A Study on Desulfurization of Hot Metal Using Different Agents

• Main Author: Lindström, David
• Format: Doctoral Thesis
• Language: English
• Published: KTH, Mikro-modellering 2014
• Subjects: desulfurization; hot metal; CaO; Mg; CaC2; ZnO; reaction mechanism; desulfurization abilities
• Online Access: http://urn.kb.se/resolve?urn=urn:nbn:se:kth:diva-144025; http://nbn-resolving.de/urn:isbn:978-91-7595-041-9

This thesis deals with desulfurization of hot metal using different agents. The aim of this study was to improve the understanding of commonly used desulfurization agents such as fluidized CaO, CaC2, commercial-CaO, Mg, and mixtures of commercial-CaO-Mg. The possibility to use ZnO for desulfurization of hot metal was also investigated. The desulfurization mechanisms and kinetics of these agents were studied. A broad comparison of the desulfurization abilities of the agents was performed under the same experimental conditions. The experimental studies were carried out in a high temperature resistance furnace at 1773 K with good quenching ability and precise control of the oxygen partial pressure. The influence of ZnO in blast furnace slag on the sulfur removal potential was studied. It was found that ZnO does not stay in blast furnace slag under relevant oxygen potentials and consequently has no influence on its sulfur removal capacity. The reaction mechanism of Mg was studied by adding pure Mg into hot metal. It was found that most Mg (about 90 %) escaped as gas in less than two seconds, only providing a little desulfurization. MgS is not formed by homogenous nucleation, but on MgO particles originating from the surface of the added Mg metal. The growth of CaS around CaC2, fluidized CaO and commercial-CaO were measured and compared. The parabolic rate constants were evaluated to be 2.4∙10-7 [cm s-1] for CaC2, and 5∙10-7 [cm s-1] for fluidized CaO particles. The bigger parabolic rate constant of fluidized CaO explains why fluidized CaO achieved a much better desulfurization of hot metal than CaC2 under the same experimental conditions. Commercial-CaO performed less satisfactory in comparison to fluidized CaO powder. This was due to both its less reactive surface and agglomeration of the particles. Agglomerates and large CaO particles lead to 2CaO.SiO2 formation which hindered further utilization of CaO for desulfurization. The 2CaO.SiO2 formation was favored by a high oxygen potential. Since the desulfurization reaction of CaO not only produced CaS but also oxygen, the local oxygen concentration around big CaO particles was higher than around small particles. When small CaO particles were added together with Mg they quickly transformed to CaS. The Mg-gas helped to distribute the CaO particles in the hot metal and improved the kinetic conditions. The desulfurization abilities of some commonly used agents, namely fluidized CaO, CaC2, commercial-CaO, Mg, mixtures of commercial-CaO-Mg, and ZnO were studied and compared under the same experimental conditions. While fluidized CaO showed the best performance, commercial-CaO mixed with 20 mass % Mg achieved the second best desulfurization. Mg-granules performed slightly better than CaC2 and commercial-CaO, but somewhat less satisfactory compared to fluidized CaO and commercial-CaO-Mg mixtures. ZnO does not influence the sulfur concentration of hot metal. === <p>QC 20140404</p>