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Rotary kilns are widely used for various high temperature industrial applications, e.g., quicklime and cement production. Most of these operations rely on fossil fuels like coal; however, there is growing interest in increasing the share of biomass fuels. During the high-temperature combustion process, ash transport onto, and reactions with, refractory bricks can significantly influence refractory wear. Ash infiltration may impair refractory performance through chemical reactions and exacerbated cracking caused by structural changes in combination with thermal shock. Analysis of spent refractory materials provides valuable insights for understanding and predicting corrosion mechanisms. In the present study, three MgO-based spent refractory bricks were collected from different locations within the burn zone of a rotary lime kiln that was cofired with a mixture of coal, olive pomace (a potassium-rich biomass), and oil. Infiltrated ash and reaction products within the refractory bricks were sampled and characterized using SEM-EDX for elemental mapping and morphology analysis. EBSD analysis was employed to measure the grain size distributions. Micrographic images revealed that all three spent refractory bricks were more sintered and cracked on their hot sides compared to their middle sections and cold sides. Si-rich and K-rich ashes from the coal and biomass fuels, respectively, all infiltrated into the refractories as well as Ca-rich constituents from the limestone/quicklime. XRD analyses revealed the formation of phases such as Mg2SiO4, Ca12Al14O33, and Ca2SiO4. No potassium from the fuel ash was found on the hot side of the refractory bricks, but some were detected deeper within the middle section and cold side of the bricks. The combined use of analytical techniques enabled detailed mapping of ash-forming elements and identification of newly formed phases from the reactions between refractory bricks, ash, and quicklime. These findings provide critical insights into fuel-specific interactions and highlight potential risks for refractory degradation.

Four limestones were calcined in atmospheres containing moderate (∼30%) and high (∼100%) CO2 levels, and the carbonation characteristics of the quicklimes during cooling in these atmospheres were studied using thermogravimetric analysis. The carbonation rates, extents, and onset temperatures varied depending on the atmosphere and parent limestone type. Scanning electron microscopy showed that the quicklimes produced from sedimentary limestones exhibited larger pores and thicker structures, especially after calcination in the high CO2 atmosphere. The quicklimes produced from metamorphic limestones exhibited smaller pores among finer structures, with no major observed differences due to the different calcination atmospheres. However, the carbonation extents differed more in the quicklimes produced from metamorphic limestones after calcination in the different atmospheres, and their carbonation rates were also generally higher. Pore filling was observed in all carbonated quicklimes. Practically, the results indicate significant carbonation of all the tested quicklimes when cooling is conducted in atmospheres containing moderate or high levels of CO2. This has ramifications for processes where such conditions can occur, especially if excessive carbonation is unacceptable; e.g., in the cooling zone of electrified lime-based production kilns.

Quicklime is a noninterchangeable multi-purpose industrial product produced by heating and calcining limestone in high-temperature kilns. Quicklime slaking reactivity (reaction rate and heat development when mixed with water) is a key quality parameter of quicklime, and it is influenced by characteristics of the limestone used as well as by the calcination conditions. In this paper results are presented from a systematic experimental study focused on how the slaking reactivity of quicklime calcined in CO₂ atmosphere depends on calcination parameters (time and temperature). Limestone samples were calcined at a range of temperatures (1000-1200 degrees C) and times (10-60 min.). CO₂ atmosphere was chosen to simulate the conditions of electrified industrial quicklime production, which is of relevance for emerging technologies aiming at efficient CO₂ separation and sequestration. The calcination parameters and specific surface area of the quicklimes produced were correlated with slaking reactivity. The results show that the calcination temperature has greater effect on the slaking reactivity than calcination time within the conditions tested. It was also found that the slaking reactivity was not easily explained by the measured specific surface area. The findings show that, from a reactivity point of view, there is potential for an electric calciner to, combined with carbon capture and storage (CCS), provide a solution for zero-emission production of quicklime of controlled medium to high reactivity.

Refractory liner bricks in the hot zone of rotary lime kilns can sustain wear and corrosion during contact with fuel ashes and quicklime (QL), a product composed mainly of CaO. The effects on a MgO-based refractory after exposure at 1400 °C for 96 h to olive pomace ash (OPA) and coal ash (CA), with and without QL, were investigated. Exposure of the refractory to only OPA caused slag intrusion with no ash deposits remaining on top, while CaMgSiO4 (monticellite) was also identified as a new phase. When exposed to only CA, the refractory exhibited dissolution into the molten slag and 0.5–2 mm cracks were found on the surface interfacing the ash. Mg2SiO4 (forsterite) and CaMgSiO4 were identified as new formed phases. Exposure of the refractory to OPA + QL and CA + QL caused less slag intrusion and substantial amounts of ash/QL deposit remained afterwards. No new phases were identified. The differences in interactions between the exposure materials and refractory were supported by thermochemical equilibrium analysis. Apparent Ca-Si–rich or Ca-rich melts were found in all the exposed samples, but potassium (K) was found to be depleted in all samples, including those involving OPA, which was rich in K. Furthermore, with the exception of exposure to only CA, the other exposures caused the cold crushing strength (CCS) of the refractory to increase compared to its original value. This was attributed to the sintering of the refractory microstructure. The CCS of the refractory decreased after exposure to only CA. The findings of this study enhance understanding of how CA and OPA impact MgO refractories in lime kilns, supporting initiatives aiming at reducing fossil fuel use. The results are encouraging and motivate further investigation.

Carbonation of quicklimes degrades their quality and can occur when process temperatures become sufficiently low. This risk can be heightened in process atmospheres containing high CO2 and steam. To assess this, carbonation experiments involving atmospheres with different CO2 concentrations and steam were performed at 700 °C on 2.5–5 mm quicklime granules derived from sedimentary and metamorphic limestones. The carbonation extents of the quicklimes derived from metamorphic limestones during the fast stage were higher, corresponding with their larger specific surface areas. However, SEM analysis revealed that these quicklimes had fine structures with relatively small pores that likely became blocked during carbonation, causing plateauing of carbonation that appeared to be mainly limited to particle surfaces. The presence of steam caused only mild enhancements in carbonation of these quicklimes. Contrastingly, the quicklimes derived from sedimentary limestones had lower specific surface areas that concurred with their thicker structures and larger pores. The carbonation extent during the initial fast stage was correspondingly lower, but carbonation progressed at a sustained rate thereafter. The resulting high carbonation extents appeared to be facilitated by the larger pore volumes available for carbonate growth, including locations inside particles. The presence of steam greatly enhanced the carbonation of these quicklimes. Overall, every quicklime exhibited high carbonation extents despite being granular-sized. Moreover, their distinctive carbonation behaviors and microstructures could be delineated by their parent limestone type. These findings should be considered when carbonation in high CO2 atmospheres may occur, e.g., during cooling in electrical lime kilns.

This study investigates the effects of a high-CO₂ atmosphere on phase evolution, burnability, and clinker mineral formation in cement raw meals using high-temperature X-ray diffraction (HT-XRD). The cement industry is a significant CO₂ emitter, primarily from limestone decomposition and fuel combustion. Innovative solutions such as carbon capture and storage (CCS) are critical, with electrification and oxy-fuel combustion showing promise. Electrification using plasma technology, which employs CO₂ as a carrier gas, offers a pathway to near-zero emissions. Four industrial raw meals from northern Europe were analyzed under conventional (20% CO₂) and high-CO₂ (95% CO₂) conditions. Chemical composition, particle size distribution, and coarse fraction analyses preceded HT-XRD data collection across temperatures up to 1500 °C. High-CO₂ conditions delayed calcite decomposition, reducing free-CaO availability and altering burnability. The timing of calcite decomposition relative to C₂S formation suggests a reaction pathway in which free CaO, released from calcite, rapidly reacts with thermally activated SiO₂ to form C₂S. Additionally, spurrite decomposition released reactive CaO and C₂S, enhancing C₃S formation at 1300–1400 °C in spurrite-rich samples. Above 1400 °C, melt formation promoted further C₃S development, leading to similar final levels in both tested atmospheres. These findings indicate that high-CO₂ conditions significantly influence clinker phase evolution and reactivity. Practical implications include optimizing raw meal composition and kiln temperature profiles in electrified and oxy-fuel systems to enhance burnability while minimizing operational issues such as spurrite-induced kiln buildup. Future research should further explore industrial scalability and raw material adjustments to enhance CO₂ efficiency during clinkerization.

Microbial exopolysaccharides (EPSs) have attracted increasing attention due to their versatile applications across diverse areas. However, large-scale production of EPSs remains challenging due to the high production costs, primarily driven by the use of synthetic carbon sources. This study demonstrates the potential of quinoa stalk hydrolysates as a sustainable alternative for EPS production using a halotolerant bacterial strain that was isolated from a hypersaline environment and termed SU4M. The bacterial isolate was identified through 16S rRNA and gyrB sequencing as a Bacillus swezeyi strain, and was then cultivated in quinoa stalk hydrolysates. The hydrolysates were produced by acid-catalyzed hydrothermal pretreatment using either sulfuric acid or phosphoric acid, followed by enzymatic saccharification. Fermentation experiments conducted in both shake flasks and bioreactors demonstrated that B. swezeyi SU4M utilized glucose from the hydrolysates efficiently, resulting in significantly higher biomass (5.1 ± 0.1 g L−1) and EPS production (1.2 ± <0.1 g L−1) compared to synthetic media (4.3 ± 0.1 g L−1 and 1.1 ± <0.1 g L−1). The kinetic analysis revealed distinct substrate consumption rates and growth patterns, with hydrolysates enhancing EPS yields under single-pulse fed-batch conditions. Advanced characterization techniques, including compositional analysis, Fourier transform infrared (FTIR) spectroscopy, 1H and 1H-13C heteronuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR), high-performance size-exclusion chromatography (HPSEC), and thermogravimetric analysis (TGA), confirmed that the EPSs derived from hydrolysates were heteropolysaccharides with close structural similarities to those obtained from synthetic media. These findings underscore the potential of quinoa stalk hydrolysates as a biobased alternative to synthetic media as a substrate for EPS production.

In the future, cement clinker formation is likely to take place in high temperatures and high carbon dioxide atmospheres in carbon-neutral production processes as part of, for example, electrified processes. The aim of this study was thus to compare the volatilisation of minor and trace elements during cement clinker formation in a high carbon dioxide atmosphere and a conventional combustion atmosphere. Raw meal samples were exposed, at high temperature, to the two different atmospheres, with elemental analysis performed before and after. For both atmospheres, the minor elements potassium and sulfur, and the trace elements rubidium, lead, thallium, caesium, cadmium and mercury were highly volatile. For most of the analysed elements, no difference was observed between the two atmospheres. However, volatilisation of potassium, sodium and sulfur was lower in the high carbon dioxide atmosphere. It is suggested that this should be further studied in relation to the molar ratio of sulfur to alkalis in the clinker and the effect on clinker quality.

Quicklime, rich in CaO(s), is generated by calcining limestone at high temperatures. Parallel-flow regenerative lime kilns are the most energy-effective industrial method available today. To prevent major disruptions in such kilns, a high raw material quality is necessary. Under some conditions, impurity-enriched material may adhere to limestone pebbles and enter the kiln. In this study, limestone and corresponding quicklime were analyzed to evaluate the extent and composition of surface impurities and assess the effect on quicklime product quality, here defined as free CaO. This was performed by sampling and analyzing limestone, quarry clay, laboratory-produced quicklime, and industrially produced quicklime with XRF, SEM/EDX, and XRD; interpretations were supported by thermodynamic equilibrium calculations. In the laboratory-produced quicklime, the surface impurities reacted with calcium forming Larnite, Gehlenite, Åkermanite and Merwinite, reducing the quicklime quality. The results showed that the limestone surface layer comprised 1.2 wt.-% of the total mass but possessed 4 wt.-% of the total impurities. The effect on industrially produced quicklime quality was lower; this indicated that the limestone surface impurities were removed while the material moved through the kiln. Multicomponent chemical equilibrium calculations showed that the quarry clay was expected to be fully melted at 1170 °C, possibly leading to operational problems.