# Process Overview

As the melt is tapped from the furnace into the ladle the refining process is performed continuously, and continues for a set amount of time after the ladle is full. The purge gas is introduced through a porous plug located at the bottom of the ladle. This creates a bubble column rising through the ladle, driving a flow while mixing the melt. On its ascent the *O*_{2} in the bubbles will react with *Si* to form *SiO*_{2 }and *SiOg*. *SiOg* will be transported into the bubble saturating the gas phase, while *SiO** _{2}* will nucleate at the bubble interface. Tang [4] writes that

*SiO*

*forms a droplet on the surface, while Schei et al. [5] writes that it can form a film around the bubble.*

_{2}*SiO*

*then reacts with the impurities in the melt, primarily*

_{2}*Al*and

*Ca,*to form a predominantly

*SiO*

_{2}

*-CaO-Al*

_{2}

*O*

_{3}slag. When the slag is formed there will be a driving force to approach equilibrium between the present phases driving a mass transport to the slag so their respective equilibrium concentration can be reached. Since the temperature of the system is high it is often assumed that the reactions can be considered instantaneous [6]. As the diffusion of species in the metal is faster than in the slag, the rate determining step for the transport of

*Al*and

*Ca*is considered to be the transport in the slag [3, 4, 6]. To sum up the overall reactions can be expressed as:

- 1.
*Si F O**2*^{=}SiO*2* - 2.
*Si F*2 O2^{=}*SiOg* - 3.
*2Ca F SiO**2*^{=}2CaO F Si

**Fig. 1 **The whole system including the falling jet. Bubbles of entrapped air are displayed in *green*

- 4. 4A +
*3SiO2 =*3Si + 2A/2*O**3* - 5.
*3CaO*+ 2A = 3Ca + A/2O3

with Fig. 1 illustrating the whole process.

To express the system it has been proposed to use a standard [2] batch reactor model [3]. By applying two-film theory to the interface the molar transfer for species i, N_{i}, from the metal to slag can be expressed:

where *k _{ip}* [

^{m}] is the mass transfer coefficient for species i in phase p,

*p*[mg] is the density of phase p, and

_{p}*M*denotes the molar mass of species i. x

_{i}[kkgj_{i;P}denotes here the mass fraction of species i in phase p, and the superscript

^{1}expresses that it is at the interface. Due to the complexity of determining the mass transfer coefficient, k

_{i}, k

_{i m}and k

_{i;S}may be combined in an overall mass transfer coefficient k

_{i;t}[2].

where *K _{i}* denotes the equilibrium constant

*K*between the two phases for

_{i}=species i. Here *y _{i}* is the raultion activity coefficient for the oxide of species i and

*f*is the henrian activity coefficient of species i in the melt. By assuming that the slag and metal is completely mixed the mass balance can be expressed as [2]:

_{i}

Here m_{p} *[kg]* is the mass of phase p, and *A _{s}* [m

^{2}] is the reaction area. In Eq. 3 x^ is the hypothetical concentration in the metal at equilibrium with the actual concentration in the slag x

_{i;S}given by

*x^Kf = y*. Assuming that

_{i}x_{i;S}*x*

_{i;S}_{t=0}= 0 and lim x

_{im}= x1 Eq. 3 can be written as:

t!1 ^{l;m}

Equation 4 poses a problem due to most of the parameters on the RHS are functions with respect to time [3]. There is also an additional problem in the fact that ladle refining of silicon is done while tapping and therefore cannot be considered a true batch process for its full duration. Kero et al. [3] writes that allowing the RHS in Eq. 4 to be constant with respect to time will still give an equation which can be useful in comparing the refining kinetics in this system. This is due to the fact that m_{m}, m_{s}, A_{s} and p_{m} all change in the same way with respect to time for every species in the melt allowing it to serve as a crude approximation, according to Kero et al.

Cussler [7] has gathered multiple expressions for *k* and from this it can be seen that some common dependencies are *k* = f *(p,* U, L, D, r, p). Here U [^{m}] is the

terminal rise velocity, L [m] is some characteristic length, D ^{m} is the diffusion

coefficient, r U is the surface energy density, and p [ms] is the dynamic viscosity. This states that *k* is a property depending not only on the thermophysical properties of the phases involved, but also on the flow and geometries. If these properties can be considered constant or their behavior similar then k_{i;t} might be considered constant, or similar in behavior as well.

An interesting point when looking at Eq. 4 is that the exponential transient behavior of the *RHS,* after integration, is shared with the much more complex CFD models from Ashrafian et al. [6] and Olsen et al. [8] on the same system. In addition it shows a decent fit with the industrial sample set from Kero et al. [3], as seen in Fig. 2, for many elements, like Ca.

The experiments performed in this work differ from the industrial case in that a clean metal is used instead of a slag. This leads to the transport of *Al* and *Ca* from the slag, with a known slag concentration, to the clean metal. However, the mass transfer behavior should not be affected by this as the steps of transport are the same in both cases. Clean metal is used due to it being considerably easier to create a synthetic slag with an accurate composition, than doping pure silicon with specific

**Fig. 2 **Normalized *Ca, Al, Mg* and *B* concentrations as functions of time. From Kero et al. [3]. Printed with permission under the Creative Commons Attribution License as stated in Kero et al. [3] amounts of *Ca* and Al. By applying the same theory as used earlier on this system, with a RHS which is not a function of time, gives: