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Impact of limestone surface impurities on quicklime product quality
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics. The Swedish Mineral Processing Research Association—MinFo, Marieviksgatan 25, Stockholm, Sweden.ORCID iD: 0000-0002-8230-8847
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics. Industrial Doctoral School for Research and Innovation, Umeå University, SE-90187 Umeå, Sweden.ORCID iD: 0000-0001-6938-3853
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics.ORCID iD: 0000-0003-1170-2203
Umeå University, Faculty of Science and Technology, Department of Applied Physics and Electronics.ORCID iD: 0000-0003-1095-9154
2024 (English)In: Minerals, E-ISSN 2075-163X, Vol. 14, no 3, article id 244Article in journal (Refereed) Published
Abstract [en]

Quicklime is produced through the thermal processing of limestone in industrial kilns. During quarry operations, fine particulate quarry dust adheres to limestone lump surfaces, increasing the bulk concentration of impurities in limestone products. During thermal processing in a kiln, impurities such as Si, Mg, Al, Fe, and Mn react with Ca, reducing quicklime product quality. Which reactant phases are formed, and the extent to which these result in a reduction in quality, has not been extensively investigated. The present study investigated as-received and manually washed limestone product samples from two operational quarries using elemental compositions and a developed predictive multi-component chemical equilibrium model to obtain global phase diagrams for 1000–1500 °C, corresponding to the high-temperature zone of a lime kiln, identifying phases expected to be formed in quicklime during thermal processing. The results suggest that impurities found on the surface of the lime kiln limestone feed reduce the main quality parameter of the quicklime products, i.e., calcium oxide, CaO (s), content by 0.8–1.5 wt.% for the investigated materials. The results also show that, in addition to the effect of impurities, the quantity of CaO (s) varies greatly with temperature. More impurities result in more variation and a greater need for accurate temperature control of the kiln, where keeping the temperature below approximately 1300 °C, that of Hatrurite formation, is necessary for a product with higher CaO (s).

Place, publisher, year, edition, pages
MDPI, 2024. Vol. 14, no 3, article id 244
Keywords [en]
calcium oxide, chemical equilibrium calculations, thermal process chemistry
National Category
Chemical Process Engineering
Identifiers
URN: urn:nbn:se:umu:diva-223093DOI: 10.3390/min14030244Scopus ID: 2-s2.0-85189068374OAI: oai:DiVA.org:umu-223093DiVA, id: diva2:1850676
Funder
Swedish Energy Agency, 50224-1Vinnova, 2015-04541Available from: 2024-04-11 Created: 2024-04-11 Last updated: 2024-07-12Bibliographically approved
In thesis
1. Effects of impurities on phase equilibrium in quicklime and cement clinker production
Open this publication in new window or tab >>Effects of impurities on phase equilibrium in quicklime and cement clinker production
2024 (English)Doctoral thesis, comprehensive summary (Other academic)
Alternative title[sv]
Effekter av orenheter på kemisk jämvikt vid produktion av bränd kalk och cementklinker
Abstract [en]

The production of quicklime and cement clinker are energy-intensive processes resulting in significant CO2 emissions. Fuel switching, electrified heating, and carbon capture have gained attention as means of addressing this. Conventional production processes are direct-fired, meaning that the impurities, which originate from either quarries or fuels, interact with the product, influencing process performance and product quality. The suggested strategies for addressing CO2 emissions will alter the process conditions. For example, introducing electrified heating using plasma would shift the process atmosphere to primarily CO2, possibly affecting volatilisation and recirculation. The overall aim of this thesis was to generate new knowledge on the impact of impurities under process conditions in the context of the shift towards more sustainable quicklime and cement clinker production. 

Limestone surface impurities and their effects on quicklime product quality were evaluated. Ash-quicklime interactions were studied both on a laboratory scale and using multicomponent chemical equilibrium calculations (MECs). The volatilisation of minor elements in cement clinker production was investigated on a laboratory scale, and using a counter-current MEC-model with both a conventional combustion atmosphere and high-CO2 atmosphere. 

The detailed analysis of the limestone surface layer showed enrichment of impurities. However, quicklime sampled from a parallel flow generative kiln (PFR) showed low amounts of reactants from surface impurities, which were suggested to contribute to build-ups and increased levels of lime-kiln dust instead. Laboratory-scale studies of coal ash and quicklime interactions and MECs showed that typical cement clinker phases are thermodynamically stable at the coal ash-quicklime interface. Porosity and pore-size distribution were evaluated in pure quicklime samples and quicklime samples exposed to olive pomace, pine bark, and wheat straw ash. Olive pomace ash affected quicklime microstructure severely by increasing porosity and pore size. The laboratory study on the volatilisation of minor and trace elements in cement clinker formation showed higher retention of K, Na, and S in a high CO2 atmosphere, likely explained by low H2O partial pressure and high CO2 partial pressure. Counter-current MECs showed lower enrichment of K, Na, and S in a high CO2 atmosphere.

Future work is suggested to investigate the fate of surface impurities entering industrial PFR kilns. Further, the effect of biomass ash on quicklime microstructure should be evaluated in a complete combustion atmosphere, as should the effects of the rolling bed and recirculation of volatile elements in the rotary kiln. The effects of an altered process atmosphere on cement clinker quality and the volatilisation of minor and trace elements are interesting topics for further studies, e.g. in a pilot-scale rotary kiln.

Place, publisher, year, edition, pages
Umeå: Umeå University, 2024. p. 76
Keywords
Thermodynamic equilibrium calculations, thermal process chemistry, olive pomace, pine bark, wheat straw, microstructure, porosity, linear intercept method, electrification, combustion atmosphere
National Category
Chemical Engineering Energy Engineering
Identifiers
urn:nbn:se:umu:diva-223880 (URN)9789180703963 (ISBN)9789180703956 (ISBN)
Public defence
2024-05-31, BIO.E.203 - Aula Biologica, Biologihuset, Umeå, 09:00 (English)
Opponent
Supervisors
Available from: 2024-05-08 Created: 2024-05-02 Last updated: 2024-07-12Bibliographically approved

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Eriksson, MatiasSandström, KarinCarlborg, MarkusBroström, Markus

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