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.

Interactions of decision mechanisms in an entrepreneurial firm’s journey to become a major player in its industry

This study discusses the interactions of different decision-making mechanisms in the process of change of a successful entrepreneurial dairy firm in Vietnam. The purpose of the study is to construct a theoretical framework, which explains the interactions between effectual and causal decision-making processes in different phases of business, and to provide a real life example with practical recommendations for entrepreneurs and managers. In order to achieve this purpose, a preliminary theoretical framework was built, using process theories applied to different decision making modes, referred to as causation and effectuation. The case was studied through ethnographic research method, with three semi-structured interviews, one unstructured interview, secondary data and observations within four months in 2013-2014. After the data was analyzed, a modified framework was drawn from the result. The finding of this study shows that there was an interaction between effectual and causal decision-making processes in different stages of the company’s development. The entrepreneur applied effectual decision-making process to develop a unique business model and a new dairy market segment. However, when a new market demand arose, the company’s resources became insufficient, they thus had to shift to causation process to adapt to market change. Simultaneously, with better-accumulated resources, the entrepreneur continued the effectuation process to create another brand new dairy market segment. This study, thus, contributes to effectuation theory, emphasizing the necessity of combining effectual and causal decision-making processes in different phases of business. It is suggested that business would develop with an effectual process until a business model is viable for growth. It continues to use this process up to a certain degree. When the market changes, the company needs to collect more means to adapt to the changes. They need to set new goals and this is a shift to the use of causal process, which builds on prediction. It uses goals and teleology as driving mechanisms and tries to exploit and fill potential resource gaps to achieve these goals. At the same time, there are new iterations that look to establish new lines or types of business with the given means, which are now well established. This again employs effectual mechanisms, which are based on evolutionary process, until they reach the stage of viable tested business model. Moreover, this study hopes to provide know-how to entrepreneurs and managers of small companies in similar situations, suggesting how to combine effectual and causal decision-making processes to deal with various circumstances in different times.

The Role Of Social Networks In New Venture Internationalization: Case Of Russian And Finnish Firms

The purpose of current master thesis research is to investigate the role of social networks in internationalization of Russian and Finnish firms. Literature review of existing empirical researches on the topic is conducted in order to identify the gap, which is fulfilled by empirical research of 4 Russian and 1 Finnish firm that have established international operations no later than 8 years since their foundation. In-depth semi-structured interviews have shown that business network has been an influencing factor in firms’ internationalization and that even if social network is not the driver of internationalization, it becomes important when a company has established international presence and is working on its enlargement. The study has both theoretical and practical contribution by contributing to research of Russian and Finnish firms’ internationalization and by showing examples of successful foreign market entry of companies from different industries. General practical implication of current thesis is that it shows the efficient ways of entrepreneurs’ social network usage in business development in international scope.

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.

Determinants of bankruptcy protection duration for Canadian firms

The present thesis examines the determinants of the bankruptcy protection duration for Canadian firms. Using a sample of Canadian firms that filed for bankruptcy protection between the calendar years 1992 and 2009, we fmd that the firm age, the industry adjusted operating margin, the default spread, the industrial production growth rate or the interest rate are influential factors on determining the length of the protection period. Older firms tend to stay longer under protection from creditors. As older firms have more complicated structures and issues to settle, the risk of exiting soon the protection (the hazard rate) is small. We also find that firms that perform better than their benchmark as measured by the industry they belong to, tend to leave quickly the bankruptcy protection state. We conclude that the fate of relatively successful companies is determined faster. Moreover, we report that it takes less time to achieve a final solution to firms under bankrupt~y when the default spread is low or when the appetite for risk is high. Conversely, during periods of high default spreads and flight for quality, it takes longer time to resolve the bankruptcy issue. This last finding may suggest that troubled firms should place themselves under protection when spreads are low. However, this ignores the endogeneity issue: high default spread may cause and incidentally reflect higher bankruptcy rates in the economy. Indeed, we find that bankruptcy protection is longer during economic downturns. We explain this relation by the natural increase in default rate among firms (and individuals) during economically troubled times. Default spreads are usually larger during these harsh periods as investors become more risk averse since their wealth shrinks. Using a Log-logistic hazard model, we also fmd that firms that file under the Companies' Creditors Arrangement Act (CCAA) protection spend longer time restructuring than firms that filed under the Bankruptcy and Insolvency Act (BIA). As BIA is more statutory and less flexible, solutions can be reached faster by court orders.

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.

CEO Compensation, Compensation Risk, and Corporate Governance: Evidence from Technology Firms

Literature suggests that CEOs of technology firms earn higher pay than CEOs of non-technology firms. I investigate whether compensation risk explains the difference in compensation between technology firms and non-technology firms. Controlling for firm size and performance, I find that CEOs in technology firms have higher pay, but also have much higher compensation risk compared to non-technology firms. Compensation risk explains the major part of the difference in CEO pay. My study is consistent with the labor market economics view that CEOs earn competitive risk-adjusted total compensation.

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.

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.

Engineering services in marsh lands drainage for the months of January, February, March and April for Fred Holmes, Joseph Simpson, D. Davidson, Rose Osborne, Henry Wilson and William Baird

Engineering services in marsh lands drainage for the months of January, February, March and April for Fred Holmes, Joseph Simpson, D. Davidson, Rose Osborne, Henry Wilson and William Baird. This is signed by S.D. Woodruff, May 1, 1857.

Engineering services in marsh lands drainage for the months of May, June, July and August 1857 for Fred Holmes, Joseph Simpson and William Baird

Engineering services in marsh lands drainage for the months of May, June, July and August 1857 for Fred Holmes, Joseph Simpson and William Baird. This is signed by S.D. Woodruff, Aug. 31, 1857.

Drivers of Local Firms’ Focus on Internal R&D in Emerging Economies and Their International Performance

Grounded on the resource-based view of the firm, the study of this thesis investigates the effect of four internal and external factors – engineer intensity, location, affiliation with the government, government funding – on Chinese firms’ decision to either invest in internal R&D activities or external R&D and the effect of this decision on the firms’ international market success. In addition, the moderating role of the presence of foreign firms in China is examined. To understand these relationships, the thesis’ theorization focuses on the issue of how firms can combine optimally the two options – “internal R&D” and “external R&D”. In this regard I juxtapose internal R&D and external R&D and compare their advantages and disadvantages. To test my model, I apply panel data from the Annual Industrial Survey Database provided by the Chinese National Bureau of Statistics. My results show that three of the four investigated factors affect Chinese firms’ resource allocation decisions; and effective resource allocation decisions lead effectively to international market success, strengthened by the presence of foreign firms in China. Moreover the findings bear several theoretical and managerial contributions. First I propose the last dimension of the “VRIO framework” – “organization” – as an endogenous component of the VRIO framework, as my study investigated how firms can effectively combine resources to generate a competitive advantage in terms of international market success. Previous academic literature so far focused on examining whether internal and external R&D are complements or substitutes. My study fills a gap in the literature by investigating the determinants of the efficient combination of the two strategies and the outcome of the combination. One of the managerial implications is that Chinese firms can learn from foreign companies that are present in China.