Carbon capture and storage technologies are required in order to reduce greenhouse gas emissions, while continuing to utilize existing fossil-fueled power generation stations. Of the many developing post-combustion CO2 capture technologies, calcium looping appears promising due to its high thermal efficiency, technical feasibility at commercial-scale, and low sorbent cost. Calcium looping has now been performed at the larger-scale, but there is still a significant quantity of information about sorbent performance, the fate of trace pollutant emissions (specifically SO2 and HCl), dual fluidized bed operating configurations, and impact of realistic operating conditions that still needs to be determined. Based on an economic analysis of the process, three key parameters serve to have the largest potential economic impact: (1) the sorbent deactivation rate, (2) the Ca/C molar ratio, and (3) the rate of sorbent attrition. Therefore, a series of bench-scale, pilot-scale, and continuous pilot-scale testing were conducted to not only explore these parameters from an improvement standpoint, but accurately determine them under conditions expected at the commercial-scale. The presence of HCl did not have a significant impact on sorbent performance provided that steam is present during calcination, although issues with downstream corrosion could be a factor. High CO2 partial pressures during calcination, coupled with high temperatures and the presence of SO2, resulted in dramatically lower cyclic carbonation conversions and a reduced high CO2 capture efficiency regime. Continuous pilot-scale testing generated realistic, and more detrimental, values for sorbent carrying capacity, Ca/C molar ratio, sorbent make-up rates, and rate of sorbent elutriation, that can now be utilized for techno-economic evaluations and scale-up of the technology.

On May 11th, 2019, atmospheric CO2 levels reached 415 ppm, a number 40% higher than the maximum level ever reached in the 800 000 years prior to the Industrial Revolution. This rise can be directly attributed to human activity, and has been linked to global temperature increase and climate change. Net CO2 emissions continue to rise as economies grow, and in 2018 global emissions reached 37.1 Gt. In order to reach the climate targets identified in the 2015 Paris Agreement, some scientists estimate that the world will need to attain net-zero anthropogenic greenhouse gas (GHG) emissions by 2050. Achieving this goal will require deployment of multiple technologies across multiple sectors. Of particular importance will be reducing or eliminating emissions associated to energy production via combustion of fossil fuels, which account for over 80% of CO2 emissions in G20 countries. One method of achieving this is to displace fossil fuel electricity generation with renewable source generation. Canada currently has 12 GW of installed wind capacity, and although it is the country’s fastest-growing source of renewable electricity, widespread deployment is inhibited by technical challenges including the time variability and geographic dispersion of sources. A potential solution to overcome the challenges facing integration of renewables is grid-scale energy storage. Many storage technologies currently exist at various levels of maturity. Although currently low on the development scale, thermochemical energy storage (TCES) has gained significant interest due to its potential to offer low-cost, short- or long-term storage of high-temperature heat using non-toxic, abundant materials. Several recent works have focused on the potential to pair the calcium looping (CaL) process, which exploits the reversible calcination of calcium carbonate, with concentrated solar power (CSP). This would enable CSP to provide continuous power to the grid while receiving discontinuous solar input, and recent projects have predicted storage cycle efficiencies in the range of 38-46%. As an extension of the work done to date, this project proposes a novel configuration of the CSP-CaL process which may offer advantages over other proposed configurations, including a reduction in process equipment requirements, elimination of pressure differentials between vessels, and a reduction in compression duty during the energy discharge period. A process simulation of the proposed system shows that it is capable of offering comparable storage cycle efficiencies, with the overall efficiency being strongly dependent on the residual conversion of calcium oxide in the carbonator as well as on the efficiencies of the power cycles employed to discharge the stored energy. In addition to the technical challenges that may come with this type of system, social and economic barriers may arise due to the fact that it will require large-scale storage of CO2, mining of natural limestone, and potentially large and complex facilities. All of these challenges must be considered and addressed in order to achieve deployment of this technology within Canada and around the world.

No description available.

Production of hydrogen from biomass steam gasification can be enhanced by using calcium oxide sorbents for CO2 capture in the gasifier. Calcium looping suffers from two main drawbacks: the need for high-purity oxygen in order to regenerate the sorbent under oxy-fuel combustion conditions and the loss of sorbent reactivity over several cycles due to sintering of pores upon calcination at high temperatures. One method of addressing the issue of oxygen supply for calcination in calcium looping is to combine the calcium looping and chemical looping processes, where the heat produced by the reduction of an oxygen-carrier by a fuel such as natural gas or gasification syngas, drives the calcination reaction. The technologies can be integrated by combining an oxygen carrier such as CuO with limestone within a composite pellet, or by cycling CuO and limestone within distinct particles. The goal of this project is thus to investigate the different sequences of solids circulation and the cyclic performance of composite limestone-CuO sorbents under varied operating conditions for this novel process configuration. Using a thermogravimetric analyzer (TGA), it was found that using composite CaO/CuO/alumina-containing cement pellets for gasification purposes required oxidation of Cu to be preceded by carbonation (Sequence 2) as opposed to the post-combustion case where the pellets are oxidized prior to carbonation (Sequence 1). Composite pellets were tested using Sequence 2 using varying carbonation conditions over multiple cycles. While the pellets exhibited relatively high carbonation conversion, the oxidation conversion underwent a decrease for all tested conditions, with the reduction in oxygen uptake particularly drastic when the pellets were pre-carbonated in the presence of steam. It appears that the production of a layer of CaCO3 fills up the pellets pores, obstructing the passage of O2 molecules to the more remote Cu sites. Limestone-based pellets and Cu-based pellets were subsequently tested in separate CaL and CLC loops respectively to assess their performance in a dual-loop process (Sequence 3). A maximum Cu content of 50% could be accommodated in a pellet with calcium aluminate cement as support with no loss in oxidation conversion and no observable agglomeration.

The new Canadian laws on CO2 emissions aim to lower the emissions of coal-fired power plants down to those of natural gas combined cycle units: 420 kg CO2/MWeh. In order to meet these requirements, calcium looping and two process variants are investigated through process simulations using Aspen Plus V8.2. The combination of calcium looping and chemical looping combustion, replacing the required air separation unit, is a way to reduce the energy penalty of the capture process. The addition of copper as an oxygen carrier in two different process configurations is compared to calcium looping and shown to reduce the efficiency penalty from 7.8% to 4.5% points but at the price of circulations rates up to about 3800 kg/s. The other improvement path studied is the implementation of calcium looping to a pressurized fluidized bed combustion unit. The pressurized carbonator acts as a reheater for the gas turbine and operating the carbonator at temperatures up to 798°C results in a reduction of the energy penalty from 5.1% to 3.1% points.

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.

No description available.

Steel is one of the most essential metals in the world, and it plays a vital role in various industries. The growing demand for steel has resulted in increased CO2 emissions, with the steel industry contributing to approximately 7% of global emissions of carbon dioxide. Among the different production methods, the electric arc furnace (EAF) has emerged as a promising option, and its market share is expected to double in the future. While the EAF exhibits high efficiency and a reduced carbon footprint in comparison to alternative production routes, there is still considerable room for improvement. In the EAF, a significant amount of input energy, ranging from 15% to 30%, is wasted through off-gas, along with a substantial amount of CO2. To better understand the current state and ongoing research in off-gas handling, a literature review and a preliminary analysis were conducted which revealed that the waste heat from the off-gas can be effectively recovered using an evaporative cooling system, yielding approximately 105 kg of steam per ton of liquid steel. This emphasizes the importance of waste heat recovery in conjunction with CO2 capture. Calcium looping stands out as a promising carbon capture technology among the available options, primarily because of its lower environmental impacts and energy penalty. Furthermore, with its operation at elevated temperatures and dependence on limestone, calcium looping presents a potential solution to reduce the emissions from steel industry. Therefore, this study focuses on the analysis of a waste heat recovery system integrated with calcium looping technology, aiming to capture CO2 and utilize waste heat from the EAF off-gas. Additionally, the potential of coal substitution with bio-coal in the EAF for achieving negative emissions is also investigated. Through a steady state analysis and by employing semi-empirical mass and energy balance equations, it was determined that capturing 90% of the CO2 emissions from a 145-ton EAF requires 12 MW of heat and 16 kg of fresh limestone per ton of liquid steel. Although the average off-gas temperature is high, it cannot be considered as a reliable heat source. Therefore, the heat demand is met by burning biomass inside the calciner. Despite the increased heat demand, the waste heat recovery system integrated with calcium looping has the potential to generate approximately 11 MW of electricity using a supercritical steam cycle. This significant output can be attributed to the elevated temperature of the off-gas and the exothermic carbonation process. The economic analysis reveals that the levelized cost for capturing and storing CO2 is 1165 SEK per ton of CO2 with a negative Net Present Value (NPV). It was noted that, a higher carbon tax could significantly enhance the economic viability of the system. Moreover, the study found that by introducing bio-coal in the EAF with a fossil coal share below 69%, it has the potential to achieve negative emissions. Furthermore, recent studies have shown an increase in the CO2 content in the off-gas when introducing bio-coal into the EAF which further enhances the efficiency and economic feasibility of carbon capture. / Stål är en av de viktigaske metallerna i världen, och det spelar en avgörande roll i olika branscher. Den ökade efterfrågan på stål har lett till ökade koldikoxidutsläpp, och stålindustrin står för cirka 7% av de globala koldioxidutsläppen. Bland de olika produktionsmetoderna har ljusbågsugnen (EAF) framstått som ett lovande alternativ, och dess marknadsandel förväntas fördubblas i framtiden. Även om EAF uppvisar hög effektivitet och ett minskat koldioxidavtryck jämfört med alternativa produktionsvägar, finns det fortfarande stort utrymme för förbättringar.  I EAF går en betydande mängd tillförd energi, mellan 15 och 30%, till spillo genom avgaserna, tillsammans med en betydande mängd CO2. För att bättre förstå det aktuella läget och pågående forskning inom hantering av avgaserna genomfördes en litteraturstudie och en preliminär analys som visade att spillvärmen från avgaserna effektivt kan återvinnas med hjälp av ett evaporativt kylsystem, vilket ger cirka 105kg ånga per ton flytande stål. Dettta understryker vikten av att återvinna spillvärme i samband med CO2-avskiljning.  Kalciumlooping framstår som en lovande teknik för koldioxidavskiljning bland de tillgängliga alternativen, främst på grund av dess lägre miljöpåverkan och energiåtgång. Eftersom kalciumlooping används vid förhöjda temperaturer och är beroende av kalksten, utgör den dessutom en potentiell lösning för att minska utsläppen från stålindustrin. Därför fokuserar denna studie på analysen av ett system för återvinning av spillvärme integrerat med kalciumlooping-teknik, i syfte att fånga in CO2 och utnyttja spillvärme från EAF-avgaserna. Dessutom undersöks potentialen för att ersätta kol med biokol i EAF för att uppnå negativa utsläpp.  Genom en steady state-analys och med hjälp av semi-empiriska mass- och energibalansekvationer fastställdes att det krävs 12 MW värme och 16 kg färsk kalksten per ton flytande stål för att fånga 90% av CO2-utsläppen från en 145-tons EAF. Även om den genomsnittliga avgastemperaturen är hög kan den inte betraktas som en tillförlitlig värmekälla. Därför tillgodoses värmebehovet genom förbränning av biomassa i kalcinatorn. Trots det ökade värmebehovet har systemet för återvinning av spillvärme integrerat med kalciumlooping potential att generera cirka 11 MW el med hjälp av en superkritisk ångcykel. Denna betydande produktion kan hänföras till den förhöjda temperaturen i avgaserna och den exoterna karbonatiseringsprocessen. Den ekonomiska analysen visar att den nivellerade kostnaden för avskiljning och lagring av CO2 är 1165 SEK per ton CO2 med ett negativt nettonuvärde (NPV). Det konstaterades att en högre koldioxidskatt skulle kunna förbättra systemets ekonomiska lönsamhet avsevärt. Dessutom visade studien att genom att introducera biokol i EAF med en andel fossilt kol under 69%, har det potential att uppnå negativa utsläpp. Nya studier har dessutom visat en ökning av koldioxidhalten i avgaserna när biokol införs i EAF, vilket ytterligare förbättrar effektiviteten och den ekonomiska genomförbarheten för koldioxidavskiljning.

Carbon capture and storage technologies are necessary to start lowering greenhouse gas emissions while continuing to utilize existing thermal power generation infrastructure. Calcium looping is a promising technology based on cyclic calcination/carbonation reactions which utilizes limestone as a sorbent. Steam is present in combustion flue gas and in the calciner used for sorbent regeneration. The effect of steam during calcination on sorbent performance has not been extensively studied in the literature. Here, experiments were conducted using a thermogravimetric analyzer (TGA) and subsequently a dual-fluidized bed pilot plant to determine the effect of steam injection during calcination on sorbent reactivity during carbonation. In a TGA, various levels of steam (0-40% vol.) were injected during sorbent regeneration throughout 15 calcination/carbonation cycles. All concentrations of steam were found to increase sorbent reactivity during carbonation. A level of 15% steam during calcination had the largest impact. Steam changes the morphology of the sorbent during calcination, likely by shifting the pore volume to larger pores, resulting in a structure which has an increased carrying capacity. This effect was then examined at the pilot scale to determine if the phase contacting patterns and solids heat-up rates in a fluidized bed were factors. Three levels of steam (0%, 15%, 65%) were injected during sorbent regeneration throughout 5 hours of steady state operation. Again, all levels of steam were found to increase sorbent reactivity and reduce the required sorbent make-up rate with the best performance seen at 65% steam.

Carbon capture and storage technologies are necessary to start lowering greenhouse gas emissions while continuing to utilize existing thermal power generation infrastructure. Calcium looping is a promising technology based on cyclic calcination/carbonation reactions which utilizes limestone as a sorbent. Steam is present in combustion flue gas and in the calciner used for sorbent regeneration. The effect of steam during calcination on sorbent performance has not been extensively studied in the literature. Here, experiments were conducted using a thermogravimetric analyzer (TGA) and subsequently a dual-fluidized bed pilot plant to determine the effect of steam injection during calcination on sorbent reactivity during carbonation. In a TGA, various levels of steam (0-40% vol.) were injected during sorbent regeneration throughout 15 calcination/carbonation cycles. All concentrations of steam were found to increase sorbent reactivity during carbonation. A level of 15% steam during calcination had the largest impact. Steam changes the morphology of the sorbent during calcination, likely by shifting the pore volume to larger pores, resulting in a structure which has an increased carrying capacity. This effect was then examined at the pilot scale to determine if the phase contacting patterns and solids heat-up rates in a fluidized bed were factors. Three levels of steam (0%, 15%, 65%) were injected during sorbent regeneration throughout 5 hours of steady state operation. Again, all levels of steam were found to increase sorbent reactivity and reduce the required sorbent make-up rate with the best performance seen at 65% steam.