Umeå University's logo

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.

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.

Calcium looping (CaL) is a promising carbon capture and storage (CCS) technology that has the potential to significantly reduce CO₂ emissions in cement production. Integrating CaL with cement production provides a viable solution to the high CO₂ emissions generated during the calcination process. This study examines the behavior of two industrial cement raw meals from different sites (A-RM and B-RM) under CaL conditions, focusing on phase composition, particle size distribution, and clinker phase evolution up to 1450 °C. Calcination and CaL experiments were conducted in a CO2-rich atmosphere, with materials characterized using quantitative X-ray diffraction (Q-XRD) and high-temperature X-ray diffraction (HT-XRD). The results showed that both raw meals absorbed similar amounts of CO₂ during the cyclic CaL experiments. A-RM formed C₂S and other silicates, while B-RM retained more free CaO due to a less effective reaction with coarser quartz (SiO₂) particles. HT-XRD revealed delayed clinker-phase evolution in the 1000–1400 °C range in CaL-treated raw meals. However, CaL-treated raw meals achieved low free CaO at 1450 °C, suggesting that optimal kiln conditions can produce the desired phase composition. These findings indicate that integrating CaL-treated raw meals into cement production requires careful optimization of operational parameters to maintain clinker quality and minimize energy consumption. Further research should focus on improving the efficiency and reactivity of CaL-treated raw meals to enhance their suitability for industrial cement production.

Natural limestones as raw material for OPC clinker manufacturing contribute to emissions of CO2gases during the production of clinker. In addition, the mining of limestone can regionally be controlledby restrictions due to environmental concerns. Slags from the steel industry can replace limestone tominimize the use of the mineral deposits. Both materials have similar chemistry and are compatible asraw materials.Utilizing slags raises questions about how slag particles will react with other raw meal components asthe temperature in the kiln increases during clinker formation. This study establishes the chemical andmineralogical aspects of replacing a portion of the limestone with slags. Of interest is how the materialsreact during the formation of the liquid phase and the formation of phases containing MgO.Three different slags were examined, a basic oxygen furnace slag BOF, a crystalline blast-furnace slagand a granulated blast-furnace slag. In the study, the microstructural causes of reactivity, as well asmineral formation in the transition zone between raw meal components, developing liquid phase andslag particles were studied. Heated raw meals were studied using HT-QXRD, QXRD, SEM andthermodynamic modeling to describe the reactions of particles at higher temperatures. The resultsshow that the formation of clinker minerals is strongly influenced by the type and amount of slag. Thus,a careful selection must be done of both composition and quantity of metallurgical slags for naturallimestone replacement in order to maintain clinker quality.

Transformative actions in CO2 emitting industries are needed to reach the Paris climate agreement.The cement industry, which is responsible for 5-7% of the global CO2 emissions, has the possibility tomake a difference.Cement production is related to two sources of CO2; 1/3 from combustion of fuels and 2/3 fromcalcination of limestone in the cement raw meal. If all the fuels were to be substituted with non-fossilelectricity, the environmental gain would be significant. Cementa and Vattenfall are evaluatingpossibilities on how electricity can be used to substitute fuels in the cement production by 2030.By using electricity for heating, several positive effects are achieved in the production process. Thecleanness of the exhaust gas will be higher due to elimination of volatiles from fuels. The energyconsumption decreases due to lesser volume of gas to be heated. This is related to the exclusion ofnitrogen gas in the process.A feasibility study comprising literature survey and small scale tests have been performed. Electricalheating techniques showing potential are; microwave heating, plasma torches, flash calcination withelectrical heating, hydrogen combustion and a combination of the mentioned techniques.The most relevant finding is that the combustion related CO2 emissions will be eliminated; thecapturing step will be enhanced since the CO2 gas from calcination is clean and accordingly the needof storage or utilization of CO2 is decreased.

This paper describes the formation of a phosphorous belite solid solution and its impact on alite formation. A sub-solidus phase relation for the ternary system silicon dioxide–calcium oxide–phosphorus pentoxide (SiO₂–CaO–P₂O₅) is reported. The ternary system is based on Rietveld refinements of X-ray diffraction patterns from experimental tests. The overall picture is based on known phase diagrams, relevant Rietveld refinements models, stoichiometric relationships as a function of increasing phosphorus pentoxide concentration and vacancy theories for solid solutions of phosphate belites. A tool is developed for predicting the chemistry of the product as well as the chemistry during heating when producing Portland cement clinker. A thermodynamic database for phase chemistry calculations of clinkering reactions has been created and evaluated. Suitable compounds and solution species have been selected from the thermochemical database included in FactSage software. Some solution compositions have been uniquely designed to allow for the proper prediction of the cement clinker chemistry. The calculated results from the developed database for heating raw materials in cement clinker production and cooling of the product are presented in this paper. The calculated results provide a good prediction of the phases and quantities formed during heating and non-equilibrium cooling. The prediction of the amounts of alite, belite and aluminoferrite phases in the product according to the Scheil method is good. The temperature interval for the existence of all of the major phases is relevant. The thermodynamic data for a solution phase of alite with substituting ions of primarily magnesium oxide and phosphorus pentoxide would improve the predictability of the developed database.

A thermodynamic process model is used as an evaluation tool. Full oxy-fuel combustion is evaluated for circulation of 20–80% of flue gases to the burn zone of a rotary kiln. The full oxy-fuel combustion simulations exhibit altered temperature profiles for the process. With 60% recirculation of flue gases, the temperature in the burn zone is comparable to the reference temperature, and carbon dioxide concentration in the flue gases increases from 33 to 76%. If water is excluded, carbon dioxide concentration is 90%. The partial oxy-fuel combustion method is evaluated for 20 and 40% recirculation of flue gases from one cyclone string to both calciners. Fuel and oxygen feed to the burning zone and calciners are optimised for the partial oxy-fuel scenario. The lowest specific energy consumption is desired while maximising the amount of carbon dioxide theoretically possible to capture. By introducing partial oxy-fuel combustion with 20% recirculation of flue gases in the carbon dioxide string, total carbon dioxide emissions increases by 4%, with 84% possible to capture. Within the limits of the model, the introduction of full oxy-fuel and partial oxyfuel combustion is possible while maintaining product quality. When simulating partial oxy-fuel combustion, the energy consumption will increase even when no power consumption for the production of oxygen is included.

Trace and minor elements like arsenic (As), cadmium (Cd), cobalt (Co), chromium (Cr), copper (Cu), mercury (Hg), manganese (Mn), nickel (Ni), lead (Pb), antimony (Sb), thin (Sn), thallium (Tl), vanadium (V) and zinc (Zn) are important in cement clinker manufacturing. Even in low concentrations these elements influence the production processes, the quality of the products and the environment. The environmental issues are the volatility of elements at high temperatures to the atmosphere and the leachability of elements from concrete products to the surroundings. If a prediction tool was available of the fate of elements to the gas phase and to the cement clinker phases several advantages could be achieved. Therefore a calculation tool is developed based on thermodynamic equilibrium calculations with a two-step method. Most of the thermodynamic data are taken from the FactSage^TM database 6.4 and the solutions phases are adjusted for cement clinker and similar applications.

The tool estimates the volatility of the elements at a temperature below onset of melt formation during production and after formation of melt. The results from the simulations are volatility of each element at low and high temperature and if the element is non-volatile it concentrates in the condensed phases.

In this article four sets of full scale industrial data from a cement clinker and a lime production plant are used to evaluate the prediction tool. The results comprise an inventory of the extent of thermodynamic data for selected trace and minor elements, thermodynamic calculations with distribution to gas or condensed phases with input from full scale measurements, the influence of oxidizing, less oxidizing and slight reducing conditions on the behavior of elements, results from full scale industrial measurements and a comparison between the calculated and the measured distribution of elements. For the cement clinker production eleven elements and for the lime production twelve elements are considered.

This article discusses the impact of oxygen (O₂) enrichment on rotary kiln lump lime production. A predictive simulation tool is utilized to investigate the effect of O₂ enrichment on the following key parameters of the lime process: kiln temperature profile, product quality, specific energy consumption and kiln production capacity. Three fuel mixes - 100% coal, 90% coal and 10% waste derived fuel oil, and 90% coal and 10% sawdust - are simulated at three oxygen levels. The oxygen levels represent three scenarios: no enrichment (21% O₂), moderate enrichment (23% O₂), and moderate-to-high enrichment (25% O₂). This work is a part of the on-going efforts to reduce the environmental impact of industrial production. Reducing emissions, utilizing biofuels and waste derived fuels, full utilization of raw materials, and energy efficiency are areas of importance for industry. In the long term, oxyfuel technology, i.e., combustion with recirculated kiln gases and pure oxygen, could allow for near-zero emission production and carbon sequestration from industry and power production. In the short term, emission reductions in lime production must be achieved through other means, such as energy efficiency. As a step on the path to a near-zero emission lime plant, this paper describes an investigation of the influence of oxygen enrichment in rotary kiln lime production. The simulated results show positive effects of O₂ enrichment, and the simulation results have been used by the kiln operator for in-house training. Results indicate that oxygen enrichment applied to lime production can reduce energy consumption and emissions.