Date of Award

8-2014

Embargo Period

3-11-2015

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Materials Science and Engineering

Advisor(s)

Richard J. Fruehan

Second Advisor

Sridhar Seetharaman

Abstract

Low phosphorus content steels are essential for steel applications where high ductility is required, such as thin sheets, deep drawn, pipelines and automobile exteriors. In the past, phosphorus control was not considered a big challenge in steel production in the US because iron ores with low phosphorus contents were readily available and considered cheap. However, in the last decade, the iron ore price has risen by roughly 400% and lower cost iron sources generally have higher phosphorus content. In integrated steel plants, phosphorus removal usually takes place during the oxygen steelmaking process (OSM) but in Japan a intermediate step for hot metal dephosphorization is commonly used. There are various types of OSM furnaces but the most widely used remains the top-blown Basic Oxygen Furnace (BOF). The BOF slag can be recycled to a sinter plant or directly to the blast furnace, ultimately increasing the phosphorus input in the process. In order to meet new demands for phosphorus control, it is necessary to improve our understanding on the thermodynamics and kinetics of the phosphorus partitioning reaction between slag and metal melts during steelmaking. Therefore, the present work has been divided in three strongly correlated sections: phosphorus equilibrium between metal and slag; analysis of plant data; and observations of the reaction kinetics. Phosphorus equilibrium between liquid metal and slag has been extensively studied since the 1940's. It is well known that CaO and FeO are the main slag constituents that help promote dephosphorization. On the other hand, dephosphorization decreases with temperature due to the endothermic nature of the reaction. Many correlations have been developed to predict the phosphorus partition ratio as a function of metal and slag composition as well as temperature. Nevertheless, there are still disagreements in the laboratory data and the equilibrium phosphorus partition can be predicted with an uncertainty of a factor of up to 5. The first part of the present work focuses on generating more reliable equilibrium data for BOF-type slags by approaching equilibrium from both sides of the reaction. The experimental results were combined with two other sets of data from different authors to produce a new correlation that includes the effect of SiO2 on the phosphorus partition coefficient, LP . Although the quantification of phosphorus equilibrium is extremely important, most industrial furnaces do not operate at equilibrium, usually due to liquid slag formation, kinetics and time constraints. Thus, it is important to know how close to equilibrium different furnaces operate in order to suggest optimal slag compositions to promote dephosphorization. The present work analyzed four large sets of data containing the chemical compositions of both slag and metal phase as well as the tapping temperature of each heat. Each set of data corresponded to different furnaces: one AOD (Argon Oxygen Decarburization), two top-blown BOFs and one Q-BOP or OBM. It was found that the bulk slag composition can greatly \mask" the data due to solid phases coexisting with the liquid slag. The author used the software package FactSage to estimate the amount of solids in the slag and liquid slag composition. It was found that the AOD is the reactor closest to equilibrium, followed by the Q-BOP (OBM) and the two top-blown BOFs. It was noted that the stirring conditions and slag composition are two key variables to enable optimum phosphorus removal. Also, over saturating the slag with CaO and MgO does not seem to benefit the process to any extent. Lastly, interesting observations on the behavior of small metal droplets reacting with slag are presented and discussed. It was found that dynamic interfacial phenomena at the metal-slag interface is likely to play a significant role in the kinetic behavior of the system, due to the exchange of surface active elements, such as oxygen, which dramatically lowers the interfacial tension and cause spontaneous emulsification. Although this phenomenon has been studied, actual quantification of changes in interfacial area remain a challenge. The author developed an experimental method to enable better quantification of spontaneous emulsification and two sets of experiments were carried. One with an Fe containing 0.2 wt.% P and another in a P-free system where pure iron was oxidized. It was found that phosphorus did not play a role in spontaneous emulsification and it was rapidly removed before the onset of dynamic interfacial phenomena. Emulsificaion was maybe caused by de-oxidation of the metal after phosphorus removal took place and the metal became super saturated with oxygen by an unknown reason. The estimated surface area rapidly increases by over an order of magnitude during the beginning and intermediate periods of the reaction. The metal drop breaks into hundreds of small droplets, effectively emulsifying the metal into the slag. With time, the surface area decreases and the metal droplets coalesce. Similar results were observed for an Fe droplet being oxidized. Spontaneous emulsification takes place regardless of the direction of oxygen transfer and the changes in surface area are similar for both cases. The last chapter describes the industrial relevance of the present work, summarizes the findings, revisits the hypotheses and presents potential future work where further research is encouraged.

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