Desulfurization of Liquid Steel Containing

Aluminum or Silicon with Lime

R. J . FRUEHAN

The r e a c t i o n m e c h a n i s m s for the d e s u l f u r i z a t i o n of i r o n c o n t a i n i n g f r o m 0.04 to 1.5 pct

a l u m i n u m or 1.1 to 3.7 pct s i l i c o n by CaO at 1600~ have b e e n e x a m i n e d . The d e s u l f u r i z a -
tion of Fe-A1 by Ca(9 is c o n s i d e r a b l y f a s t e r than that of F e - S i . T h e b a s i c d i f f e r e n c e b e -
t w e e n the two p r o c e s s e s is that Fe-A1 a l l o y s can be d e s u l f u r i z e d by the f o r m a t i o n of
A1203, w h e r e a s for F e - S i m e l t s it is n e c e s s a r y to f o r m Ca2SiO4. T h e r a t e of d e s u l f u r i z a -
tion of F e - S i a l l o y s by Ca(3 is c o n t r o l l e d by the f o r m a t i o n of the g a s e o u s i n t e r m e d i a t e s ,
SiS and S, and is the s a m e as that for d e s u l f u r i z a t i o n in v a c u u m . T h e r a t e of d e s u l f u r i z a -
tion of F e - A 1 m e l t s is fast, and is a p p a r e n t l y c o n t r o l l e d by the diffusion of s u l f u r to the
liquid m e t a l - C a O i n t e r f a c e . E x p e r i m e n t s w e r e a l s o conducted to d e m o n s t r a t e that s u l f u r
could be t r a n s f e r r e d to CaO by the g a s e o u s i n t e r m e d i a t e s SiS and S.

THE o v e r a l l d e s u l f u r i z a t i o n r e a c t i o n s of F e - C , Si-S alloys at 1400~ About 8 g of the a l l o y was con-

F e - S i , and Fe-A1 a l l o y s with CaO can be r e p r e s e n t e d
by
S + CaO + C = CaS + CO [1]
S + 2CaO + ~Si = CaS + ~CaeSiO4 [2]
3S + 4CaO + 2A1 = 3CaS + CaA1204. [3]
As d i s c u s s e d in p r e v i o u s p u b l i c a t i o n s , ~-3 the r e a c t i o n s
as w r i t t e n r e p r e s e n t the o v e r a l l r e a c t i o n ; to u n d e r -
s t a n d the d e s u l f u r i z a t i o n m e c h a n i s m the i n d i v i d u a l
s t e p w i s e r e a c t i o n s should be c o n s i d e r e d .
F o r e x a m p l e , Eq. [2] has a m i n i m u m of t h r e e p h a s e s
p r e s e n t , a s s u m i n g that the CaO is i m p r e g n a t e d with
liquid s l a g . F o r this case t h e r e is only a line of
contact b e t w e e n the t h r e e p h a s e s which is not f a v o r -
able for r a p i d d e s u l f u r i z a t i o n . It has b e e n p r o p o s e d
that an i m p o r t a n t step in the d e s u l f u r i z a t i o n of F e - S i
m e l t s is the f o r m a t i o n of the v a p o r s p e c i e s SiS and
that the CaO m e r e l y acts as a getter for the s u l f u r -
b e a r i n g g a s e s . It is one of the p u r p o s e s of the p r e s e n t
work to p r o v e this h y p o t h e s i s . The d e s u l f u r i z a t i o n of
F e - A 1 m e l t s m u s t p r o c e e d by m e a n s of a n o t h e r type
of m e c h a n i s m s i n c e t h e r e is no s i g n i f i c a n t a l u m i n u m -
s u l f u r v a p o r s p e c i e s . The m e c h a n i s m of d e s u l f u r i z a -
tion of Fe-A1 alloys with CaO will a l s o be e x a m i n e d .
It has b e e n r e c e n t l y p r o p o s e d by T u r k d o g a n 4 that
liquid s t e e l c a n be d e s u l f u r i z e d e f f i c i e n t l y by i n j e c t -
i n g CaO with A1 or Si. By doing so a l a r g e CaO7
l i q u i d - m e t a l s u r f a c e a r e a is p r o v i d e d and a l o c a l l y
high A1 or Si content at the i n t e r f a c e will e x i s t , both
of which a r e f a v o r a b l e for r a p i d d e s u l f u r i z a t i o n . The
p r e s e n t work was u n d e r t a k e n to d e t e r m i n e whether
the d e s u l f u r i z a t i o n r e a c t i o n s a r e fast enough to make
this p r o p o s e d p r o c e s s f e a s i b l e .
EXPERIMENTAL
T o d e m o n s t r a t e the e f f e c t i v e n e s s of s u l f u r t r a n s f e r
f r o m l i q u i d - i r o n a l l o y s to CaO via the gas phase, a
s e r i e s of e x p e r i m e n t s was made with F e - 3 . 0 pct C-
R. J. FRUEHAN is with U.S. Steel Research Laboratory, Monroe-
ville, PA 15146
Manuscript submitted October 5, 1977.
ISSN 0360-2141/78/0612-0287500.75/0
METALLURGICALTRANSACTIONS B 9 1978AMERICANSOCIETYFOR METALSAND
THE METALLURGICALSOCIETYOF AIME
t a i n e d in a ZrO2 c r u c i b l e (1.7 c m ID) and 1 g of g r a n u -
l a r CaO p a r t i c l e s w e r e s u s p e n d e d above the m e l t in a
p l a t i n u m b a s k e t at a p r e d e t e r m i n e d d i s t a n c e (x) of 0.3,
0.8, or 2.5 c m above the m e l t . The s a m p l e s w e r e
heated in a v e r t i c a l tube f u r n a c e (4.0 c m ID) with a top
flow of A r at 1.5 1//min. T h e l i m e p a r t i c l e s , p r e v i o u s l y
c a l c i n e d at 1500~ w e r e within the s i z e r a n g e f r o m
0.5 to 1 m m and had an i n t e r n a l p o r e a r e a of 0.3 m2//g.
T h e i n i t i a l s u l f u r c o n t e n t of the m e l t was 0.1 pct and
the Si c o n t e n t v a r i e d up to 3.8 pct. S e p a r a t e d u p l i -
cate e x p e r i m e n t s w e r e a l s o conducted in which t h e r e
was no CaO p r e s e n t , with the d i s t a n c e by which the
c r u c i b l e wall extended above the m e l t b e i n g the s a m e
as the d i s t a n c e above the m e l t at which the CaO was
suspended.
In a s e c o n d s e r i e s of e x p e r i m e n t s 5000 g of an F e - C -
S, Fe-A1-S, or F e - S i - S alloy c o n t a i n e d i n a 9.6 c m ID
z i r c o n i a c r u c i b l e was heated in a n induction f u r n a c e
in a p r o t e c t i v e a t m o s p h e r e of flowing A r . A f t e r the
t e m p e r a t u r e r e a c h e d 1600~ a s a m p l e of the m e l t was
taken by s u c t i o n into a s i l i c a tube, a f t e r which pow-
d e r e d l i m e (<0.1 mm) was added. U s u a l l y 125 g of
CaO was used; however, in s e v e r a l c a s e s d u p l i c a t e
e x p e r i m e n t s w e r e conducted in which 80 or 160 g of
CaO w e r e u s e d . In a l l c a s e s the l i m e was s u f f i c i e n t
to cover the e n t i r e s u r f a c e of the m e l t , and t h e r e was
no d i f f e r e n c e in the r e s u l t s when the a m o u n t of CaO
used was v a r i e d within this r a n g e . S a m p l e s w e r e t a k e n
at r e g u l a r i n t e r v a l s and a n a l y z e d for s u l f u r and
a l u m i n u m , s i l i c o n , or c a r b o n . E x p e r i m e n t s w e r e a l s o
made with F e - A 1 - S a l l o y s u n d e r v a c u u m (10 Pa) with
no CaO addition; the p r o c e d u r e used has b e e n d e s c r i b e d
previously.~
RESULTS AND DISCUSSION
The r e s u l t s o b t a i n e d with the CaO s u s p e n d e d 0.8 c m
above the s u r f a c e of the 8 g m e l t a r e shown in F i g . 1.
A s i m i l a r r e l a t i o n s h i p was o b t a i n e d with the Ca(3 for
each of the other d i s t a n c e s above the m e l t . T h e r a t e
of d e s u l f u r i z a t i o n i n c r e a s e d with i n c r e a s i n g Si c o n t e n t
of the m e l t . It is also i m p o r t a n t to note that with 3.8
pct Si in the m e t a l the r a t e of d e s u l f u r i z a t i o n was
VOLUME 9B, JUNE 1978-287
 In F i g . 2 the slopes of the line for In (pet S / p c t S o ) v s
Lime a r e pioLted vs l / x ; the expected b e h a v i o r is ob-
served.
It is p o s s i b l e to e s t i m a t e the r a t e of d e s u l f u r i z a t i o n
f r o m the t h e r m o d y n a m i c s of F e - C - S i - S alloys, the
f r e e e n e r g y of f o r m a t i o n of SiS, and a n e s t i m a t e d value
of rn. At 1400~ the e q u i l i b r i u m c o n s t a n t K for Eq.
[9] is 0.496
s + s i : sis(g) [9]
-0.8 Psis
K=
a s i f s pct S

% F o r an alloy c o n t a i n i n g 3.8 pct Si and 3 pct C the

3.8O% Si
a c t i v i t y coefficient of s u l f u r (fs) is 5 and the a c t i v i t y
-,,2 [ I l
200 400 600 of s i l i c o n (asi) is 0.001.1 T h e r e f o r e the e q u i l i b r i u m
TIME, rain p a r t i a l p r e s s u r e os SiS is given by
Fig. 1--Desulfurization of Fe-3.0 pct C-X alloys at 1400~ by
vapor transport to porous lime granules suspended 0.8 em PSiS = 2.5 • 10 "a (wt pct S), a i m
above the melt. [10]
P s i s = 2.5 x 102 (wt pct S) Pa.
about the s a m e with or without the CaO at a d i s t a n c e
of 0.8 cm above the m e l t . T h e s e r e s u l t s s u g g e s t that It is p o s s i b l e to e s t i m a t e m by u s i n g Eq. [8]. The
the r a t e is c o n t r o l l e d p r i m a r i l y by diffusion of SiS value of D is e s t i m a t e d to be 3 c m 2 / s f r o m the data
v a p o r through the s t a g n a n t gas l a y e r over the m e l t . and equations given by H i r s c h f e l d e r , e t a l . 6 At a dis"
The r e a c t i o n of SiS with CaO on the pore w a i l s of Lance of x = 0.8 c m the c a l c u l a t e d v a l u e of k ' m is 7
the l i m e p a r t i c l e s may be r e p r e s e n t e d , for e x a m p l e , • 10 -5 s "I c o m p a r e d with the o b s e r v e d value of 4 • 10 -~
by s -z. The a g r e e m e n t is good c o n s i d e r i n g the u n c e r t a i n -
t i e s in the t h e r m o d y n a m i c s and the e s t i m a t i o n of m .
SiS(g) + 2CaO = CaS + ~Ca2SiO4 + ~ S i ( / ) . [4] I n p r e v i o u s work done in v a c u u m 1 it was found that
the r a t e of d e s u l f u r i z a t i o n of F e - S i - S alloys was p r i -
T h e e q u i l i b r i u m p a r t i a l p r e s s u r e of SiS for this r e a c - m a r i l y c o n t r o l l e d by a slow c h e m i c a l r e a c t i o n for the
t i o n at 1400~ is 2 • 10 "~ Pa, z'5 which is s e v e r a l o r d e r s f o r m a t i o n of SiS, the r a t e of which was 1/10 the r a t e
of m a g n i t u d e lower than that at the s u r f a c e of the a l - for f r e e v a p o r i z a t i o n of SiS. At 1400~ the r a t e con-
loys i n v e s t i g a t e d . T h e r e f o r e , the p a r t i a l p r e s s u r e of s t a n t for the f o r m a t i o n of SiS is 0.02 s -z. A p p r o x i m a t -
SiS at the CaO s u r f a c e can be a s s u m e d to be z e r o and ing m by D / x gives x = 25 /zm as the c r i t i c a l d i s t a n c e
the r a t e e q u a t i o n for d e s u l f u r i z a t i o n c a n be r e p r e s e n t e d b e t w e e n the lime p a r t i c l e s and the s u r f a c e of the m e l t
by
for a p p r o a c h to the m a x i m u m r a t e of d e s u l f u r i z a t i o n ;
d pct S 3200 A that is, the r a t e i n c r e a s e s as the d i s t a n c e between the
dt - RTW m PSiS [5] CaO p a r t i c l e and the m e l t d e c r e a s e s u n t i l that d i s t a n c e
is 25 tzm. T h e r e f o r e , in w e l l - s t i r r e d l i q u i d - F e alloys
where
c o n t a i n i n g s i l i c o n , the r a t e of d e s u l f u r i z a t i o n by l i m e in
A = s u r f a c e a r e a of the m e l t (2.27 cm2), d i r e c t contact with the m e l t will be c l o s e to that
R = gas c o n s t a n t , a c h i e v e d in v a c u u m . T h i s c o n c l u s i o n w i l l be f u r t h e r
W = weight of the m e l t (8 g), s u b s t a n t i a t e d by the r e s u l t s to follow.
T = a b s o l u t e t e m p e r a t u r e (K),
Psis = the e q u i l i b r i u m vapor p r e s s u r e of SiS which is
,=
p r o p o r t i o n a l to the s u l f u r content.
The i n t e g r a t e d f o r m of this equation is

ln Pct S = - k ' m t [6]

pct So 8 I
w h e r e k ' is a c o n s t a n t dependent on the p r e s s u r e of
SiS,
As shown in Appendix A the mass-transfer coeffi- K

cient, m, is expected to v a r y with the d i s t a n c e f r o m

the m e l t to the CaO and is given by 4

1 1 x
m m o
+
D
[7]

w h e r e m o is the m a s s - t r a n s f e r coefficient at the top

I I I
of the c r u c i b l e o r at the CaO p a r t i c l e s and D is the 1 2 3
i n t e r d i f f u s i v i t y . In the p r e s e n t work m o is r e l a t i v e l y 1
~. cm t
l a r g e and Eq. 7 r e d u c e s to
Fig. 2--Rate constant for the desulfurization of Fe-3.8 pet
D Si-3 pct C melts at 1400~ as a function of the reciprocal of
.~ : - . [8]
X the diffusion distance to lime particles above the melt.

288 V O L U M E 9B, J U N E 1 9 7 8 METALLURGICAL TRANSACTIONS B

 T y p i c a l r e s u l t s obtained with 5000 g m e l t s at 1600~ 0,OOlB I |
with CaO in d i r e c t contact with F e - A 1 a l l o y s are g i v e n
in F i g . 3 for an initial sulfur content of 0.1 pct and in 3S + 2AI + 3CaO = AI20 3 + 3CaS
Fig. 4 for 0.031 pct i n i t i a l s u l f u r . The A1 content ~ EQUILIBRIUM

changed during the c o u r s e of the e x p e r i m e n t , partly b e -

0.0OB O 20 MINVTES
c a u s e of the r e a c t i o n i t s e l f but p r i m a r i l y b e c a u s e of
~ 9 120 MINUTES
oxygen pickup f r o m the a t m o s p h e r e . In the e x p e r i m e n t s
in w h i c h no CaO was added at a t m o s p h e r i c p r e s s u r e
or in v a c u u m , there was no a p p r e c i a b l e d e s u l f u r i z a -
Lion, indicating that there is no s i g n i f i c a n t v o l a t i l e a l u - u~
m i n u m - s u l f u r s p e c i e s as in the c a s e of s i l i c o n . 0.004
The i n i t i a l rate of d e s u l f u r i z a t i o n of F e - A 1 m e l t s
i s v e r y rapid. A s shown in F i g . 5, within l e s s than 20
rain the sulfur content was reduced below that for
e q u i l i b r i u m with A1203.
0.00"2
3S + 3CaO + 2A1 = 3CaS + A12Oa. [11]
FIowever, in g e n e r a l e v e n at long t i m e s , 120 min,
the s u l f u r content w a s s t i l l higher than that in e q u i l i - 4CaO + 2AI + 3S =
3CaS + CaAI204
b r i u m with CaA1204. 5 In s e v e r a l c a s e s the sulfur con- EQUILIBRIUM
tent of the m e t a l i n c r e a s e d at long t i m e s b e c a u s e the I I I I i
0.2 0.4 0.6
A1 content was d e c r e a s i n g . It appears that the r e a c -
AI, wt %
tion s e q u e n c e
F i g . 5 - - S u l f u r c o n t e n t s a s a f u n c t i o n of a l u m i n u m contents at
S + CaO = O + CaS [12] 20 and 120 rain.

2A1 + 3 0 = A1203 [13 ]

0.1
is v e r y rapid and goes to c o m p l e t i o n e a s i l y . The f o r -
0,06
0,1q
l I I I I
0.04
Al(initi~) /Ill fir~l
O 0.06 0.03
0,05 E] 0,60 0.04
9 0,14 0.0O 0.02
9 0.42 0.36
9 1,51 1.50
0,02
0.01

Si
'~ 0.01 O
u~ 0.006

0.004
0.005
0
3.70% Si
0.602

0.602 ~ 9I
0.601 I ~ "I ~ I
40 80 1120
o.601 I I I I I I
20 40 60 60 160 120 140 TIME, rain
TIME, rain F i g . 6 - - D e s u l f u r i z a t i o n of F e - S i a n d F e - C m e l t s by CaO a t
F i g . 3 - - D e s u l f u r i z a t i o n of F e - A 1 m e l t s w i t h C a O a t 1600~ 1600~ at atmospheric pressure.

0.04~ l l I l I I m a t i o n of the a l u m i n a t e is apparently m u c h s l o w e r

s i n c e this r e q u i r e s a s o l i d - s o l i d r e a c t i o n
AI(5 minuZe~l All~al~

002
D 0,09 0.04 A1203 + CaO = CaA1204 [14]
O 0,32 0,20
or the d i r e c t r e a c t i o n indicated by Eq. [3].
001
T h e i n i t i a l rate of d e s u l f u r i z a t i o n of F e - A 1 a l l o y s
by CaO is v e r y fast and is p o s s i b l y c o n t r o l l e d by the
0.606
diffusion of s u l f u r f r o m the bulk to the liquid m e t a l -
CaO s u r f a c e . The integrated f o r m of the rate equation
for m a s s - t r a n s f e r c o n t r o l i s given by

In pct S t - pct S e = - k t [15]

pct S o - pct S e
w h e r e h is the m u s s - t r a n s f e r c o e f f i c i e n t for an in-
d u c t i v e l y s t i r r e d m e l t . A s s u m i n g that the A1 c o n c e n -
o.ooi I I I I I I
20 40 60 80 100 120 140 tration at the s u r f a c e is a p p r o x i m a t e l y equal to that
TIME, min in the bulk and the o x y g e n potential is d e t e r m i n e d by
F i g . 4 - - D e s u l f u r i z a t i o n of F e - A I m e l t s w i t h C a O at 1600~ the A1 - AI~O~ e q u i l i b r i u m , it i s p o s s i b l e to c a l c u l a t e

METALLURGICAL TRANSACTIONS B VOLUME 9B, JUNE 1978-289

 0 ' I I r r a t e c o n t r o l l i n g r e a c t i o n is the f o r m a t i o n of SiS
%.
AI (0,32- 0,04)
St + S -- SiS(g). [18]
SO (0,10-0,031)
1 --
The r e m a i n i n g r e a c t i o n s for d e s u l f u r i z a t i o n a r e fast

,:Z: 2P
and it is u n c l e a r what the exact r e a c t i o n s might be.
F o r e x a m p l e the r e a c t i o n might p r o c e e d by Eq. [4]
or a s follows:
=

%. SiS(g) + CaO : CaS + SiO(g) [19]

3-- ,% 8
%. SiO(g) + 2CaO + O = Ca2SiO4. [20]
X As d i s c u s s e d e a r l i e r , if the r a t e of d e s u l f u r i z a t i o n
4 I I of F e - S i a l l o y s is c o n t r o l l e d by the f o r m a t i o n of SiS,
o 4 8 the r a t e should be the s a m e as that o b s e r v e d in
TIME, rain v a c u u m . The r a t e e q u a t i o n d e r i v e d p r e v i o u s l y 1,2 is
Fig. 7--Desulfurization of Fe-A1 melts by CaO at 1600~ in
an inductively stirred melt. In pct S _ 100A (klaSi + k2)fst [21]
pcs% w
the e q u i l i b r i u m s u l f u r content (pet Se). U s i n g the where
a v e r a g e A1 c o n t e n t s the r e s u l t s a r e plotted in F i g . 7 /el = the r a t e c o n s t a n t for the f o r m a t i o n of SiS,
in a c c o r d a n c e with Eq. [15]. It should be noted that in /e2 = the r a t e p a r a m e t e r for f r e e v a p o r i z a t i o n of S,
g e n e r a l t h e r e is a dual diffusion p r o c e s s , with A1 a l s o A = the s u r f a c e a r e a of the melt,
diffusing to the s u r f a c e , but for this r o u g h a p p r o x i m a - W= the weight of the melt,
tion this was n e g l e c t e d . The r e s u l t s fit the e q u a t i o n asi = the a c t i v i t y of s i l i c o n .
o v e r a f a i r l y wide r a n g e of A1 contents; and the slope
of the l i n e , which is the m a s s - t r a n s f e r coefficient, F r o m the t h e r m o d y n a m i c p r o p e r t i e s for the alloys
a g r e e s within a f a c t o r of two with that c a l c u l a t e d f r o m given p r e v i o u s l y 2 the r a t e c o n s t a n t s d e r i v e d f r o m the
the e q u a t i o n s developed by M a c h l i n 7 for m a s s t r a n s f e r s l o p e s of the r a t e c u r v e s in F i g . 5 a r e plotted in Fig.
in an i n d u c t i v e l y s t i r r e d m e l t . T h i s a g r e e m e n t is 8 in a c c o r d a n c e with Eq. [21] along with the r e s u l t s of
r e a s o n a b l e c o n s i d e r i n g the a p p r o x i m a t i o n s made in the p r e v i o u s work o b t a i n e d in v a c u u m . 2 8-~ The p r e s e n t
calculations. r e s u l t s obtained at a t m o s p h e r i c p r e s s u r e with CaO
Although the r e s u l t s a r e i n s u f f i c i e n t to prove con- a r e in e x c e l l e n t a g r e e m e n t with those obtained under
c l u s i v e l y that the i n i t i a l r a t e of d e s u l f u r i z a t i o n of v a c u u m with no CaO. T h e r e f o r e the r a t e of d e s u l f u r i z a -
F e - A 1 a l l o y s by CaO in the p r e s e n t work is c o n t r o l l e d tion of F e - S i - S alloys by CaO is p r i m a r i l y c o n t r o l l e d
by the diffusion of s u l f u r to the s u r f a c e , this a s s u m p - by the r a t e of f o r m a t i o n of SiS and S, and the rate is
tion a p p e a r s r e a s o n a b l e and the r e s u l t s a r e c o n s i s t e n t the s a m e as that achieved in v a c u u m .
with this i n t e r p r e t a t i o n . In any case the r a t e is v e r y
f a s t and t h e r e is no e v i d e n c e of a slow c h e m i c a l r e a c - SUMMARY AND CONCLUSIONS
tion.
As shown in F i g . 6, the r a t e of d e s u l f u r i z a t i o n of T h e m e c h a n i s m s of d e s u l f u r i z a t i o n of s t e e l contain-
F e - S i a l l o y s is c o n s i d e r a b l y s l o w e r than that of Fe-A1 ing A1 o r Si by CaO have b e e n e x a m i n e d . F o r F e - S i
a l l o y s . F o r F e - S i a l l o y s the d e s u l f u r i z a t i o n r e a c t i o n a l l o y s the i m p o r t a n t step in the p r o c e s s is the f o r m a -
in which SiO2 is f o r m e d is not t h e r m o d y n a m i c a l l y tion of SiS(g). The r a t e of d e s u l f u r i z a t i o n is c o n t r o l l e d
f a v o r a b l e u n d e r the c o n d i t i o n s of the p r e s e n t work

2S + 2CaO + Si = SiOz + 2CaS. [16]

J
J
T h e e q u i l i b r i u m s u l f u r c o n t e n t for Eq. [16] at 1 pct Si t 9
J
is over 0.1 pct. 5 D e s u l f u r i z a t i o n by the f o r m a t i o n of J
f
CaSiO3 is a l s o not f a v o r a b l e , with e q u i l i b r i u m s u l f u r f
f
content b e i n g 0.07 pct at 1 pct Si. It is t h e r e f o r e f
p
n e c e s s a r y for Ca2SiO4 to f o r m a s i n d i c a t e d by Eq. [2],
for which the e q u i l i b r i u m s u l f u r c o n t e n t is about 0.001 J
J
pct at 1 pct Si. V
x /
It is difficult to conceive that the d e s u l f u r i z a t i o n VA //
m e c h a n i s m is by the d i r e c t r e a c t i o n given by Eq. [2] V o/f OHNO a ISHIDA
/ VACUO SEFIGAL
b e c a u s e it r e q u i r e s Si and S a t o m s in the m e t a l to col- v /
SEHGAL & MITCHELL
o /
lide s i m u l t a n e o u s l y with a CaO p a r t i c l e . It a l s o does -- V jl Mt FRUEHAN & TURKDOGAN
not s e e m likely that the m e c h a n i s m c o n s i s t s of a f o r - CoO O PRESENT WORK
(ATMOSPHERIC PRESSURE)
m a t i o n of SiO2 f i r s t , followed by the s o l i d - s o l i d r e a c - ~d
J
0
tion (
J I I I I J I I
SiO2 + 2CaO = Ca2SiO4. [17] 2 4 s 8 lo
~x lo 4

The following m e c h a n i s m i n v o l v i n g the v a p o r s p e c i e s Fig. 8--Desulfurization r a t e c o n s t a n t a s a f u n c t i o n of s i l i c o n

SiS is p r o p o s e d for the r e a c t i o n m e c h a n i s m . The slow activity at 1600~

2 9 0 - V O L U M E 9B, J U N E 1978 METALLURGICAL TRANSACTIONS B

by the r a t e of f o r m a t i o n of SiS and is the s a m e as that 6 I I T I I I
a c h i e v e d in v a c u u m when no CaO is p r e s e n t . T h e r a t e
of d e s u l f u r i z a t i o n of F e - A 1 with CaO is c o n s i d e r a b l y
5
f a s t e r , and the i n i t i a l r a t e in the p r e s e n t w o r k is
p r o b a b l y c o n t r o l l e d by the m a s s t r a n s f e r of s u l f u r to
the r e a c t i o n i n t e r f a c e . T h e b a s i c d i f f e r e n c e b e t w e e n
the d e s u l f u r i z a t i o n of F e - A 1 and F e - S i a l l o y s with CaO
is that f o r F e - A 1 a l l o y s s i g n i f i c a n t d e s u l f u r i z a t i o n can
o c c u r when the r e a c t i o n p r o d u c t is the s i m p l e oxide
A1203, for which the d i r e c t r e a c t i o n s a r e f a s t . F o r
F e - S i a l l o y s it is n e c e s s a r y to f o r m Ca2SiO4 to a c h i e v e
a p p r e c i a b l e d e s u l f u r i z a t i o n . T h e f o r m a t i o n of t h i s X = 0.8 cm
m o r e c o m p l e x oxide is slow and r e q u i r e d the u se of
the g a s e o u s i n t e r m e d i a t e s SiS and S f o r a f a s t r e a c - .~
X = 1,9cm
O

tion. Th e t r a n s f e r of s u l f u r to CaO by SiS and S was

d e m o n s t r a t e d in a s e p a r a t e s e t os e x p e r i m e n t s . T h e J I I I t i
t e c h n i q u e p r o p o s e d by T u r k d o g a n f o r d e s u l f u r i z i n g 2 4 6 8 10 12

s t e e l by the i n j e c t i o n of A1 and CaO with an i n e r t gas u, cm/s

(Ar fo r e x a m p l e , t h r o u g h a Q - B O P t u y e r e ) a p p e a r s Fig. A-2--Mass-transfer coefficient for Pb in flowing Ar at

ll00~
f e a s i b l e in that the k i n e t i c s of the r e a c t i o n a r e f a s t .

,sf , , , ,
APPENDIX A
u = 1.6 eml~
Gas-Phase Mass-Transfer Coefficient for
Crucible Geometry
Many experimental investigations of the rate of crn/s
1.0
chemical reactions involving liquid metals use an
experimental arrangement similar to the one employed
E
in part of the present study; that is, liquid metal in a
crucible supported in a vertical tube furnace with the
reacting or neutral gas flowing in the reaction tube.
Since in many cases gas-phase mass transfer may be
affecting the rate of the reaction, the gas-phase mass
transfer for this experimental geometry was investi-
gated. In a previous measurement of the rate of oxi-
0 u
:: .6 cm/s
I
dation of carbon by CO2 with a similar experimenta!

, I , I /
8 1.0 2.0

X. cm
Fig. A-3--Mass-transfer coefficientfor vaporizationof Pb in
He and Ar at II00~ as a functionof the distance X.
geometry, it was found that the mass transfer coeffi-
cient (m) was given approximately byz3
D
m = - [A-1]
x
d -- ~ X = 0.8 cm
where

D = interdiffusivity,
x = the d i s t a n c e f r o m the top of the c r u c i b l e to the
reaction surface.
In this s i m p l e a n a l y s i s no a c c o u n t was t a k e n of the
gas v e l o c i t y or the m a s s - t r a n s f e r c o e f f i c i e n t when x
=0.
In the p r e s e n t w o r k the r a t e of v a p o r i z a t i o n of Pb
in flowing A r or He was m e a s u r e d . T h e liquid Pb w a s
c o n t a i n e d in an a l u m i n a c r u c i b l e with a 2.5 c m ID and
I I I I I I
2 4 6 8 10 12 was heated in a v e r t i c a l tube f u r n a c e with a 5.5 c m
u, cm/s ID. Th e A r or He e n t e r e d f r o m the top of the f u r n a c e
Fig. A - l - - M a s s - t r a n s f e r coefficient for Pb in flowing He at and the gas v e l o c i t y at t e m p e r a t u r e v a r i e d f r o m 0.8
1100~ to 12.8 c m / s . T h e d i s t a n c e x was v a r i e d f r o m 0.1 to

METALLURGICAL TRANSACTIONS B VOLUME 9B, JUNE 1978-291

1.9 c m . T h e r a t e of v a p o r i z a t i o n w a s m e a s u r e d w i t h a
s e m i m i c r o r e c o r d i n g b a l a n c e and a l l m e a s u r e m e n t s
w e r e m a d e at l l 0 0 ~
The mass-transfer c o e f f i c i e n t is g i v e n b y
Jpb(RT)
m- PPb [A-2]
where
Jpb = t h e f l u x of P b in m o l e s / c m 2 s,
R = the gas constant,
T = absolute temperature,
PPb = t h e v a p o r p r e s s u r e of P b . 14
The measured mass-transfer coefficients for flowing
He and A r a r e g i v e n in F i g s . A - 1 and A - 2 a s a f u n c -
t i o n of g a s v e l o c i t y .
O n t h e b a s i s of p r e v i o u s w o r k it is r e a s o n a b l e to
a s s u m e t h a t the m a s s - t r a n s f e r coefficient will be
g i v e n a p p r o x i m a t e l y by
1 _ 1 + x [A-3]
m m o D of 12.8 e m / s a n d x = 0.8 e m is 4.9 c m / s , c o m p a r e d
w h e r e m o i s the m a s s - t r a n s f e r c o e f f i c i e n t f o r the
l i m i t i n g c a s e w h e n x = 0. T h e e x p e r i m e n t a l r e s u l t s
a r e p l o t t e d in a c c o r d a n c e w i t h E q . [A-3] in F i g . A - 3
f o r g a s v e l o c i t i e s of 1.6 and 12.8 c m / s . T h e e x p e r i -
m e n t a l r e s u l t s fit E q . [ A - 3 ] r e a s o n a b l y w e l l , and t h e
s l o p e s of t h e l i n e s a r e n e a r l y i n d e p e n d e n t of g a s v e l o c -
i t y . T h e g a s v e l o c i t y h a s a l a r g e i n f l u e n c e on t h e i n -
tercept or the mass-transfer coefficient when x
= O(mo).
T h e s l o p e s of the l i n e s s h o u l d be p r o p o r t i o n a l to 1//9.
T h e s l o p e of the l i n e s f o r He g i v e a v a l u e of 7.1 c m 2 / s
f o r t h e i n t e r d i f f u s i v i t y of P b and He, w h i c h is in e x -
c e l l e n t a g r e e m e n t w i t h the v a l u e of 7.2 c m 2 / s c a l c u -
l a t e d f r o m the d a t a and e q u a t i o n s g i v e n by H i r s c h f e l d e r ,
e t a l . 6 In the c a s e of A r t h e s l o p e s g i v e v a l u e s of 2.0
and 2.2 f o r the i n t e r d i f f u s i v i t y of P b and A t , w h i c h is
s o m e w h a t l a r g e r t h a n the c a l c u l a t e d v a l u e of 1.5 cm2//s.
H o w e v e r , the g e n e r a l b e h a v i o r is in good a g r e e m e n t
with Eq. [A-3].
T h e v a l u e of m o b e c o m e s i m p o r t a n t f o r low g a s
v e l o c i t i e s and l i g h t e r g a s e s . F o r e x a m p l e the u s e of
the s i m p l e E q . [ A - l ] , w h i c h n e g l e c t s m o , c o u l d l e a d to
s i g n i f i c a n t e r r o r s in t h e c a s e of H e . It is a p p a r e n t the
g a s v e l o c i t y a f f e c t s the v a l u e of m o . F o r a j e t s t r e a m
i m p i n g i n g on a f l a t s u r f a c e , S c h o l t z and T r a s s ~ o b -
tained a correlation experimentally for the mass-
transfer coefficient. The average mass-transfer co-
e f f i c i e n t f o r t h e e n t i r e p l a t e (m) is g i v e n b y
292-VOLUME 9B, JUNE 1978
= 0.5 D v "~/4 d 1/4 S c 1/3 R e 3/4 [A-4]
w h e r e d is the n o z z l e d i a m e t e r , in the p r e s e n t c a s e
the d i a m e t e r of t h e f u r n a c e , and r is the r a d i u s of the
p l a t e . A l t h o u g h t h e gas s t r e a m in the p r e s e n t e a s e is
not a j e t and t h e R e y n o l d s n u m b e r (10 to 50) is l o w e r
t h a n t h a t r e c o m m e n d e d (>500) t h i s is the b e s t c o r r e l a -
t i o n a v a i l a b l e . T h e c a l c u l a t e d v a l u e s f o r A r and He
f o r t h e p r e s e n t e x p e r i m e n t a l c o n d i t i o n s a r e a b o u t 11
c m / s and 12.8 c m / s , a s c o m p a r e d w i t h the o b s e r v e d
v a l u e of m o of 5.5 and 11 e m / / s r e s p e c t i v e l y . W h e r e a s
the a g r e e m e n t f o r He i s e x c e l l e n t , that f o r A r i s not
v e r y good. H o w e v e r , the g e n e r a l a g r e e m e n t is f a i r
c o n s i d e r i n g t h a t t h e e x p e r i m e n t a l c o n d i t i o n s do not
s a t i s f y the l i m i t a t i o n s of E q . [ A - 4 ] .
It is r e c o m m e n d e d t h a t if it is n e c e s s a r y to e s t i m a t e
the g a s - p h a s e m a s s - t r a n s f e r c o e f f i c i e n t f o r the e x -
p e r i m e n t a l g e o m e t r y c o n s i d e r e d , E q . [A-4] s h o u l d be
u s e d to c a l c u l a t e m o and E q . [A-3] to c a l c u l a t e m . F o r
e x a m p l e , in t h e p r e s e n t w o r k the c a l c u l a t e d m a s s -
t r a n s f e r c o e f f i c i e n t f o r P b in He at a g a s - f l o w r a t e
w i t h 4.5 c m / s o b s e r v e d e x p e r i m e n t a l l y . F o r s i m i l a r
c o n d i t i o n s f o r A r the c a l c u l a t e d v a l u e is 1.6 c m / s and
the o b s e r v e d is 1.9 c m / s . T h e s e v a l u e s c o m p a r e
reasonably well so that the effect gas-phase mass
t r a n s f e r m a y h a v e on t h e o v e r a l l k i n e t i c s of t h e r e a c -
t i o n o r p r o c e s s b e i n g c o n s i d e r e d c a n be e s t i m a t e d .
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METALLURGICAL TRANSACTIONS B