A reaction engineering approach to homogeneously catalyzed glycerol hydrochlorination

The production of biodiesel through transesterification has created a surplus of glycerol on the international market. In few years, glycerol has become an inexpensive and abundant raw material, subject to numerous plausible valorisation strategies. Glycerol hydrochlorination stands out as an economically attractive alternative to the production of biobased epichlorohydrin, an important raw material for the manufacturing of epoxy resins and plasticizers. Glycerol hydrochlorination using gaseous hydrogen chloride (HCl) was studied from a reaction engineering viewpoint. Firstly, a more general and rigorous kinetic model was derived based on a consistent reaction mechanism proposed in the literature. The model was validated with experimental data reported in the literature as well as with new data of our own. Semi-batch experiments were conducted in which the influence of the stirring speed, HCl partial pressure, catalyst concentration and temperature were thoroughly analysed and discussed. Acetic acid was used as a homogeneous catalyst for the experiments. For the first time, it was demonstrated that the liquid-phase volume undergoes a significant increase due to the accumulation of HCl in the liquid phase. Novel and relevant features concerning hydrochlorination kinetics, HCl solubility and mass transfer were investigated. An extended reaction mechanism was proposed and a new kinetic model was derived. The model was tested with the experimental data by means of regression analysis, in which kinetic and mass transfer parameters were successfully estimated. A dimensionless number, called Catalyst Modulus, was proposed as a tool for corroborating the kinetic model. Reactive flash distillation experiments were conducted to check the commonly accepted hypothesis that removal of water should enhance the glycerol hydrochlorination kinetics. The performance of the reactive flash distillation experiments were compared to the semi-batch data previously obtained. An unforeseen effect was observed once the water was let to be stripped out from the liquid phase, exposing a strong correlation between the HCl liquid uptake and the presence of water in the system. Water has revealed to play an important role also in the HCl dissociation: as water was removed, the dissociation of HCl was diminished, which had a retarding effect on the reaction kinetics. In order to obtain a further insight on the influence of water on the hydrochlorination reaction, extra semi-batch experiments were conducted in which initial amounts of water and the desired product were added. This study revealed the possibility to use the desired product as an ideal “solvent” for the glycerol hydrochlorination process. A co-current bubble column was used to investigate the glycerol hydrochlorination process under continuous operation. The influence of liquid flow rate, gas flow rate, temperature and catalyst concentration on the glycerol conversion and product distribution was studied. The fluid dynamics of the system showed a remarkable behaviour, which was carefully investigated and described. Highspeed camera images and residence time distribution experiments were conducted to collect relevant information about the flow conditions inside the tube. A model based on the axial dispersion concept was proposed and confronted with the experimental data. The kinetic and solubility parameters estimated from the semi-batch experiments were successfully used in the description of mass transfer and fluid dynamics of the bubble column reactor. In light of the results brought by the present work, the glycerol hydrochlorination reaction mechanism has been finally clarified. It has been demonstrated that the reactive distillation technology may cause drawbacks to the glycerol hydrochlorination reaction rate under certain conditions. Furthermore, continuous reactor technology showed a high selectivity towards monochlorohydrins, whilst semibatch technology was demonstrated to be more efficient towards the production of dichlorohydrins. Based on the novel and revealing discoveries brought by the present work, many insightful suggestions are made towards the improvement of the production of αγ-dichlorohydrin on an industrial scale.

Improvement of Energy Efficiency in a Gold Mining Industry: Case Study of a Russian Gold Mining Company

The issue of energy efficiency is attracting more and more attention of academia, business and policy makers worldwide due to increasing environmental concerns, depletion of non-renewable energy resources and unstable energy prices. The significant importance of energy efficiency within gold mining industry is justified by considerable energy intensity of this industry as well as by the high share of energy costs in the total operational costs. In the context of increasing industrial energy consumption energy efficiency improvement may provide significant energy savings and reduction of CO2 emission that is highly important in order to contribute to the global goal of sustainability. The purpose of this research is to identify the ways of energy efficiency improvement relevant for a gold mining company. The study implements single holistic case study research strategy focused on a Russian gold mining company. The research involves comprehensive analysis of company’s energy performance including analysis of energy efficiency and energy management practices. This study provides following theoretical and managerial contributions. Firstly, it proposes a methodology for comparative analysis of energy performance of Russian and foreign gold mining companies. Secondly, this study provides comprehensive analysis of main energy efficiency challenges relevant for a Russian gold mining company. Finally, in order to overcome identified challenges this research conceives a guidance for a gold mining company for implementation of energy management system based on the ISO standard.

Engineering an improved adenovirus packaging cell line

Recombinant human adenovirus (Ad) vectors are being extensively explored for their use in gene therapy and recombinant vaccines. Ad vectors are attractive for many reasons, including the fact that (1) they are relatively safe, based on their use as live oral vaccines, (2) they can accept large transgene inserts, (3) they can infect dividing and postmitotic cells, and (4) they can be produced to high titers. However, there are also a number of major problems associated with Ad vectors, including transient foreign gene expression due to host cellular immune responses, problems with humoral immunity, and the creation of replication competent adenoviruses (RCA). Most Ad vectors contain deletions in the E1 region that allow for insertion of a transgene. However, the E1 gene products are required for replication and thus must be supplied in trans by a helper ceillille that will allow for the growth and packaging of the defective virus. For this purpose the 293 cell line (Graham et al., 1977) is used most often; however, homologous recombination between the vector and the cell line often results in the generation of RCA. The presence of RCA in batches of adenoviral vectors for clinical use is a safety risk because tlley . may result in the mobilization and spread of the replication-defective vector viruses, and in significant tissue damage and pathogenicity. The present research focused on the alteration of the 293 cell line such that RCA formation can be eliminated. The strategy to modify the 293 cells involved the removal of the first 380 bp of the adenovirus genome through the process of homologous recombination. The first step towards this goal involved identifying and cloning the left-end cellular-viral jUl1ction from 293 cells to assemble sequences required for homologous recombination. Polymerase chain reaction (PCR) was performed to clone the junction, and the clone was verified through sequencing. The plasn1id PAM2 was then constructed, which served as the targeting cassette used to modify the 293 cells. The cassette consisted of (1) the cellular-viral junction as the left-end region of homology, (2) the neo gene to use for positive selection upon tranfection into 293 cells, (3) the adenoviral genome from bp 380 to bp 3438 as the right-end region of homology, and (4) the HSV-tk gene to use for negative selection. The plasmid PAM2 was linearized to produce a double strand break outside the region of homology, and transfected into 293 cells using the calcium-phosphate technique. Cells were first selected for their resistance to the drug G418, and subsequently for their resistance to the drug Gancyclovir (GANC). From 17 transfections, 100 pools of G418f and GANCf cells were picked using cloning lings and expanded for screening. Genomic DNA was isolated from the pools and screened for the presence of the 380 bps using PCR. Ten of the most promising pools were diluted to single cells and expanded in order to isolate homogeneous cell lines. From these, an additional 100 G41Sf and GANef foci were screened. These preliminary screening results appear promising for the detection of the desired cell line. Future work would include further cloning and purification of the promising cell lines that have potentially undergone homologous recombination, in order to isolate a homogeneous cell line of interest.

Investigating the potential of thecamoebians (testate amoebae) as bio-indicators of impact of oil sands mining operations on freshwater environments in Northeastern Alberta, Canada

Thecamoebian (testate amoeba) species diversity and assemblages in reclamation wetlands and lakes in northeastern Alberta respond to chemical and physical parameters associated with oil sands extraction. Ecosystems more impacted by OSPM (oil sands process-affected material) contain sparse, low-diversity populations dominated by centropyxid taxa and Arcella vulgaris. More abundant and diverse thecamoebian populations rich in difflugiid species characterize environments with lower OSPM concentrations. These shelled protists respond quickly to environmental change, allowing year-to-year variations in OSPM impact to be recorded. Their fossil record thus provides corporations with interests in the Athabasca Oil Sands with a potential means of measuring the progression of highlyimpacted aquatic environments to more natural wetlands. Development of this metric required investigation of controls on their fossil assemblage (e.g. seasonal variability, fossilization potential) and their biogeographic distribution, not only in the constructed lakes and wetlands on the oil sands leases, but also in natural environments across Alberta.

Introduction to engineering : a case study of an interdisciplinary course in Mathematics, Science and Technology

This thesis research was a qualitative case study of a single class of Interdisciplinary Studies: Introduction to Engineering taught in a secondary school. The study endeavoured to explore students' experiences in and perceptions of the course, and to investigate the viability of engineering as an interdisciplinary theme at the secondary school level. Data were collected in the form of student questionnaires, the researcher's observations and reflections, and artefacts representative of students' work. Data analysis was performed by coding textual data and classifying text segments into common themes. The themes that emerged from the data were aligned with facets of interdisciplinary study, including making connections, project-based learning, and student engagement and affective outcomes. The findings of the study showed that students were positive about their experiences in the course, and enjoyed its project-driven nature. Content from mathematics, physics, and technological design was easily integrated under the umbrella of engineering. Students felt that the opportunity to develop problem solving and teamwork skills were two of the most important aspects of the course and could be relevant not only for engineering, but for other disciplines or their day-to-day lives after secondary school. The study concluded that engineering education in secondary school can be a worthwhile experience for a variety of students and not just those intending postsecondary study in engineering. This has implications for the inclusion of engineering in the secondary school curriculum and can inform the practice of curriculum planners at the school, school board, and provincial levels. Suggested directions for further research include classroom-based action research in the areas of technological education, engineering education in secondary school, and interdisciplinary education.

Glacial stratigraphy and micromorphology of the Pine Point Pb-­‐Zn mining district, Northwest Territories

This investigation aims to gain a better understanding of the glacial history of the Pine Point Mining district, Northwest Territories, by examining the sedimentological properties of the glacial sediments including, geochemical analysis, heavy mineral concentrate analysis, clast macro-­‐fabrics, pebble lithologies, and micromorphological investigation. Four till units were identified, and three were associated with identified erosional bedrock features and streamlined landforms in the area, indicating a minimum of three ice flow directions. Sedimentological properties suggest that these units were all Type-­B tectomict/mélange till, emplaced as part of a soft subglacial deformable bed. The lack of ice-­‐marginal advance and retreat sequences within the studied till, suggests the Middle Wisconsinan Laurentide Ice margin was likely north and west of the Pine Point area, as opposed to along the margin of the Canadian Shield and Western Sedimentary Basin where it has been suggested to have existed.

Towards reverse engineering of Photosystem II: Synergistic Computational and Experimental Approaches

ABSTRACT Photosystem II (PSII) of oxygenic photosynthesis has the unique ability to photochemically oxidize water, extracting electrons from water to result in the evolution of oxygen gas while depositing these electrons to the rest of the photosynthetic machinery which in turn reduces CO2 to carbohydrate molecules acting as fuel for the cell. Unfortunately, native PSII is unstable and not suitable to be used in industrial applications. Consequently, there is a need to reverse-engineer the water oxidation photochemical reactions of PSII using solution-stable proteins. But what does it take to reverse-engineer PSII’s reactions? PSII has the pigment with the highest oxidation potential in nature known as P680. The high oxidation of P680 is in fact the driving force for water oxidation. P680 is made up of a chlorophyll a dimer embedded inside the relatively hydrophobic transmembrane environment of PSII. In this thesis, the electrostatic factors contributing to the high oxidation potential of P680 are described. PSII oxidizes water in a specialized metal cluster known as the Oxygen Evolving Complex (OEC). The pathways that water can take to enter the relatively hydrophobic region of PSII are described as well. A previous attempt to reverse engineer PSII’s reactions using the protein scaffold of E. coli’s Bacterioferritin (BFR) existed. The oxidation potential of the pigment used for the BFR ‘reaction centre’ was measured and the protein effects calculated in a similar fashion to how P680 potentials were calculated in PSII. The BFR-RC’s pigment oxidation potential was found to be 0.57 V, too low to oxidize water or tyrosine like PSII. We suggest that the observed tyrosine oxidation in BRF-RC could be driven by the ZnCe6 di-cation. In order to increase the efficiency of iii tyrosine oxidation, and ultimately oxidize water, the first potential of ZnCe6 would have to attain a value in excess of 0.8 V. The results were used to develop a second generation of BFR-RC using a high oxidation pigment. The hypervalent phosphorous porphyrin forms a radical pair that can be observed using Transient Electron Paramagnetic Resonance (TR-EPR). Finally, the results from this thesis are discussed in light of the development of solar fuel producing systems.

Engineering school notebook which belonged to S.D. Woodruff

Engineering school notebook which belonged to S.D. Woodruff. This book contains logarithm notes, plane trigonometry, surveying and content of land. The outer page is torn and the notebook is quite discoloured. This does not affect the text. It has no covers, n.d.

Engineering school notebook which belonged to S.D. Woodruf

Engineering school notebook which belonged to S.D. Woodruff. This book contains questions for exercise as well as other mathematical topics. It also contains a page which has the title “The Cataract of Niagara in North America” and quite a few pages of repetitive lines as in “writing lines”. Some of the pages are loose or torn and the notebook is discoloured. This does not affect the text. This book has no covers, n.d.

Union Pacific Railway from Kansas City , Omaha, St. Joseph to Denver, San Francisco, Portland, Helena, Butte, Boise, Leadville, Durango, Deadwood and all cities and mining camps in the west schedule

Union Pacific Railway from Kansas City , Omaha, St. Joseph to Denver, San Francisco, Portland, Helena, Butte, Boise, Leadville, Durango, Deadwood and all cities and mining camps in the west schedule, Jan. 15, 1882.

Estimate from the County of Welland to S.D. Woodruff for engineering services in marsh lands drainage for 1 year

Estimate from the County of Welland to S.D. Woodruff for engineering services in marsh lands drainage for 1 year, Dec. 1857.

Engineering services in marsh lands drainage for the months of October, November and December

Engineering services in marsh lands drainage for the months of October, November and December. This is signed by S.D. Woodruff, Dec. 31, 1856.