Alkali metal-containing compounds are readily released during thermal conversion of solid fuels, and may have both detrimental and beneficial effects on chemical looping combustion. Here, we characterize alkali interactions with the inner walls of a laboratory-scale reactor under oxidizing, reducing and inert conditions at temperatures up to 900 °C. KCl aerosol particles are continuously introduced to the stainless steel reactor and the alkali concentration is measured on-line with a surface ionization detector. Aerosol particles evaporate at temperatures above 500 °C and KCl molecules rapidly diffuse to the reactor wall. Up to 92% of the alkali reaching the wall below 700 °C remains adsorbed, while re-evaporation is important at higher temperatures, where up to 74% remains adsorbed. Transient changes in alkali concentration are observed during repeated redox cycles, which are associated with changes in chemical composition of the wall material. Metal oxides on the reactor wall are partially depleted under reducing conditions, which allow for the formation of a new potassium-rich phase that is stable in a reducing atmosphere, but not under inert conditions. The observed wall effects are concluded to be extensive and include major transient effects depending on gas composition, and the implications for laboratory studies and improved experimental methodology are discussed. 

Chemical-Looping Combustion (CLC) of biofuels is a promising technology for cost-efficient CO2 separation and can lead to negative CO2 emissions when combined with carbon capture and storage. A potential challenge in developing CLC technology is the effects of alkali metal-containing compounds released during fuel conversion. This study investigates the interactions between alkali and an oxygen carrier (OC), CaMn0.775Ti0.125Mg0.1O3-δ, to better understand the fate of alkali in CLC. A laboratory-scale fluidized bed reactor is operated at 800–900 °C in oxidizing, reducing and inert atmospheres to mimic CLC conditions. Alkali is fed to the reactor as aerosol KCl particles, and alkali in the exhaust is measured online with a surface ionization detector. The alkali concentration changes with gas environment, temperature, and alkali loading, and the concentration profile has excellent reproducibility over repeated redox cycles. Alkali-OC interactions are dominated by alkali uptake under most conditions, except for a release during OC reduction. Uptake is significant during stable reducing conditions, and is limited under oxidizing conditions. The total uptake during a redox cycle is favored by a high alkali loading, while the influence of temperature is weak. The implications for the understanding of alkali behavior in CLC and further development are discussed. 

Regarding the importance of rheological properties of water based drilling fluids, the effects of silica nanospheres, multiwall carbon nanotubes (MWCNTs) and two types of their hybrid, i.e. H1 (80 wt.% silica nanosphere/20 wt.% MWCNT) and H2 (50 wt.% silica nanosphere/50 wt.% MWCNT) on the viscosity and density of distilled water were investigated. According to the results, viscosity and density of the nanofluids increased with the concentration, while they were reduced by increasing the temperature. At high concentrations, the least increase in the viscosity of distilled water by adding the nanomaterials is related to H2 (8.2% increase at 1.0 wt.%). Likewise, the optimum operating temperature at higher concentrations was 20 C. As the results show, increase in the density of distilled water by adding the nanomaterials is insignificant, that in the worst case it did not exceed 0.9%. The least increase in the density of base fluid at high concentrations was for H1. 

Chemical looping combustion of biomass-sourced fuels (bio-CLC) is a novel bio-energy with carbon capture and storage (BECCS) technology for power and heat generation with net negative CO2 emissions. In this study, a new 10 kWth CLC pilot designed for high-volatiles biomass fuels was commissioned with ilmenite oxygen carrier and five different biomass fuels of varying volatile and alkali content fractions. The system was tested for its ability to convert high and low volatile content biomass, while achieving high carbon capture efficiency. The new pilot achieved carbon capture close to 100% for high-volatiles biomass, and >94% for low-volatiles biomass char fuels. Furthermore, due to the implementation of a volatiles distributor, the new pilot demonstrated an improvement of up to 10 percentage points of gas conversion efficiency for high-volatiles biomass vs. the previous generation reactor. Gaseous alkali emissions were measured with a surface ionization detection system. Flue gas alkali release levels were found to rise with higher fuel alkali content. Alkali emissions were found to be approximately similar in the AR and the FR for all but the straw pellet mixture fuel (highest alkali content fuel). For the straw pellet mixture, gaseous alkali release levels in the AR were up to seven times higher than those of the FR. In all cases, over 96% of the fuel’s alkalis were absorbed by the ilmenite bed material. Ilmenite’s strong alkali absorption characteristics were concluded to be the key determinant of gas-phase release of biomass alkali in the conducted experiments. 

Alkali release was studied in a 10 kWthchemical looping pilot operated with a Linz-Donawitz (LD) slag oxygen carrier (OC) and three biomass fuels. Experiments were performed at three temperatures and in three operation modes: chemical looping combustion (CLC), chemical looping gasification (CLG), and oxygen-carrier-aided combustion (OCAC). Gas-phase alkali release was measured with a surface ionization detector (SID). Fuel reactor (FR) gas-phase alkali emissions increased with the temperature. This occurred as a result of increased evaporation of KCl and enhanced decomposition of alkali salts during char conversion. Air reactor (AR) alkali emissions were lower than in the FR and independent of the operating temperature. In comparison of operating modes, CLC and CLG modes resulted in similar gas-phase alkali emissions due to the similar extent of char conversion. In contrast, operation of the reactor system in OCAC mode resulted in significantly lower levels of gas-phase alkalis. The difference in alkali emission was attributed to the steam-rich atmosphere of CLC. The effect of steam was further investigated in CLC and OCAC tests. Lowering steam concentrations in CLC operation resulted in lower gas-phase alkali emissions, while introducing steam to the FR during OCAC operation resulted in higher alkali emissions. It was concluded that steam likely enhances gas-phase K release through a reaction of K2CO3within the fuel char with steam to produce KOH(g). Solid sampling and analysis for K content was used along with SID measurements to develop a K mass balance for the reactor system. Mass balance results for the straw pellet fuel tests showed that LD slag OC absorbs approximately 15-51% of fuel K, 2.2% of fuel K is released to the gas phase, and up to 3.4% of fuel K is captured in the AR fly ash. The residual 40-80% of fuel K was determined to leave the FR as K-rich fly ash. 

Two manganese ores with different iron content were investigated as oxygen carriers for chemical looping conversion of simulated biomass volatiles. The aim was to study the performance of the oxygen carriers with regards to combustion and potential use for chemical-looping gasification of wood-based biomass. The oxygen carriers were studied in a 300 W chemical-looping reactor system with circulation of oxygen carriers between the fluidized air and fuel reactors. The temperature was 850-900 °C and the fuel flow rates were 0.6-3 Lmin-1. The Mn ore with higher iron content showed significant oxygen release at 900 °C under inert conditions, as well as full conversion of CO, H2 and methane at low fuel flow. The other Mn ore showed little methane conversion and poorer conversion of the other gases when compared at similar fuel flows. However, the gas composition attained was rather similar if compared for a similar overall gas conversion. Nonetheless, a slightly higher syngas fraction and H2 to CO ratio in the product stream was obtained with the Mn ore with lower iron content. In all cases the syngas fraction in the product gas increased with temperature and fuel flow. The formation of fines (attrition rate), particle size distribution, and the bulk density of the oxygen carriers were measured to evaluate their mechanical properties during chemical looping of biomass volatiles. 

Two oxygen carriers were tested with respect to chemical looping combustion (CLC) and chemical looping gasification (CLG). Ilmenite, a natural ore composed mainly of iron–titanium oxide, and LD Slag, an iron-based industrial waste, were investigated at 850 and 900 °C in a continuous operation in a 0.3 kW chemical-looping reactor system using synthetic biomass volatiles as fuel. CLC and CLG conditions were simulated in the fuel reactor by changing the fuel flow rates. In the case of ilmenite the syngas yield and methane conversion increased with fuel flow rate. Consequently, the syngas to hydrocarbon ratio was higher for ilmenite. Methane conversion improved for both tested oxygen carriers with increasing the operating temperature. Oxygen release was observed in the case of LD Slag. The H2/CO ratio was between 0.7 and 0.8 for both oxygen carriers at the higher fuel flows. With respect to CLC, ilmenite showed higher gas conversion than LD slag. Analysis of the particles revealed that ilmenite possessed better mechanical properties and formed less dust compared to LD Slag during the continuous operation with fuel. 

Tar management is one of the key components to achieve high energy efficiency and low operational costs connected to thermal gasification of biomass. Tars contain a significant amount of energy, and unconverted tars result in energy efficiency losses. Also, heavy tars can condense downstream processes, resulting in increased maintenance. Dual fluidized beds for indirect gasification operated with active bed material can be a way to better convert and control the tar generated in the process. Using an active material to transport oxygen in an indirect dual reactor gasification setup is referred to as chemical-looping gasification (CLG). A higher oxidative environment in the gas phase, in addition to possible catalytic sites, could mean lower yields in comparison to normal indirect gasification. This paper investigates the effect of using Steel converter slag (LD slag), a byproduct of steel manufacturing, as an oxygen-carrying bed material on tar species generated in a 10 kWth dual fluidized bed biomass gasifier. The results are compared to the benchmark oxygen carrier ilmenite and conventional silica sand. Three different solid biofuels were used in the reactor system: steam exploded pellets, pine forest residue and straw. Tar was absorbed from the raw syngas using a Solid Phase Adsorption (SPA) column and was analyzed using GC-FID. Bench-scale experiments were also performed to investigate benzene conversion of LD slag and ilmenite at different oxidation levels. The findings of this study suggest that oxygen carriers can be used to decrease the tars generated in a dual fluidized bed system during gasification. Phases in LD slag possess catalytic properties, resulting in a decreased ratio of heavy tar components compared to both ilmenite and sand. Temperature and fuel load showed a significant effect on the tar generation compared to the circulation and steam ratio in this reactor system. Increased temperature generated lower tar yields and lower ratios of heavy tar components for LD slag in contrast to sand.

Paper-based packaging is a complex multi-material composed of paper (fibers), plastics, and metals, making efficient material recycling complicated. Currently, most of the fibers are recycled into new paper products while the residual material is commonly incinerated. Therefore, to improve the circularity and reduce the fossil dependency chemical recycling is needed. In this study, recycling of the residual materials was evaluated by thermal and catalytic pyrolysis. First, screening tests were performed using five reject materials and four catalysts in an analytical scale and then, a selection of catalyst and reject materials were evaluated in lab-scale followed by a techno-economic assessment. Experimental results indicated that the conversion was more efficient if the reject had high content of plastics compared to fibers, leading to products with increased heating value, higher hydrocarbon yield and less reactive oxygenates compared to the rejects with low plastic ratio. In the thermal pyrolysis 54 % of the weight of the feedstock and 70 wt% of the carbon in the feedstock ended up in a solid organic product (wax) which contained hydrocarbons and alcohols. In the analytical catalytic pyrolysis, HZSM-5 gave the best result in terms of cracking, deoxygenation, and aromatization. Ex-situ catalytic pyrolysis using HZSM-5 resulted in an improved quality of organic liquid with reduced hydrocarbon length as well as deoxygenated and aromatic compounds. The yield of the organic liquid was up to 19 wt% and contained mainly monoaromatics. The techno-economic evaluation showed, for processing 100,000 tons year−1 residual material, the total plant investment and the annual profit are about 29 and 12 million Euros, respectively, if no incentive for treating the residual material.

Highly stabilized mesoporous core-shell-structured oxygen carriers (OCs) were fabricated by a repetitive coating process of alumina supports using the mesopore-forming surfactant assembly method. The wet coating strategy, along with the sol-gel process, was used for the synthesis of mesoporous material-shelled OCs with various shell compositions (i.e., zirconia, titania). The cyclic performance of the synthesized OCs during chemical looping combustion (CLC) was investigated in a thermogravimetric analyzer (TGA). The mesoporous-shelled OCs demonstrated significantly better performance compared to the OCs without mesoporous shells. The synthesized OCs with a mesoporous zirconia/titania shell reveal a unique oxygen capacity of 100% based on active metal oxide for supported NiO and Fe2O3. Also, the synthesized OCs showed no activity loss after 10 cycles. This was attributed to the exceptional core-shell coating strategy, in which the thermally stable mesoporous Zr/Ti layers prevent the sintering and over-reaction of the active metal oxide crystals with the alumina support. 

Carbon dioxide (CO2) capture is a process that can significantly reduce the amount of CO2 in the atmosphere. In this study, several solid sorbents were examined for their CO2 capturing performance over 30 carbonation-calcination cycles. The sorbents included natural calcined Cadomin limestone (denoted as CD), hydrated calcined Cadomin pellets (denoted as CP), core/shell sorbets with CD and CP as cores, and mesostructured silica (denoted as CD@Si and CP@Si, respectively) and titania (denoted as CD@Ti and CP@Ti) as shells. The core/shell sorbents were prepared with a protective porous shell using the mesoporous silica and titania layers. The surface morphology and porosity of all sorbents were qualified using scanning electron microscopy and were quantified using nitrogen physisorption. X-ray diffraction was also used to identify the crystal phase composition of the sorbents before and after calcination. The CP@Ti pellets showed the best performance in the retention of CO2 uptake over 30 cycles with an activity loss of 50.9%. This is attributed to the formation of a protective layer of thermally stable mesoporous titania using a sol-gel method, which prevented the aggregation of CaO crystals and sorbent sintering. Although the modified core/shell sorbents exhibited an improvement in maintaining the stability of the cyclic operation compared to natural limestone, further study is needed to understand the core/shell sintering phenomenon at high temperatures using other novel materials.

A steel slag from the Linz-Donawitz process, called LD-slag, having significant calcium and iron-fractions, was investigated as an oxygen carrier in a recently developed 10 kWth chemical-looping combustor with three high-volatile biomass fuels. In order to improve operability, the LD-slag was found to require heat-treatment at high temperatures before being used in the unit. In total, operation with the biomasses was conducted for more than 26 h at temperatures of 870–980 °C. The fuel thermal power was in the range of 3.4–10 kWth. The operation involved chemical looping combustion (CLC), chemical looping gasification (CLG) and oxygen carrier aided combustion (OCAC). Around 12 h was in CLC operation, 13.3 h was conducted in CLG-conditions, while the remaining 0.7 h was OCAC. Here, the results obtained during the CLC part of the campaign is reported. Increased temperature in the fuel reactor and higher airflows to the air reactor both lead to better combustion performance. Steam concentration in the fuel reactor has little effect on the performance. The LD-slag showed higher oxygen demand (31.0%) than that with ilmenite (21.5%) and a manganese ore (19.5%) with the same fuel and normal solids circulation. However, with the LD-slag, there is possibility to achieve a lower oxygen demand (15.2%) with high solids circulation. © 2023 The Author(s)

Finding a suitable oxygen carrier is crucial for the development of Chemical Looping Combustion (CLC). A new manganese ore was tested with different biomass fuels in a recently commissioned 10 kWth unit. The ore maintains the capability of generating O2 gas in N2 after continuous operations with the fuels, however, the concentration was relatively low within 0.45–1.0 vol% at 820 to 975 °C. Influence of temperature, solids circulation and fuel power was examined for different fuels. Temperature increase enhances the carbon capture and reduces the oxygen demand, while the solids circulation and fuel power should be carefully controlled. Using biomass char the oxygen demand can be lowered to 2.6% while the carbon capture was close to 99%. The manganese ore showed a higher reactivity than the often-used ilmenite. Thus, a decrease of 8–10% in oxygen demand was achieved by using the manganese ore in comparison to ilmenite. During the 42 h of hot operation, defluidisation was not observed. Based on the analysis of the 35 fine samples collected, the initial attrition after first hours of operation was high, but gradually decreased to a relatively stable value of 0.27 and 0.12 wt%/h for hot and fuel operations, respectively, corresponding a lifetime of 370–830 h. 

Manganese ores are promising oxygen carriers for chemical looping combustion (CLC), due to their high reactivity with combustible gases. In this work, a manganese ore called EB (Elwaleed B, originating from Egypt) is studied for its reaction rate with CH4, CO and H2 and the data are used in an analytically solved reactor model. The reactivity of fresh and three used EB samples from previous operation in a 10 kWth pilot was examined in a batch fluidized bed reactor with CH4 and syngas (50%CO + 50%H2). In comparison with other manganese ores, the EB ore has a lower rate of reaction with CH4, while showing a significantly higher reactivity with syngas. Nevertheless, this manganese ore always presents a better conversion of CH4 and syngas than the benchmark ilmenite. Mass-based reaction rate constants were obtained using a pseudo first-order reaction mechanism: 1.1·10-4 m3/(kg·s) for CH4, 6.6·10-3 m3/(kg·s) for CO and 7.5·10-3 m3/(kg·s) for H2. These rate constants were used in an analytical reactor model to further investigate results from previous operation in the 10 kWth unit. According to the analytical model, in the 10 kWth operation, 98% of the char in the biomass fuels was gasified before leaving the fuel reactor, while the char gasification products (CO and H2) have a 90% contact efficiency with the bed material. On the contrary, the volatiles have a much lower contact efficiency with the oxygen carrier bed, i.e. 20%, leading to low conversion of volatiles released. Thus, the results emphasize the importance of improving the contact between volatiles and bed material in order to promote combustion performance in the CLC process. 

Chemical looping gasification (CLG) is an emerging process that aims to produce valuable chemical feedstocks. The key operational requirement of CLG is to limit the oxygen transfer from the air reactor (AR) to the fuel reactor (FR). This can be accomplished by partially oxidizing the oxygen carrier in the AR, which may lead to a higher reduction degree of the oxygen carrier under the fuel conversion. A highly reduced oxygen carrier may experience multiple issues, such as agglomeration and defluidization. Given such an interest, this study examined how the variation of the mass conversion degree of ilmenite may affect the conversion of pine forest residue char in a fluidized bed batch reactor. Ilmenite was pre-reduced using diluted CO and then underwent the char conversion at 850, 900, 950, and 975 °C. Our investigations showed that the activation energy of the char conversion was between 194 and 256 kJ/mol, depending upon the mass conversion degree of ilmenite. Furthermore, the hydrogen partial pressure in the particle bed increased as the oxygen carrier mass conversion degree decreased, which was accompanied by a lower reaction rate and a higher reduction potential. Such a hydrogen inhibition effect was confirmed in the experiments; therefore, the change in the mass conversion degree indirectly affected the char conversion. Langmuir-Hinshelwood mechanism models used to evaluate the char conversion were validated. On the basis of the physical observation and characterizations, the use of ilmenite in CLG with biomass char as fuel will likely not suffer from major agglomeration or fluidization issues.

Iron sand as an industrial by-product has a reasonable iron content (35 wt% Fe) and low economical cost. The reactivity of iron sand as an oxygen carrier was examined in a bubbling fluidized bed reactor using both gaseous and solid fuels at 850–975 °C. Pre-reductions of iron sand were performed prior to fuel conversion to adapt the less-oxygen-requiring environment in chemical looping gasification (CLG). Based on the investigations using CO and CH4, iron sand has an oxygen transfer capacity of around 1 wt%, which is lower than that of ilmenite. The conversion of pine forest residue char to CO and H2 was higher when using iron sand compared to ilmenite. Depending on the mass conversion degree of iron sand, the activation energy of pine forest residue char conversion using iron sand was between 187 and 234 kJ/mol, which is slightly lower than that of ilmenite. Neither agglomeration nor defluidization of an iron sand bed occurred even at high reduction degrees. These suggests that iron sand can be utilized as an oxygen carrier in CLG. Furthermore, this study presents novel findings in the crystalline phase transformation of iron sand at various degrees of oxidation, altogether with relevant thermodynamic stable phases. 

The second-generation bio aviation fuel production via Chemical Looping Gasification (CLG) of biomass combined with downstream Fischer-Tropsch (FT) synthesis is a possible way to decarbonize aviation sector. The CLG process has the advantage of producing undiluted syngas without the use of an air-separation unit (ASU) and improved syngas yield compared to the conventional gasification processes. This study is based on modelling the full chain process of biomass to liquid fuel (BtL) with LD-slag and Ilmenite as oxygen carriers using Aspen Plus software, validating the model results with experimental studies and carrying out a techno-economic analysis of the process. For the gasifier load of 80 MW based on LHV of fuel entering the gasifier, the optimal model predicts that the clean syngas has an energy content of 8.68 MJ/Nm3 with a cold-gas efficiency of 77.86%. The optimized model also estimates an aviation fuel production of around 340 bbl/day with 155 k-tonne of CO2 captured every year and conversion efficiency of biomass to FT-crude of 38.98%. The calculated Levelized Cost of Fuel (LCOF) is 35.19 $ per GJ of FT crude, with an annual plant profit (cash inflow) of 11.09 M$ and a payback period of 11.56 years for the initial investment.

In this study, a series of core-shell structured spheriform CO2 sorbents were synthesized by using CaO-based pellets as cores and different mesoporous metal oxides (e.g. alumina, ceria, and yttrium-stabilized zirconia) as shells through a repeated wet impregnation coating process. Cyclic CO2 capture performance of the obtained sorbents was investigated using a thermogravimetric analyzer. Among all the core/shell sorbents under study, the pellets coated with a layer of alumina exhibit the best performance in the retention of CO2 uptake over 20 cycles with the lowest activity loss of only 30.4 %, attributed to the existence of the thermal stable porous alumina shell which prevents the sintering and the aggregation of the CaO grains. Moreover, the attrition study using an air-jet apparatus and a standard test method reveals that such sorbents exhibit enhanced attrition resistance due to the protection of the porous shell providing them with a great potential for application in fluidized bed conditions.

The second-generation bio aviation fuel production via Chemical Looping Gasification (CLG) of biomass combined with downstream Fischer-Tropsch synthesis is a possible way to decarbonize the aviation sector. Although CLG has a higher syngas yield and conversion efficiency compared to the conventional gasification processes, the fraction of biogenic carbon which is converted to biofuel is still low (around 28%). To increase carbon utilization and biofuel yield, incorporation of two types of electrolyzers, Polymer Electrolyte Membrane (PEM) and Molten Carbonate Electrolysis Cell (MCEC), for syngas conditioning has been investigated. Full chain process models have been developed using an experimentally validated CLG model in Aspen Plus for Iron sand as an oxygen carrier. Techno-economic parameters were calculated and compared for different cases. The results show that syngas conditioning with sustainable hydrogen from PEM and MCEC electrolyzers results in up to 11.5% higher conversion efficiency and up to 8.1 % higher biogenic carbon efficiencies in comparison to the syngas conditioning with water gas shift reactor. The study shows that the lowest carbon capture rates are found in the configurations with the highest biogenic carbon efficiency which means up to 14% more carbon ends up in FT crude compared to the case with conventional WGS conditioning. Techno-economic analysis indicates that syngas conditioning using PEM and MCEC electrolyzers would result in an increase of the annual profit by a factor of 1.4 and 1.7, respectively, when compared to using only WGS reactors. 

Zirconia-stabilized Ca-based sorbent has been previously investigated for cyclic CO2 capture processes; however, the cost of pure zirconia may be a matter of concern. The cost of sorbent can be decreased by addition of a low cost second metal oxide with zirconia-stabilized Ca-based sorbent. This study examined a number of mixed metal oxides supports, such as alumina, silica, titania, magnesia and molybdena, with zirconia (ZrO2) for stabilization of calcium (Ca) based sorbents directly produced from a co-precipitation method. Selected metal oxide supports (i.e. alumina and silica) are commonly used in catalytic steam gasification. The proposed novel strategy aimed at enhancing sorbent stability, increasing surface area, decreasing cost of zirconia-stabilized sorbents and investigating the effects of the common used supports in catalytic steam gasification on the performance of Ca-based sorbents. The optimal composition for the activity of ceramic-stabilized calcium oxide (CaO) samples under mild operating conditions was determined to be 10 wt.% ceramic incorporated in the sorbent. The results indicated considerable sorbent stability and capacity improvement for mixed metal oxide zirconia-stabilized CaO over those of pure CaO, which showed significant cyclic capacity decay under similar conditions. Among the studied materials, aluminum zirconate, calcium zirconate, and zirconium molybdate stabilized sorbents showed the best initial uptake and performances in severe operating conditions over 60 cycles. However, titania, silica and magnesia supports showed negative effect on the sorbent performance. 

Calcium oxide (CaO) has been investigated as a high-temperature performance sorption material for carbon capture due to its high carbon dioxide (CO2) capacity, low cost, and environmental benignity. Unfortunately, commercialized application of CaO materials has been hindered by severe capacity loss during cycling operations. In an attempt to overcome these problems, this study investigated the effects of adding zirconia-based ceramic dopants and coating sorbents with highly crystalline zirconium dioxide (ZrO2) layers derived from the hydrolysis of zirconium butoxide to control the growth of ZrO2 crystals. Uncoated natural Cadomin delivered a high CO2 capture capacity of more than 13 mol CO2/kg, while the zirconia-coated sorbents showed excellent cycling stability corresponding to a maximum capacity of retention of 79% after 21 cycles at high temperatures. More importantly, the highly crystalline ZrO2-coated sorbents doped by zirconia-based sorbents exhibited a significantly lower decay capacity compared to the uncoated sorbents, which could be attributed to the formation of a perovskite structure that is resistant at high temperatures and a high-temperature-resistant ceramic layer through the solid-state reaction of the highly mesoporous crystalline ZrO2 layer with CaO. These results shed light on the development of sorbents with special structures and superior chemical and mechanical properties for high-performance calcium looping or regenerative calcium cycle processes. (Graph Presented). 

Calcium (Ca) based sorbents utilized in the carbon dioxide (CO2) capture process at high temperatures have displayed considerable activity loss during extended use, due to sintering. Refractory zirconium-based ceramics, however, have shown excellent performances as thermal barrier coatings in many high-tech applications; and, the recent doping of zirconia in Ca-based sorbents has exhibited excellent sustainability in the activity stability in cyclic CO2 capture operations. In this work, we doped sorbents, at loadings of 10 wt%, with a few zirconium-based ceramics, such as alkaline earth metal zirconate (calcium zirconate, CaZrO3), which has the chemical structure of perovskite, and rare earth metal zirconates, which have the chemical structure of pyrochlore. These materials were prepared through the wet co-precipitation method, in order to achieve the optimal uptake capacity and stability in cyclic CO2 capture operations. Among the sorbents tested, the CaZrO3-doped sorbents exhibited excellent performance, remarkable thermal stability and sintering resistant. Therefore, the sorbents were stable though 30 carbonation–calcination cycles. The sorbent showed a CO2 capture capacity of 12 mol CO2/kg sorbent, with an activity loss of 19.6% through carbonation at 675 °C for 10 min and calcination at 850 °C for 10 min. Among the rare earth metal zirconate ceramics, samarium zirconate (Sm2Zr2O7) exhibited the best stability with an activity loss of 23.4% loss, but at a lower uptake of 7.2 mol CO2/kg sorbent at the same carbonation–calcination conditions. In comparison, Cadomin (a natural calcium carbonate) at the same conditions resulted in a capture capacity of 13.5 mol CO2/kg sorbent and an activity loss of 69%. Surface area characterizations showed that incorporation of the ceramics to the calcium based sorbents significantly improved the surface morphology and textural properties of the sorbents. X-ray diffraction results indicated that the improved resistance of the sorbent could be due to forming of ceramic structures such perovskite-type CaZrO3 at a relatively low temperature (around 850 °C compared to higher temperatures required for pyrochlore-type ceramic formation), which made a stable sorbent structure for the carbonation process. 

The greenhouse gas emissions from the boiler of pulp and paper industries can be minimized by adapting chemical looping combustion (CLC) technology. This work aims to analyze the energy, exergy, economic, and exergoeconomic performance of an industrial scale CLC plant for district heat and electricity generation using waste bark from the paper and pulp industry. The CLC plant with one natural ore and one industrial waste oxygen carrier (OC) is modeled using Aspen Plus. The performance of the CLC plant has been compared to Örtofta combined heat and power plant without CO2 capture and with post-combustion CO2 capture as the reference cases. Results showed that the CLC-based power plant is energetically, exegetically, and economically efficient compared to the reference cases. The circulating fluidized bed boiler unit contributes the highest exergy destruction (about 50–80%). Among the CO2 capture plants, the CLC plant with ilmenite has the lowest levelized cost of district heat (4.58 € GJ−1), and a payback period (9.69 years) followed by the CLC plant with LD slag (5.91 € GJ−1 and 11.84 years), and the plant with PCC (6.94 € GJ−1 and 13.58 years). The exergoeconomic analysis reveals that the CLC reactors have the highest cost reduction potential, followed by the steam turbine.