Oxygen

Atomic number 8
Density, 20 C (68 F) 1.13 g/cm3
Atomic weight 16
Melting point -218.4 C (-361.1 F)
Boiling point -182.96 C (-297.33 F)
GENERAL
Steelmaking is a process of controlled oxidation. That is, the production of "pure"
steel containing specified concentrations of carbon and other alloying elements proceeds
by the selective oxidation and removal of excessive carbon, phosphorus, silicon and
manganese from blast furnace iron (hot metal), scrap and pre-reduced pellets, the metallic
raw materials from which steel is derived. The steelmaker's main dilemma is to effect the
most complete and efficient removal of these impurities through oxidation, but to do so in
such a way that the resulting oxides are slagged off as much as possible by the time the
heat is cast or teemed. In general, the subject of oxygen may be divided into two broad
areas of concern: the use of the gas in oxygen steelmaking and the efficient removal or
control of residual oxides, once refining is completed.
OXYGEN STEELMAKING
History. One of the most important technological advances in steelmaking to
occur in this century is the use of essentially pure oxygen to refine blast furnace iron.
This development began modestly enough in both the US and Europe with the oxygen
enrichment of open hearth atmospheres, followed by crude lancing in the years following
World War II. To be sure, the principles had been understood for decades, but the
unavailability of sufficient quantities of the gas at reasonable costs precluded commercial
exploitation. It was, after all, hard to beat the price or availability of air and iron oxide.
 As soon as "tonnage oxygen" became a reality, however, developments followed
in fairly rapid order. Blast enrichment, in the OH and BF, and in the Thomas-Gilchrist
converters in Europe, were established as fairly common practices for increased
production efficiencies. The 1950s saw the first rapid growth of oxygen steelmaking. In
North America, it took the form of improved roof lancing techniques, mostly aimed at
increasing the output of the OH, upon which steelmaking then relied. Oxygen lancing in
the EF is also widely practiced, even though it is strictly speaking a spin-off of the
original development.
Concurrent with the beginnings of oxygen usage here, developments in Europe
took a different and far more important turn. Investigators in several countries recognized
that pure oxygen could not only augment existing steelmaking practices, but also actually
become a principal part of them. Following many experimental trials, the first "heat" of
oxygen steel was made in Switzerland in 1948 and the first actual oxygen converter
(called an L-D, originally for Linz, Austria, its location, and Prof. Durrer, the Swiss
inventor) began production in 1952. The process is popularly known in Europe today as
Linz-Donawitz, the site of another early converter. The process was originally intended
for low-phosphorus Central European iron ores. Steelmakers using the more common
European high-phos ores (as in the Thomas-Gilchrist process) soon developed lime
injection techniques, without which the new converter was thermodynamically
unworkable. North American mills were not faced with this problem.
The value of oxygen steelmaking was quickly recognized throughout the world
and within a decade, many converters had been built with vessel capacities almost ten
times that of the original Austrian unit. Today, the 350-ton range is seen in several
installations, and oxygen steelmaking has become the leading refining process in the
world. Several variants exist, but those found in North America take two forms: the top-
blown converter, or BOF (BOP) which is quite similar to the original L-D, and the
bottom-blown (Q-BOP) converter, which may be thought of as a descendent of the
Thomas-Gilchrist, or basic Bessemer.
Oxygen requirements. As mentioned above, the BOF required the development of
high-capacity oxygen plants before it could become a commercial reality. Such plants,
which rely on air liquification and fractional distillation, are usually located "on site" or
very near to it. Their product is 99.5% O2; the major impurity is argon. Some nitrogen
may be present as well, but its concentration is so low as to contribute only trace amounts
to the N content of the liquid steel.
Oxygen availability must be sufficient to deliver 48-57 m^3 (1700-2000 ft^3) per
ton of steel. Delivery rates are typically 565-710 m^3/min (20,000-25,000 ft^3/min) or
more at pressure of 1.45 MPa (210 psig).
Steelmaking. In the BOF, oxygen is impinged on the surface of the liquid metal in
the vessel through a water-cooled, multiported, retractable lance, creating a violent
frothing action. Lance design is a critical factor for the success of the practice since it
affects behavior of the metal in the vessel, yield and lining life. In the Q-BOP, oxygen is
introduced through tuyeres in the vessel bottom, much as in a Bessemer converter. To
protect the tuyere refractories from rapid wear, the incoming oxygen is shrouded by an
annular flow of a protective gas such as methane (natural gas) or propane.
The charge to an oxygen converter consists of hot metal, scrap, lime and often
some dolomitic burned lime, iron oxide (mill scale) and possibly limestone. Proportions
will vary depending on the availability, temperature and composition of the hot metal, the
price and availability of scrap and the operating parameters of the furnace. A typical hot
metal/scrap ratio is around 72/28, but this can vary somewhat. More scrap will be
charged during periods of limited hot metal availability (prevalent during early BOF
operations and still felt today when, say, BFs are down for reline) or when scrap prices
are particularly favorable. When this occurs, it may become necessary to preheat the
scrap, increase the temperature of the hot metal, or use auxiliary fuels. Solid fuels are
added directly to the vessel and include calcium carbide, coke, silicon steel scrap, silicon
carbide and ferrosilicon. The latter two are preferred for several reasons. Coke may make
the production of low carbon heats difficult; calcium carbide presents awkward handling
problems, etc. Alternatively, fuel may be mixed directly with the main oxygen source, as
in the so-called oxy-fuel blowing technique. This does, however, require higher oxygen
delivery rates.
Oxygen lancing, using a variety of lance techniques, is practiced in electric arc
furnaces to speed up the process, reduce power consumption, and provide fast and
efficient reductions in carbon level. Roof mounted lances are impractical to EFs, so they
are usually simply inserted through a port in the charging door or furnace wall. Oxy-fuel
burners are becoming more prevalent to further shorten heat times.
DEOXIDATION
Once a heat has been purified of the elements phosphorus, silicon and manganese
it is quite saturated with oxygen, which exists as FeO dissolved in the bath. Typical
oxygen contents at low carbon levels, below 0.10%, may run to 900-1000 ppm (0.09-
0.10%) or a little more (Fig. 2).
However, from this point on until the addition of solid deoxidizers, the oxygen
concentration will mainly be determined by the equilibrium between oxygen and carbon
for the particular ambient temperature, with residual manganese having a strong effect
below about 0.06% C. As temperature rises, the amount of oxygen in equilibrium with a
particular deoxidizer (carbon or otherwise) increases. Thus, it is common practice to
depict solubility isotherms for a range of temperatures of interest to steelmakers. Such
curves are shown in Figs. 3 and 4. It should be noted that true thermodynamic
equilibrium is probably never achieved in a process that proceeds as rapidly as
steelmaking and, if it is achieved, it is certainly too complex to depict on any one
diagram. However, the curves are very valuable in that they indicate the relative strengths
of the deoxidizers, the changes in their rates of deoxidation with concentration, if any,
and (as in Fig. 5) interactive effects. Most important, though, they depict the limit of
oxygen possible for a given concentration of deoxidizer.
Fig. 6, for example, shows that aluminum and titanium are stronger deoxidizers
than silicon, that carbon is stronger than silicon at high concentrations but not at low, and
that both are stronger than vanadium, chromium or manganese. Note that this figure
depicts the situation at 1600 C (2912 F) and at one atmosphere pressure. Under reduced
pressure, as in a vacuum degasser, the partial pressure of CO above the melt is reduced
and the deoxidizing power of carbon increases, surpassing that of silicon at all
concentrations. The AOD works on the same principle, but uses argon gas instead of
vacuum to reduce the CO partial pressure.
Low carbon steels, then, will have inherently higher oxygen content than high
carbon steels at tap unless the gas is removed by other means. Aside from vacuum carbon
deoxidation and the AOD, the "other means" are the solid deoxidizers. Aluminum,
ferrosilicon, silicomanganese and calcium silicon are the most common. For a more
thorough description of all the deoxidizers, see the appropriate chapters under their
principal constituents.
One other aspect of the solution isotherms should be noted, as it has been put to
important use in the past years. The development of so-called solid electrolytes (often
solutions of oxides having the ability to transport ions such as O= and to convert this to a
measurable EMF) has made possible the almost instantaneous determination of dissolved
bath oxygen. This is the principle behind the oxygen probe. With a probe and a
thermocouple to simultaneously record the bath temperature (they are customarily
mounted in the same unit) plus a calibration against the applicable solubility isotherm, it
becomes possible to determine (a) the carbon content via the oxygen value and (b) the
amount of deoxidizer(s) required to complete the steelmaking process.

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