This thesis encompasses CO2 mitigation using three different processes: i) natural gas-fired combined cycle with chemical looping combustion (CLC), ii) trigeneration of electrical power, hydrogen and district heating with extended CLC, iii) steam-based gasification of biomass integrated in an advanced power cycle. In CLC, a solid oxygen carrier circulates between two fluidised-bed reactors and transports oxygen from the combustion air to the fuel; thus, the fuel is not mixed with air and an inherent CO2 separation occurs. In this thesis, CLC has been studied as an alternative process for CO2 capture in a natural gas-fired combined cycle (NGCC). The potential efficiency of such a process using a turbine inlet temperature of 1200 °C and a pressure ratio of 13 is between 52 and 53 % when including the penalty for CO2 compression to 110 bar. It is shown that this efficiency cannot be further improved by including an additional CO2 turbine. Two conceivable reactor designs for CLC in an NGCC are presented. Top-firing has been studied as an option to overcome a temperature limitation in the CLC reactor system. The degree of CO2 capture is shown versus the temperature in the CLC reactor and its combustion efficiency. CLC has the potential to reach both a higher efficiency and a higher degree of CO2 capture than conventional post combustion CO2 capture technique. However, further research is needed to solve technical problems as, for example, temperature limitations in the reactor to reach this potential. Extended CLC (exCLC) is introduced, in which hydrogen is not only produced but also inherently purified. The potential efficiency of a novel tri-generation process for hydrogen, electricity and district heating using exCLC for CO2 capture is investigated. The results show that a thermal efficiency of about 54% might be achieved. A novel power process named evaporative biomass air turbine (EvGT-BAT) for biomass feedstock is presented. This process contains a steam-based gasification of biomass, which is integrated in an externally fired gas turbine cycle with top-firing. In the EvGT-BAT process, the steam-based gasification is conducted in an entrained-flow tubular reactor that is installed in the SFC as a heat exchanger. The EvGT-BAT process has the potential to generate electrical power from biomass with an efficiency of 41 %.

Carbon dioxide is considered to be the major source of GHG responsible for global warming; man-made CO₂ contributes approximately 63. 5% to all greenhouse gases. The cement industry is responsible for approximately 5% of global anthropogenic carbon dioxide emissions emitting nearly 900 kg of CO₂ for every 1000 kg of cement produced! Amine absorption processes in particular the monoethanolamine (MEA) based process, is considered to be a viable technology for capturing CO₂ from low-pressure flue gas streams because of its fast reaction rate with CO₂ and low cost of raw materials compared to other amines. However, MEA absorption process is associated with high capital and operating costs because a significant amount of energy is required for solvent regeneration and severe operating problems such as corrosion, solvent loss and solvent degradation. This research was motivated by the need to design size and cost analysis of CO₂ capture process from cement industry. MEA based absorption process was used as a potential technique to model CO₂ capture from cement plants. In this research four cases were considered all to reach a CO₂ purity of 98% i) the plant operates at the highest capacity ii) the plant operates at average load iii) the plant operates at minimum operating capacity and iv) switching to a lower carbon content fuel at average plant load. A comparison among four cases were performed to determine the best operating conditions for capturing CO₂ from cement plants. A sensitivity analysis of the economics to the lean loading and percent recovery were carried out as well as the different absorber and striper tray combinations.

The Solid Oxide Fuel Cell (SOFC) is a promising technology for electricity generation. It converts the chemical energy of the fuel gas directly to electricity energy and therefore, very high electrical efficiencies can be achieved. The high operating temperature of the SOFC also provides excellent possibilities for cogeneration applications. In addition to producing power very efficiently, the SOFC has the potential to concentrate CO₂ with a minimum of an overall efficiency loss. Concentration of CO₂ is a desirable feature of a power generation process so that the CO₂ may be subsequently sequestered thus preventing its contribution to global warming. The primary purpose of this research project was to investigate the role of the SOFC technology in power generation processes and explore its potential for CO₂ capture in power plants. <br /><br /> This thesis introduces an AspenPlus^TM SOFC stack model based on the natural gas feed tubular internal reforming SOFC technology. It was developed utilizing existing AspenPlus^TM functions and unit operation models. This SOFC model is able to provide detailed thermodynamic and parametric analysis of the SOFC operation and can easily be extended to study the entire process consisting of the SOFC stack and balance of plant. <br /><br /> Various SOFC-based power generation cycles were studied in this thesis. Various options for concentrating CO₂ in these power generation systems were also investigated and discussed in detail. All the processes simulations were implemented in AspenPlus^TM extending from the developed natural gas feed tubular SOFC stack model. The study shows that the SOFC technology has a promising future not only in generating electricity in high efficiency but also in facilitating CO₂ concentration, but the cost of the proposed processes still need be reduced so SOFCs can become a technical as well as economic feasible solution for power generation.

A multi-period optimal energy planning program for Ontario has been developed in mixed-integer non-linear programming using General Algebraic Modeling System, GAMS. The program applies both time-dependent and time-independent constraints. These include, but not limited to, construction time, fluctuation of fuel prices, and CO2 emission reduction target. It also offer flexibility of fuel balancing and fuel switching of the existing boilers and option purchasing of Carbon credit if the reduction target is not achievable. The objective function incorporates all these constraints as well as minimizes over all the cost of electricity and meets the projected electricity demand over the 30 years horizon. A number of Ontario study cases are performed utilizing this 30 years model. These cases include a number of CO2 emission reduction target from 6% to 75% below that of 1990 levels by 2014, doubling of natural gas over the forecasted price in 2020, an arbitrary year. A study case in appliance with the Environmental Protection Act where no new or existing coal-fired power stations are available after 2014, as well as study cases where no new nuclear power stations are available. The overall cost of the electricity for different CO2 emission reduction targets increases linearly with slope of ~ 5. The fuel switching, fuel balancing for coal stations, and retrofitting of the carbon capture and storage are the main strategy in order to keep the cost of electricity relative low and satisfy the CO2 emission constraints. Nuclear power is an essential supply technology to the fleet especially when CO2 emission is concerned. An additional 248 Mt of CO2 emission is observed over the reference case when no new nuclear supply is offered. Eliminating all coal technologies by 2014 in accordance to the Environmental Protection Act may also reduce the CO2 emission with less additional expenditure normally associated with the emission reduction processes. This however also reduces the energy port folio diversity, forcing the system to depend on a smaller group of supply technologies and decreasing the reliability of the system overall. These results help us better understand the factors affecting the fleet’s structure. It may also help plan the energy direction of Ontario and perhaps serve as an example for other provinces, territories, states, and even countries.

In Canada, coal-fired power plants are the largest anthropogenic point sources of atmospheric CO₂. The most promising near-term strategy for mitigating CO₂ emissions from these facilities is the post-combustion capture of CO₂ using MEA (monoethanolamine) with subsequent geologic sequestration. While MEA absorption of CO₂ from coal-derived flue gases on the scale proposed above is technologically feasible, MEA absorption is an energy intensive process and especially requires large quantities of low-pressure steam. It is the magnitude of the cost of providing this supplemental energy that is currently inhibiting the deployment of CO₂ capture with MEA absorption as means of combatting global warming. The steam cycle of a power plant ejects large quantities of low-quality heat to the surroundings. Traditionally, this waste has had no economic value. However, at different times and in different places, it has been recognized that the diversion of lower quality streams could be beneficial, for example, as an energy carrier for district heating systems. In a similar vein, using the waste heat from the power plant steam cycle to satisfy the heat requirements of a proposed CO₂ capture plant would reduce the required outlay for supplemental utilities; the economic barrier to MEA absorption could be removed. In this thesis, state-of-the-art process simulation tools are used to model coal combustion, steam cycle, and MEA absorption processes. These disparate models are then combined to create a model of a coal-fired power plant with integrated CO₂ capture. A sensitivity analysis on the integrated model is performed to ascertain the process variables which most strongly influence the CO₂ energy penalty. From the simulation results with this integrated model, it is clear that there is a substantial thermodynamic advantage to diverting low-pressure steam from the steam cycle for use in the CO₂ capture plant. During the course of the investigation, methodologies for using Aspen Plus® to predict column pressure profiles and for converging the MEA absorption process flowsheet were developed and are herein presented.

Carbon dioxide is considered to be the major source of GHG responsible for global warming; man-made CO₂ contributes approximately 63. 5% to all greenhouse gases. The cement industry is responsible for approximately 5% of global anthropogenic carbon dioxide emissions emitting nearly 900 kg of CO₂ for every 1000 kg of cement produced! Amine absorption processes in particular the monoethanolamine (MEA) based process, is considered to be a viable technology for capturing CO₂ from low-pressure flue gas streams because of its fast reaction rate with CO₂ and low cost of raw materials compared to other amines. However, MEA absorption process is associated with high capital and operating costs because a significant amount of energy is required for solvent regeneration and severe operating problems such as corrosion, solvent loss and solvent degradation. This research was motivated by the need to design size and cost analysis of CO₂ capture process from cement industry. MEA based absorption process was used as a potential technique to model CO₂ capture from cement plants. In this research four cases were considered all to reach a CO₂ purity of 98% i) the plant operates at the highest capacity ii) the plant operates at average load iii) the plant operates at minimum operating capacity and iv) switching to a lower carbon content fuel at average plant load. A comparison among four cases were performed to determine the best operating conditions for capturing CO₂ from cement plants. A sensitivity analysis of the economics to the lean loading and percent recovery were carried out as well as the different absorber and striper tray combinations.

The Solid Oxide Fuel Cell (SOFC) is a promising technology for electricity generation. It converts the chemical energy of the fuel gas directly to electricity energy and therefore, very high electrical efficiencies can be achieved. The high operating temperature of the SOFC also provides excellent possibilities for cogeneration applications. In addition to producing power very efficiently, the SOFC has the potential to concentrate CO₂ with a minimum of an overall efficiency loss. Concentration of CO₂ is a desirable feature of a power generation process so that the CO₂ may be subsequently sequestered thus preventing its contribution to global warming. The primary purpose of this research project was to investigate the role of the SOFC technology in power generation processes and explore its potential for CO₂ capture in power plants. <br /><br /> This thesis introduces an AspenPlus^TM SOFC stack model based on the natural gas feed tubular internal reforming SOFC technology. It was developed utilizing existing AspenPlus^TM functions and unit operation models. This SOFC model is able to provide detailed thermodynamic and parametric analysis of the SOFC operation and can easily be extended to study the entire process consisting of the SOFC stack and balance of plant. <br /><br /> Various SOFC-based power generation cycles were studied in this thesis. Various options for concentrating CO₂ in these power generation systems were also investigated and discussed in detail. All the processes simulations were implemented in AspenPlus^TM extending from the developed natural gas feed tubular SOFC stack model. The study shows that the SOFC technology has a promising future not only in generating electricity in high efficiency but also in facilitating CO₂ concentration, but the cost of the proposed processes still need be reduced so SOFCs can become a technical as well as economic feasible solution for power generation.

As reserves of conventional crude oil are depleted, there is a growing need to develop unconventional oils such as heavy oil and bitumen from oil sands. In terms of recoverable oil, Canadian oil sands are considered to be the second largest oil reserves in the world. However, the upgrading of bitumen from oil sands to synthetic crude oil (SCO) requires nearly ten times more hydrogen (H₂) than the conventional crude oils. The current H₂ demand for oil sands operations is met mostly by steam reforming of natural gas. With the future expansion of oil sands operations, the demand of H₂ for oil sand operations is likely to quadruple in the next decade. As natural gas reforming involves significant carbon dioxide (CO₂) emissions, this sector is likely to be one of the largest emitters of CO₂ in Canada. <br> <br>In the current H₂ plants, CO₂ emissions originate from two sources, the combustion flue gases from the steam reformer furnace and the off-gas from the process (steam reforming and water-gas shift) reactions. The objective of this study is to develop a process that captures CO₂ at minimum energy penalty in typical H₂ plants. <br> <br>The approach is to look at the best operating conditions when considering the H₂ and steam production, CO₂ production and external fuel requirements. The simulation in this study incorporates the kinetics of the steam methane reforming (SMR) and the water gas shift (WGS) reactions. It also includes the integration of CO₂ capture technologies to typical H₂ plants using pressure swing adsorption (PSA) to purify the H₂ product. These typical H₂ plants are the world standard of producing H₂ and are then considered as the base case for this study. The base case is modified to account for the implementation of CO₂ capture technologies. Two capture schemes are tested in this study. The first process scheme is the integration of a monoethanolamine (MEA) CO₂ scrubbing process. The other scheme is the introduction of a cardo polyimide hollow fibre membrane capture process. Both schemes are designed to capture 80% of the CO₂ from the H₂ process at a purity of 98%. <br> <br>The simulation results show that the H₂ plant with the integration of CO₂ capture has to be operated at the lowest steam to carbon (S/C) ratio, highest inlet temperature of the SMR and lowest inlet temperatures for the WGS converters to attain lowest energy penalty. H₂ plant with membrane separation technology requires higher electricity requirement. However, it produces better quality of steam than the H₂ plant with MEA-CO₂ capture process which is used to supply the electricity requirement of the process. Fuel (highvale coal) is burned to supply the additional electricity requirement. The membrane based H₂ plant requires higher additional electricity requirement for most of the operating conditions tested. However, it requires comparable energy penalty than the H₂ plant with MEA-CO₂ capture process when operated at the lowest energy operating conditions at 80% CO₂ recovery. <br> <br>This thesis also investigates the sensitivity of the energy penalty as function of the percent CO₂ recovery. The break-even point is determined at a certain amount of CO₂ recovery where the amount of energy produced is equal to the amount of energy required. This point, where no additional energy is required, is approximately 73% CO₂ recovery for the MEA based capture plant and 57% CO₂ recovery for the membrane based capture plant. <br> <br>The amount of CO₂ emissions at various CO₂ recoveries using the best operating conditions is also presented. The results show that MEA plant has comparable CO₂ emissions to that of the membrane plant at 80% CO₂ recovery. MEA plant is more attractive than membrane plant at lower CO₂ recoveries.

A multi-period optimal energy planning program for Ontario has been developed in mixed-integer non-linear programming using General Algebraic Modeling System, GAMS. The program applies both time-dependent and time-independent constraints. These include, but not limited to, construction time, fluctuation of fuel prices, and CO2 emission reduction target. It also offer flexibility of fuel balancing and fuel switching of the existing boilers and option purchasing of Carbon credit if the reduction target is not achievable. The objective function incorporates all these constraints as well as minimizes over all the cost of electricity and meets the projected electricity demand over the 30 years horizon. A number of Ontario study cases are performed utilizing this 30 years model. These cases include a number of CO2 emission reduction target from 6% to 75% below that of 1990 levels by 2014, doubling of natural gas over the forecasted price in 2020, an arbitrary year. A study case in appliance with the Environmental Protection Act where no new or existing coal-fired power stations are available after 2014, as well as study cases where no new nuclear power stations are available. The overall cost of the electricity for different CO2 emission reduction targets increases linearly with slope of ~ 5. The fuel switching, fuel balancing for coal stations, and retrofitting of the carbon capture and storage are the main strategy in order to keep the cost of electricity relative low and satisfy the CO2 emission constraints. Nuclear power is an essential supply technology to the fleet especially when CO2 emission is concerned. An additional 248 Mt of CO2 emission is observed over the reference case when no new nuclear supply is offered. Eliminating all coal technologies by 2014 in accordance to the Environmental Protection Act may also reduce the CO2 emission with less additional expenditure normally associated with the emission reduction processes. This however also reduces the energy port folio diversity, forcing the system to depend on a smaller group of supply technologies and decreasing the reliability of the system overall. These results help us better understand the factors affecting the fleet’s structure. It may also help plan the energy direction of Ontario and perhaps serve as an example for other provinces, territories, states, and even countries.

The use of novel hyperbranched aminosilica (HAS) materials created through the ring-opening polymerization of aziridine from mesoporous silica supports was proposed for the adsorption of CO2 from dilute sources. The limits of the adsorptive performance of these adsorbents were investigated via the preparation of sets of materials with a range of aminopolymer loadings on several different silica supports with different pore space characteristics. Relationships were determined between the materials' amine loadings and the CO2 adsorption performance. Adsorbents with substantial remaining pore volume displayed universal adsorption kinetics when normalized by amine loading. However, materials with blocked pores displayed substantially slower adsorption kinetics due to hindered mass transfer. In both humid and dry conditions, the HAS adsorbent was found to have a surprisingly large CO2 capacity in light of the 250-fold reduction in CO2 partial pressure from 10% CO2 (flue gas application) to 400 ppm CO2 (air capture application). Finally, a new series of linear aminosilicas was created through the reaction of existing aminosilicas with N-protected-aziridines. Specifically, reaction of aminosilane-functionalized silicas with N-methylaziridine resulted in the linear growth of methylaminoethyl groups, effectively increasing the amine loading of the adsorbent by a stoichiometric amount of an additional amine per attached silane.