel; These are different than inputs typically used for emissions modeling such as engine speed, throttle position, and torque suggesting that UFP emissions modeling could be improved by using other commonly measured engine operating parameters.

Ultrafine particles (UFPs) with diameters smaller than 100 nm are omnipresent in ambient air. They are important sources for fine particles produced through the agglomeration and/or vapor condensation. With their unique properties, UFPs have also been manufactured for industrial applications. But, from the toxicological and health perspective, ultrafine particles with high surface-to-volume ratios often have high bio-availability and toxicity. Many recent epidemiologic studies have evidence UFPs are highly relevant to human health and disease. In order to better investigate UFPs, better instrumentation and measurement techniques for UFPs are thus in need. The overall objective of this dissertation is to advance out current knowledge on UFPs generation and measurement. Accordingly, it has two major parts: (1) ultrafine particle generation for laboratory aerosol research via electrospray (ES), and (2) ultrafine particle measurement for ambient aerosol monitor and personal exposure study via the development of a cost-effective and compact electrical mobility particle sizer. In the first part, to provide monodisperse nanoparticles, a new single capillary electrospray with a soft X-ray photoionizer as a charge reduction scheme has been developed. The soft X-ray effects on electrospray operation, particle size distribution and particle charge reduction were evaluated. To generate ultrafine particles with sufficient mass concentration for exposure/toxicity study, a TSE twin-head electrospray (THES) was evaluated, as well. The configuration and operational variables of the studied THES has been optimized. Three different nanoparticle suspensions were sprayed to investigate material difference. In the second part, to develop a miniature electrical mobility based ultrafine particle sizer (mini e-UPS), a new mini-plate aerosol charger and a new mini-plate differential mobility analyzer (DMA) have been developed. The performances of mini-plate charger and mini-plate DMA were carefully evaluated for ultrafine particles, including intrinsic/extrinsic charging, extrinsic charge distribution, DMA sizing accuracy and DMA transfer function. A prototype mini e-UPS was then assembled and tested by laboratory generated aerosol. Also a constrained least square method was applied to recover the particle size distribution from the current measured by a mini Faraday Cage aerosol electrometer.