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Oxidation of Chromium: Methods To Minimize Chromium Losses in Electric Arc Furnance Applyingthermodynamics Applications

Chromium is lost during electric arc furnace steelmaking but can be minimized by efficient reduction from slag. Chromium oxidizes during steelmaking when it reacts with oxygen in solution, gas, or oxides in slag. Reduction of chromium oxide in slag depends on the reductant used and controlling slag chemistry to ensure high chromium oxide reduction without contaminating the melt. Calcium carbide has been shown to be an effective reductant for chromium oxide in the temperature range of 1550 to 1700°C. However, more work is still needed to overcome operational challenges for routine use of calcium carbide in electric arc furnaces for stainless steel production.

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273 views

Oxidation of Chromium: Methods To Minimize Chromium Losses in Electric Arc Furnance Applyingthermodynamics Applications

Chromium is lost during electric arc furnace steelmaking but can be minimized by efficient reduction from slag. Chromium oxidizes during steelmaking when it reacts with oxygen in solution, gas, or oxides in slag. Reduction of chromium oxide in slag depends on the reductant used and controlling slag chemistry to ensure high chromium oxide reduction without contaminating the melt. Calcium carbide has been shown to be an effective reductant for chromium oxide in the temperature range of 1550 to 1700°C. However, more work is still needed to overcome operational challenges for routine use of calcium carbide in electric arc furnaces for stainless steel production.

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METHODS TO MINIMIZE CHROMIUM LOSSES IN ELECTRIC ARC

FURNANCE APPLYINGTHERMODYNAMICS APPLICATIONS


Chromium is an important alloying element of stainless steel. But about 97% is lost by melting of steels in
the electric arc furnace (EAF). However to minimize the loss of chromium the efficient reduction of
chromium from slag is essentential.

OXIDATION OF CHROMIUM
Stainless have relatively high chromium contents, but very low carbon contents. Carbon can be removed by
oxidation, but as carbon is oxidized to very low levels, its activity drops rapidly, which makes chromium
oxidation favorable. Chromium oxidation occurs during stainless steelmaking when chromium reacts with
oxygen dissolved in steel, gaseous oxygen and oxides present in the slag. The reaction of Cr with dissolved
oxygen is considered to be the main oxidation mechanism. The oxidation of chromium with oxygen in
solution in the melt occurs parallel to the oxidation of other elements, e.g., carbon, aluminium, silicon and
manganese and it depends on the temperature and the activity of these elements and oxygen.
The standard free energy of oxidation (∆G°) of these elements is given by the following relations:
3[Cr] + 4[O] = (Cr3O4)
∆G0 = -244,800 + 109,6T
The equilibrium constant is for every of these reactions deduced from the change of standard free energy
and it is written for the oxidation of chromium as:
lg K1=53,521/T -23,96
and
K1 =aCr3O4 / a3Cr ∙ a4ₒ = aCr3O4 / f3Cr ∙ f4o ∙ w3Cr ∙ w4o
At high content of chromium in the melt the activity of oxygen and of carbon is lower, as both interaction
coefficients are negative.

Carbon, with an over critical content, delays the oxidation of chromium. The equilibrium between
chromium and carbon was for the pressure of pco = 1 bar and different temperature in Figure determined
applying the following relations and considering the coefficient of interaction of first order:
Cr2O3 + 4C = 3cr + 4CO
Log[(Cr)3/4 ∙ Pco/ac] = -11520/T + 7,64
REDUCTION OF CHROMIUM

The efficient reduction of the furnace slag depends on the selection of the suitable reductant dependent on
the used procedure and the control of the furnace slag which should ensure a high level of reduction of
chromium oxide from the slag and should not contaminate the melt. The importance is, the decrease of
chromium losses during the oxidative melting with the blowing in of different reductants. The first measure
for the control of the content of Cr2O3 is the use of a charge and alloys (FeSi) with a high content of silicon
ensuring the content of 0,3 % Si after the melting of the charge. During the discharge, the reduction of
chromium oxides is continued
with silicon in solution. However, for an efficient reduction of Cr2O3 is necessary with blowing of carbon in
to slag. The blowing of carbon is carried out with parallel blowing in of oxygen . The reduction of
chromium oxide is more efficient on conditions of:
– high activity of Cr2O3 by increased basicity,
– high activity of carbon, ac = 1 at the blowing in of carbon,
– low partial pressure,
– low activity of chromium in the metallic phase,
– high temperature.
When this carbide reacts with oxides in the slag, the product of the reaction are chromium, lime and carbon
monoxide.
(Cr2O3) + CaC2 = 2[Cr] + 2CO(g) + (CaO)
The change of Gibbs free energy in dependence on temperature for the reactions of chromium oxide
with silicon, carbon and calcium carbide are shown in Figure. It is clear that the reduction of chromium with
carbon is more efficient by high temperature, therefore in practice it is performed with the parallel blowing
in of oxygen. The reaction between silicon and chromium oxide is not strongly temperature dependent and
occurs, for this reason, also at lower temperature. The suitabilty of calcium carbide as reductant is shown by
the reaction between this carbide and chromium oxide, which has a lower Gibbs energy in the temperature
range of 1550 to 1700 °C.
CONCLUSION
Hence it can be concluded that the CaC2 has proven to be a good reducing agent. However, a lot of
operational challenges still need to be overcome for the routine use of CaC2 in the EAF in the manufacture
of stainless steel.

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