A dissertation submitted to the Faculty of Engineering and the Built Environment, University of the Witwatersrand, Johannesburg, in partial fulfilment of the requirements for the degree of Master of Science in Engineering, 2016 / Global climate change is among the major challenges the world is facing today, and can be attributed to enhanced concentrations of Greenhouse Gases (GHG), such as carbon dioxide (CO2), in the atmosphere. Therefore, there is an urgent need to mitigate CO2 emissions, and carbon capture and storage (CCS) is amongst the possible options to reduce CO2 emissions. Against this background, this work investigated the synthesis and performance evaluation of Polyaspartamide (PAA) adsorbent for CO2 capture. In particular, the effect of the presence of water-soluble amines in the amine-grafted poly-succinimide (PSI) (referred to as Polyaspartamide (PAA) adsorbent), was investigated. Methyl Amine (MA) and Mono-Ethanol Amine (MEA) were employed as water-soluble amines and the effect of changes in their concentration on CO2 adsorption capacity was investigated as well. Water-soluble amines were incorporated to allow water solubility of the adsorbent paving the way for freeze-drying to improve the geometric structure (surface area, pore volume and pore size) of the adsorbent. Initially, the PSI was loaded with Ethylenediamine (EDA), forming PSI-EDA. The water-soluble amines were grafted to PSI-EDA, with the EDA added to improve the chemical surface of the adsorbent for CO2 capture. NMR and FTIR analyses were performed and confirmed the presence of MA and MEA amine groups in the PAA, thereby indicating the presence of the grafted amines on the backbone polymer. BET analysis was performed and reported the pore volume, pore size and surface area of the freeze-dried material. It was observed that the physical properties did not change significantly after the freeze-drying compared to literature where freeze-drying was not employed. An increase in adsorption capacity with an increase in MA and MEA concentrations in MA-PAA and MEA-PAA samples was observed. At low amine concentrations (20% amine and 80% EDA grafted), MEA-PAA was observed to exhibit higher adsorption capacity compared to the MA-PAA samples. At high amine (100% amine grafted) concentrations, MA-PAA samples displayed higher adsorption capacity. Three runs were performed on each sample and the results obtained were reproducible. The best adsorption capacity obtained was 44.5 g CO2/kg Ads. Further work was then performed to understand the effects of operating variables on CO2 adsorption as well as the interactive effect using the Response Surface Methodology approach. The experiments were done by use of CO2 adsorption equipment attached to an ABB gas analyzer. A central composite design of experiment method with a total of 20 experiments was employed to investigate three factors, namely, temperature, pressure and gas flow rate. Six regression models were drawn up and mean error values computed by use of Matlab, followed by response surfaces as well as contours, showing the influence of the operating variables on the adsorption capacity as well as interaction of the factors were then drawn up. The results obtained displayed that each of the factors investigated, temperature, pressure and gas flowrate had an incremental effect on the adsorption capacity of PAA, that is, as each factor was increased, the adsorption capacity increased up to a point where no more increase occurred. Adsorption was seen to increase for both an increase in gas flowrate and adsorption pressure to a maximum, thereafter it starts to decrease. A similar trend was observed for the interaction between temperature and pressure. However, the interaction between gas flowrate and temperature was such that, initially as the temperature and the gas flowrate increase, the adsorption capacity increases to a maximum, thereafter, the temperature seizes to have an effect on the adsorption capacity with a combined effect of decreasing temperature and increasing gas flowrate resulting in a further increase in adsorption capacity. It was confirmed that the operating variables as well as the flow regime have an effect on the CO2 adsorption capacity of the novel material. The highest adsorption capacity was obtained in the pressure range 0.5 bar to 1.7 bar coinciding with the temperature range of 10 oC to 45 oC. The interaction of gas flowrate and adsorption pressure was such that the highest adsorption capacity is in the range 0.8 bar to 1.5 bar which coincides with the gas flowrate range from 35 ml / min to 60 ml / min. In conclusion, the best adsorption capacity of 44.5 g / kg via the TGA and 70.4 g / kg via the CO2 adsorption equipment was obtained from 100 % MA grafted PSI. / GR2016

Vinyltrialkoxysilanes are grafted onto polyolefins via a radical mechanism; in a subsequent step, the pendant alkoxysilanes hydrolyze and condense upon exposure to water, resulting formation of crosslinks. Straight chain hydrocarbons were used as model compounds to investigate the regioselectivity of vinyltrimethoxysilane grafting. To stabilize the water-sensitive grafted products, the methoxy groups were substituted using phenyllithium. It was found that this reaction must be carried out for a minimum of three days to ensure full substitution. The grafted products were then separated on a weight basis using semi-preparative HPLC. Analysis of the di-grafted fraction using edited HSQC and HSQC-TOCSY NMR showed that radical propagation occurs via 1,4- and 1,5-intramolecular hydrogen shifts along the hydrocarbon backbone, resulting in multiple grafts per backbone. Post-combustion carbon capture targets CO₂ emissions from large point sources for capture and sequestration. A new class of potential carbon capture agents known as reversible ionic liquids (RevILs) has been synthesized and evaluated in terms of potential performance parameters (e.g. CO₂ capacity, viscosity, enthalpy of regeneration). These RevILs are silylated amines, which react with CO₂ to form a salt comprising an ammonium cation and a carbamate anion that is liquid at room temperature. Structural modifications of the basic silylamine skeleton result in drastic differences in the performance of the resulting RevIL. Systematic variation of the silylated amines allowed determination of a structure-property relationship, and continued iterations will allow development of an ideal candidate for scale-up. The properties and potential applications of gold nanoparticles (AuNP) are highly dependent on their size and shape. These properties are commonly controlled during liquid-phase synthesis through the use of capping agents, which must be removed following synthesis. Reverse micelles can also be used to control the morphology of AuNP during their synthesis. When RevILs are used in the formation of these reverse micelles, either as the disperse phase or as the surfactant, the built-in switch can be used to release the nanoparticles following their synthesis. This release on command could decrease the post-synthetic steps required to clean and purify AuNP prior to use. We have successfully synthesized AuNP using a number of different RevILs.

Thesis (M.E.S.)--The Evergreen State College, 2007. / Title from title screen viewed 1/17/2008. Includes bibliographical references (p. 123-126).

Thesis (Ph.D.)--Massachusetts Institute of Technology, Engineering Systems Division, Technology and Policy Program, 2007. / Title from document title page. Includes bibliographical references. Available in PDF format via the World Wide Web.

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This paper models the supply curve of carbon sequestration on Pacific Northwest rangelands. Rangeland managers have the ability to sequester carbon in agricultural soils by implementing alternative management practices on their farms. Their low adoption rate in practice suggests a high opportunity cost associated with their implementation. To increase their adoption, a payment for ecosystem services plan is proposed, where the public compensates farms for lost profits. The TOA-MD model is used to estimate the resulting sequestration incentivized by payments for soil carbon sequestration. Methodological questions of geographical stratification and estimating variation from available data are tested. Sensitivity analysis is also run on key assumptions in the study. Results show that while the economic potential of both systems is much lower than the technical potential, at reasonable CO��� payment levels rangeland sequestration could be a significant mitigation strategy for Pacific Northwest states. / Graduation date: 2012

Of all the strategies to reduce carbon emissions, carbon dioxide (CO₂) geological sequestration is an immediately available option for removing large amounts of the gas from the atmosphere. However, our understanding of the transition behavior between Forchheimer and Darcy flow through porous media during CO₂ injection is currently very limited. In addition, the kinetic mass transfer of SO₂ and CO₂ from CO₂ stream to the saline and the fully coupling between the changes of porosity and permeability and multiphase flow are two significant dimensions to investigate the brine acidification and the induced porosity and permeability changes due to SO₂ co-injection with CO₂. Therefore, this dissertation develops a multiphase flow, contaminant transport and geochemical model which includes the kinetic mass transfer of SO₂ into deep saline aquifers and obtains the critical Forchheimer number for both water and CO₂ by using the experimental data in the literature. The critical Forchheimer numbers and the multiphase flow model are first applied to analyze the application problem involving the injection of CO₂ into deep saline aquifers. The results show that the Forchheimer effect would result in higher displacement efficiency with a magnitude of more than 50% in the Forchheimer regime than that for Darcy flow, which could increase the storage capacity for the same injection rate and volume of a site. Another merit for the incorporation of Forchheimer effect is that more CO₂ would be accumulated in the lower half of the domain and lower pressure would be imposed on the lower boundary of the cap-rock. However, as a price for the advantages mentioned above, the injection pressure required in Forchheimer flow would be higher than that for Darcy flow. The fluid flow and contaminant transport and geochemical model is then applied to analyze the brine acidification and induced porosity and permeability changes due to SO₂ co-injection. The results show that the co-injection of SO₂ with CO₂ would lead to a substantially acid zone near the injecting well and it is important to include the kinetic dissolution of SO₂ from the CO₂ stream to the water phase into the simulation models, otherwise considerable errors would be introduced for the equilibrium assumption. This study provides a useful tool for future analysis and comprehension of multiphase Darcy-Forchheimer flow and brine acidification of CO₂ injection into deep saline aquifers. Results from this dissertation have practical use for scientists and engineers concerned with the description of flow behavior, and transport and fate of SO₂ during SO₂ co-injection with CO₂ in deep saline aquifers.

In my thesis, I address two important issues: (i) the creation of a price signal through the use of carbon markets (or cap-and-trade schemes) and (ii) the necessity to reach a global agreement on greenhouse gas emission reduction policies. It consists of three separate papers. Chapters 2 and 3 of this thesis emphasize theoretically and empirically the fact that achieving international cooperation on climate change is very difficult. Chapter 3 suggests that the global nature of the climate change problem and the design of climate agreements (i.e. the means available to reduce CO2 emissions) may explain this failure. Chapter 2 shows theoretically that asymmetric information between countries may exacerbate the free-rider problem. These two chapters also provide some possible solutions to the lack of international cooperation. To address the issue of information asymmetry, chapter 2 proposes the creation of institutions in charge of gathering and certifying countries' private information before environmental negotiations. If achieving international cooperation is still not possible, chapter 3 suggests that regional cooperation may supplement global treaties. Chapter 1 presents an example of such a regional agreement to reduce CO2 emissions. The EU emissions trading system is a cornerstone of the European Union's policy to combat climate change. However, as it is highlighted in chapter 1, the design of such regional carbon markets really matters for their success in reducing carbon emissions. This chapter shows the interactions between intertemporal permit trading and the incentives of firms to undertake long-term investments in abatement technologies. / Doctorat en Sciences économiques et de gestion / info:eu-repo/semantics/nonPublished

In the literature, some studies argue that affluence and the financial sector encourages low-carbon investments which result in lower emissions while others find that they enhance emissions. Contemporary studies barely consider agriculture, employment generation and the degree of financial development as determinants of emissions. In view of these, the thesis investigates the impact of economic and financial development on CO2 emissions in sub-Saharan Africa (SSA). Applying the EKC and STIRPAT framework, the study modelled three functional forms which were estimated using an unbalanced panel data of 45 SSA countries by employing static and dynamic analytical methods. The models were re-estimated for 24 low (LIC), 13 lower-middle (LMIC), six upper-middle (UMIC) and two high-income countries (HIC). The study found evidence that empirical results differ in terms of the (sub-) sample of countries, estimation methods and functional forms. In detail, the study found different CO2 emissions-economic development relationships for the income groups. However, there is evidence of a linkage between later developments of the economies with lower emissions in LIC and UMIC while this linkage does not exist in LMIC and HIC. The study also found that financial development lowers CO2 in UMIC while it enhances emissions in LIC, LMIC and HIC. Despite this, there is evidence of a linkage between later developments of financial sectors with higher emissions in LIC and HIC and a linkage between later developments of financial sectors with lower CO2 in UMIC in SSA meanwhile no linkage was found for LMIC. The study concludes that not all economic development increases the level of CO2 emissions and not all financial development limits CO2 emissions in SSA during the study period. Generally, the main contributory variables to CO2 emissions are income, trade openness, energy consumption, population density and domestic credit to private sector to GDP. The main reducing factors of CO2 emissions are agriculture and official exchange rate. The thesis recommends that SSA needs to be more responsive to a cleaner CO2 environment by moving away from the conduct of unclean development strategy to intensified green investments. / Economics / D. Phil. (Economics)

L'objectif de notre thèse vise à évaluer les résultats engrangés par les marchés du carbone. Afin de pouvoir explorer différents aspects des marchés du carbone à un niveau mondial et en raison de la diversité des instruments qui se cachent derrière ce vocable, nous avons choisi de réaliser une thèse par article. Sur base de nos analyses empiriques nous avons pu vérifier dans quelle mesure les avantages et les limites théoriques des marchés du carbone se sont réalisés en pratique. <p><p>Une hypothèse forte des marchés du carbone dotés d’un système de plafonnement est qu’ils permettraient de garantir le respect des objectifs climatiques. Cette hypothèse ne s’est pas révélée exacte. En générant plus d’un milliard de crédits, dont un nombre important de crédits issus de projets, et en ne parvenant pas à empêcher des défections, le système mis en place par le Protocole de Kyoto n’est pas parvenu à garantir le plafonnement des émissions dans les pays développés. Il en va de même pour les systèmes liés à Kyoto comme le système communautaire d'échange de quotas d'émissions (SCEQE).<p><p>Dans la plupart des configurations des règles ad hoc et peu transparentes ont nui à l’objectif environnemental. La comptabilité commune de différents gaz à effet de serre, malgré des incertitudes importantes sur les pouvoirs de réchauffement globaux a également été néfaste à l'intégrité du système. <p><p>Le lien à des mécanismes de projets trouvant leur légitimité dans une preuve de l’additionnalité souvent floue demeure problématique. Notre analyse a ainsi mis en avant la problématique de l'enregistrement de projets hydrauliques dont la décision de construction est antérieure aux marchés du carbone.<p><p>En théorie, le mécanisme d’échange a pour conséquence que les acteurs confrontés à des coûts de réduction faibles soient encouragés à réduire leurs émissions. Dans la pratique, notre analyse montre que peu d’acteurs connaissent leur coût de réduction marginal, empêchant dès lors la concrétisation de cet idéal d’une réduction au moindre coût. Nous avons aussi mis en avant le fait qu’un prix identique par tonne de CO2 réduite n’est pas adapté au soutien de technologies nouvelles, souvent plus onéreuses au début de leur cycle de développement. <p><p>Finalement, un des principaux mérites des marchés du carbone a peut-être été leur acceptabilité auprès des décideurs politiques et économiques. Il est manifeste que les marchés permettent d'internaliser le carbone à un niveau international sans passer par une difficile harmonisation des politiques fiscales. C'est clairement une des raisons de leur adoption rapide et dans de nombreux pays.<p><p>Les marchés du carbone ont aussi joué un rôle important en matière de sensibilisation aux changements climatiques. Ils ont permis de faire progresser la comptabilité carbone et la compréhension des technologies sobres en carbone. <p><p>L’effondrement récent du prix du carbone montre que ce nouvel instrument qui, en théorie, est efficace pour atteindre un objectif de réduction prédéfini, ne permet pas, dans la pratique, par manque d’ambition ou en raison d’erreurs dans la conception, de financer la transition vers une nouvelle économie sobre en carbone. Il apparaît dès lors nécessaire de réformer cet instrument mais aussi de développer progressivement des alternatives afin de ne pas uniquement faire reposer la réussite de l’atteinte des objectifs climatiques sur les seuls marchés du carbone et ainsi augmenter la résilience des politiques climatiques aux aléas de marchés financiers, par ailleurs eux-mêmes soumis à de nombreux tourments depuis 2008.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished