Increased levels of carbon dioxide in the atmosphere are now widely attributed as a leading cause for global climate change. As such, research efforts into the capture and sequestration of CO2 from large point sources (flue gas capture) as well as the ambient atmosphere (air capture) are gaining increased popularity and importance. Supported amine materials have emerged as a promising class of materials for these applications. However, more fundamental research is needed before these materials can be used in a practically relevant process. The following areas are considered critical research needs for these materials: (i) process design, (ii) material stability, (iii) kinetics of adsorption and desorption, (iv) improved sorbent adsorption efficiency and (v) understanding the effects of water on sorbent adsorption behavior. The aim of the studies presented in this thesis is to further the scientific community’s understanding of supported amine adsorbents with respect to stability, adsorption efficiency and adsorption behavior with water.

Amine functionalized silicas are promising chemisorbent materials for post-combustion CO₂ capture due to the high density of active sites per unit mass of adsorbent that can be obtained by tuning the synthesis protocol, thus resulting in high equilibrium CO₂ adsorption capacities. However, when compared to physisorbents, they have a few disadvantages. Firstly, oxidative degradation of the amine groups reduces the lifetime of these adsorbent materials. Furthermore, rapid heat release following the reaction between amines and CO₂ results in large local temperature spikes which may adversely affect adsorption equilibria and kinetics. Thirdly, there is a lack of fundamental understanding of CO₂-amine adsorption thermodynamics, which is key to scaling up these materials to an industrial-scale adsorption process. In this dissertation the qualitative and quantitative understanding of these three critical aspects of aminosilica adsorbents have been furthered so these materials can be better evaluated and further tuned as adsorbents for post-combustion CO₂ capture applications.

Polymeric hollow fiber sorbents were functionalized with amine moieties for improving the carbon dioxide sorption capacity from flue gas to reduce the greenhouse gas emissions from coal-fired power plants. Three different experimental pathways were studied to form the amine-functionalized hollow fiber sorbents. Aminosilane functionalized cellulose acetate (CA) fibers, polyethyleneimine (PEI) functionalized polyamide-imide (PAI, Torlon® fibers and PEI post-infused and functionalized Torlon®-silica fibers were formed. CO₂ equilibrium sorption capacity data were collected by using the pressure decay sorption cell and thermal gravimetric analyzer. Other physio-chemical properties of the amine-functionalized fiber sorbents were characterized by using fourier-transform infrared spectroscopy, elemental analysis, and scanning electronic microscopy. Different reaction conditions were studied on the effect of sorption isotherms. Aminosilane-CA fibers were the first proof-of-concept for forming the amine functionalized polymer hollow fibers. PEI-PAI fibers were designed as a new method to reach enhanced sorption capacities than Aminosilane-functionalized CA fibers. PEI post-infused and functionalized Torlon®-silica fibers have further enhanced sorption capacity; however they easily degrade with similar reaction for forming PEI-PAI fibers. Lumen-side barrier layers were created successfully via post-treatment technique of using the crosslinked Neoprene® polymer onto PEI-functionalized PAI fibers. PEI-functionalized PAI fibers also have good cyclic stability and low heat of sorption.

Aqueous piperazine (PZ) blended with N-(2-aminoethyl) piperazine (AEP) is an attractive solvent for CO₂ capture from coal-fired power plants. Blending PZ with AEP can remediate the precipitation issue of concentrated PZ while maintaining its high CO₂ absorption rate, and high resistance to degradation. 5 m PZ/2 m AEP also shows a milder nitrosamine issue than concentrated piperazine. A rigorous thermodynamic model was developed in Aspen Plus® to predict properties of PZ/AEP/H₂O/CO₂, using the electrolyte-Nonrandom Two-Liquid (eNRTL) activity coefficient model. A sequential regression was performed to represent CO₂ solubility, speciation, and amine volatility data over operationally significant loading and temperature ranges. The model predicts a CO₂ cyclic capacity of 0.78 mol/kg (PZ + AEP + water) for 5 m PZ/2 m AEP, compared to 0.50 mol/kg for 7 m MEA and 0.86 mol/kg for 8 m PZ. The predicted heat of absorption is 75 to 80 kJ/mol CO₂ at the operating loading range (0.290-0.371 mol CO₂/mol alkalinity). Although 5 m PZ/2 m AEP has a slightly lower CO₂ capacity than 8 m piperazine, its higher heat of absorption may offset the negative effect on energy consumption. Speciation for PZ/AEP/H₂O at various CO₂ loading and temperature was also predicted, from which behavior of CO₂ in the amine system was proposed. / text

Carbon dioxide (CO₂) capture and sequestration (CCS) at fossil-fueled power plants is a critical technology for CO₂ emissions mitigation during the transition to a sustainable energy system. Post-combustion amine scrubbing is a relatively mature CO₂ capture technology, but barriers to implementation include high capital costs and energy requirements that reduce net power output by 20-30%. Capture energy requirements are typically assumed constant, but work investigates whether flexibly operating amine scrubbing systems in response to electricity market conditions can add value to CO₂ capture facilities while maintaining environmental benefits. Two versatile optimization models have been created to study the electricity system implications of flexible CO₂ capture. One model assesses the value of flexible capture at a single facility in response to volatile electricity prices, while the other represents a full electricity system to study the ability of flexible capture to meet electricity demand and reliability (ancillary) service requirements. Price-responsive flexible CO₂ capture has limited value at market conditions that justify CO₂ capture investments. Solvent storage can add value for price arbitrage by allowing flexible operation without additional CO₂ emissions, but only with favorable capital costs. The primary advantage of flexible CO₂ capture is an increased ability to provide grid reliability services and improve grid resiliency at minimum and maximum electricity demand. Flexibility mitigates capacity shortages because capture energy requirements need not be replaced, and variable capture at low demand helps respond to intermittent renewable generation. / text

Novel solvents utilizing a reversible CO₂ induced property switch are presented. The synthetic procedure for designing the solvents is discussed, along with detailed characterizations on both solvent forms to serve as a tool for optimal solvent identification as well as future solvent design. A reflectance infrared spectroscopic technique is introduced to allow for the examination of CO₂ and solvent composition under high pressures and temperatures. The magnitude of solvent property changes afforded by this "switch" creates opportunities for sustainable processing; discussed are the application to coupling reactions and separations, and CO₂ capture. The switchable solvents are shown to serve as effective media for running reactions, with the switch providing facile recovery of products and catalysts for solvent recycling. Lastly, the switch itself is exploited to provide for the separation of CO₂ from low partial pressure feed streams, and structure-property relationships were successfully used to develop next generation materials with enhanced absorption capacities. The viscosity of the solvents, as a function of temperature and composition, is also presented.

As concerns mount about the rise in atmospheric CO₂ concentrations, many different routes to reduce CO₂ emissions have been proposed. Of these, post-combustion CO₂ capture from coal-fired power stations is often the most controversial, as the CO₂ capture system will remove generating capacity from the grid whereas many of the other solutions involve increasing the generating capacity of the grid with low CO₂-emission plants. Despite this, coal-fired power stations represent a major point source for CO₂ emissions, and if a consensus is reached on the need to reduce CO₂ emissions, a low-cost method for capturing and storing the CO₂ released by these power plants needs to be developed. The overarching goal of this research is to design and develop a novel hollow fiber sorbent system for post-combustion CO₂ capture. To achieve this goal, three objectives were developed to guide this research: i) develop a conceptual framework for hollow fiber sorbents that focuses on the energetic requirements of the system, ii) demonstrate that hollow fiber sorbents can be created, and a defect-free lumen layer can be made, iii) perform proof-of-concept CO₂ sorption experiments to confirm the validity of this approach to CO₂ capture. Each of these objectives is addressed in the body of this dissertation. Work on the first objective showed that fiber sorbents can combine the energetic advantages of a physi-/chemi-sorption process utilizing a solid sorbent while mitigating the process deficiencies associated with using solid sorbents in a typical packed bed. All CO₂ capture technologies--including fiber sorbents--were shown to be highly parasitic to a host power plant in the absence of effective heat integration. Fiber sorbents have the unique advantage that heat integration is enabled most effectively by the hollow fiber morphology: the CO₂-sorbing fibers can behave as "adsorbing heat exchangers." A dry-jet, wet-quench based hollow fiber spinning process was utilized to spin fibers that were 75wt% solid sorbent (zeolite 13X) and 25wt% support polymer (cellulose acetate). The spinning process was consistent and repeatable, allowing for production of large quantities of fibers. The fibers were successfully post-treated with an emulsion-based polymer (polyvinylidene chloride) to create a defect-free lumen side coating that was an excellent barrier to both water and gas permeation. A film study was conducted to elucidate the dominant factors in the formation of a defect-free film, and these factors were used for the creation of defect-free lumen layers. The work discussed in this thesis shows that the second objective of this work was definitively achieved. For the third objective, sorption experiments conducted on the fiber sorbents indicated that the fiber sorbents CO₂ uptake is simply a weighted average of the support material CO₂ uptake and the solid sorbent uptake. Furthermore, kinetic experiments indicate that CO₂ access to the sorbents is not occluded noticeably by the polymer matrix. Using the fiber sorbents in a simulated rapid thermal swing adsorption cycle provided evidence for the fiber sorbents ability to capture the sorption enthalpy released by the CO₂-13X interaction. Finally, a slightly more-pure CO₂ product was able to be generated from the fiber sorbents via a thermal swing/inert purge process.

The thermal degradation of polyvinyl chloride (PVC) is a significant processing challenge which can lead to deleterious mechanical and optical properties in a wide range of products. Synergetic studies on PVC model compounds and blends of bulk PVC provide unique insights into the thermal degradation and stabilization pathways in the presence of common additives. Model PVC compounds were selected to replicate specific defects (e.g., allylic, vicinal and tertiary) and tacticity (i.e., utilizing stereochemistry to investigate tacticity) commonly found in PVC. Model studies were conducted neat (solvent-free) with metal carboxylates. Experimental results highlight that the allylic and tertiary defects are more reactive than pristine PVC and isotactic sites are more reactive than their syndiotactic counterparts. Zinc stearate was found to act not in the role of substituent, but as a Lewis acid by facilitating dehydrochlorination of labile chlorides. This prevents the accumulation of hydrogen chloride and autocatalytic chain unzipping. In contrast, calcium stearate delayed the formation of zinc chloride, a much stronger Lewis acid than zinc stearate, through an ion exchange process to form calcium chloride. Thermal weight loss studies using blends of bulk PVC proved critical in transferring mechanistic insights into the context of a polymeric matrix. Post-combustion carbon capture has traditionally involved the use of aqueous alkanol amine solutions. The regeneration of such systems, however, can be costly and energy intensive. We have developed an alternative system utilizing silylated alkylamines to reversibly capture CO2 under near ambient conditions. The silyl amines developed capture CO2 through chemical reaction to form reversible ionic liquids (RevIL). RevILs utilize no added water and are tunable by molecular design allowing us to influence industrially relevant carbon capture properties such as viscosity, temperature of reversal, and enthalpy of regeneration, while maximizing overall CO2 capture capacity. We demonstrate a strong structure-property relationship among the silyl amines where minor structural modifications lead to significant changes in the bulk properties of the RevIL. Amine containing substrates are important building blocks for a variety of biological and pharmaceutical compounds. However, application of the otherwise versatile Suzuki reaction to these substrates has proved challenging due to either ligation of the amine to the palladium or to electronic effects slowing the oxidative addition step. Conventional methods to overcome these challenges involve protection-deprotection strategies or the use of designer ligands to facilitate reaction. We have shown that application of CO2 pressure and adjusting the water content of the reaction system facilitate the Suzuki coupling of 4-amino-2-halopyridines in high yield with the simple Pd(TPP)2Cl2 catalyst. The protocol was expanded to 2-halopyridines. The results of these investigations will be discussed.

Thermodynamics is important for the design of amine scrubbing CO₂ capture processes. CO₂ solubility and amine volatility in aqueous amines were measured at high temperature and pressure. A rigorous thermodynamic model was developed for MEA-CO₂-H₂O in Aspen Plus®. CO₂ solubility at 80-190°C was obtained from total pressure measurements. Empirical models as a function of temperature and loading were developed for CO₂ solubility from 40 to 160°C in aqueous monoethanolamine (MEA), piperazine (PZ), 1-methylpiperazine (1MPZ), 2-methylpiperazine (2MPZ), PZ/2MPZ, diglycolamine® (DGA®), PZ/1MPZ/1,4-dimethylpiperazine (1,4-DMPZ), and PZ/methyldiethanolamine (MDEA). The high temperature CO₂ solubility data for MEA is comparable to literature and compatible with previous low temperature data. For MEA and PZ, amine concentration does not have obvious effects on the CO₂ solubility. The heat of CO₂ absorption derived from these models varies from 66 kJ/mol for 4 m (molal) PZ/4 m 2MPZ and to 72, 72, and 73 kJ/mol for MEA, 7 m MDEA/2 m PZ, and DGA. The heat of absorption estimated from the total pressure data does not vary significantly with temperature. At 0-0.5 loading ([alpha]), 313-413 K, 3.5-11 m MEA (mol fraction x is 0.059-0.165), the empirical model of MEA volatility is ln(PMEA/xMEA) = 30.0-8153/T-2594[alpha]²/T. In 7 m MEA with 0.2 and 0.5 loading, PMEA is 920 and 230 Pa at 120°C. At 0.3-0.5 loading, the enthalpy of MEA vaporization, -[Delta]Hvap,MEA, is about 70-73 kJ/mol MEA. At 0.25-0.4 loading, 313-423 K, 4.7-11.3 m PZ (x is 0.078-0.169), the empirical model of PZ volatility is ln(PPZ/xPZ) = -123+21.6lnT+20.2[alpha]-18174[alpha]²/T. In 8 m PZ with 0.3 and 0.4 loading, PPZ is 400 and 120 Pa at 120°C, and 2620 and 980 Pa at 150°C. At 0.25-0.4 loading, -[Delta]Hvap,PZ is about 85-100 kJ/mol PZ at 150°C and 66-80 kJ/mol PZ at 40°C. [Delta]Hvap,PZ has a larger dependence on CO₂ loading than [Delta]Hvap,MEA in rich solution because of the more complex speciation/reactions in PZ at rich loading. Specific heat capacity of 8 m PZ is 3.43-3.81 J/(g•K) at 70-150°C. Two new thermodynamic models of MEA-CO₂-H₂O were developed in Aspen Plus® starting with the Hilliard (2008) MEA model. One (Model B) includes a new species MEACOOH and it gets a better prediction than the other (Model A) for CO₂ solubility, MEA volatility, heat of absorption, and other thermodynamic results. The Model B prediction matches the experimental pKa of MEACOOH, and the measured concentration of MEACOO-/MEACOOH by NMR. In the prediction the concentration of MEACOOH is 0.1-3% in 7 m MEA at high temperature or high loading, where the heat of formation of MEACOOH has effects on PCO₂ and CO₂ heat of absorption. Model B solved the problems of Model A by adding MEACOOH and matched the experimental data of pKa and speciation, therefore MEACOOH may be considered an important species at high temperature or high loading. Although mostly developed from 7 m MEA data, Model B also gives a good profile for 11 m (40 wt%) MEA. / text

Abstract: Global decarbonization requires addressing local challenges and advancing appropriate technologies. In this dissertation, an investigation of appropriate carbon capture technologies for CO2 capture from heavy fuel oil (HFO) fired power plants, common locally, is presented. Two emerging technologies are considered, chemical looping combustion (CLC) and calcium looping (CaL). In a preliminary study, CLC and CaL implementation at an HFO-fired power plant are modeled using Aspen software, and based on the results, CaL is selected for further experimental investigation. Briefly, CaL is a high temperature separation process that utilizes limestone-derived CaO tosimultaneously concentrate CO2 and capture SO2 from flue gas. The solid CaO particles are cycled between carbonation and calcination, CaO + CO2 ⇋ CaCO3, in a dual fluidized bed system and experience capture capacity decay with cycling. Structurally distinct limestones were procured from the two geologic regions where limestone is mined in Saudi Arabia. Using bubbling fluidized bed reactor systems, the capture performance of these two limestones, and a German limestone of known performance, were compared. The combined and individual influence of flue gas H2O and SO2 content, the influence of textural changes caused by sequential calcination/carbonation cycles, and the impact of CaSO4 accumulation on the sorbents’ capture performance were examined. It was discovered that metamorphosed limestone-derived sorbents exhibit atypical capture behavior: flue gas H2O negatively influences CO2 capture performance, while limited sulfation can positively influence CO2 capture. The morphological characteristics influencing sorbent capture behavior were examined using imaging and material characterization tools, and a detailed discussion is presented. Saudi Arabian limestones’ deactivation rates were examined by thermogravimetric analysis. A quantitative correlation describing sulfation deactivation was developed. The validity of amending the conventional semi-empirical sorbent deactivation model with the novel correlation was supported by subsequent pilot scale (20 kWth) experiments. Solving process mass and energy balances, reasonable limits on operating parameters for CaL implementation at HFO-fired power plants were calculated. The influence of power plant configuration, carbonator design, and limestone source on power plant energy efficiency are considered and a discussion is presented. Finally a commentary on the potential of this technology for local implementation and required future work is presented.