The effect of the reactivity of lime on

desulphurization efficiency in the basic oxygen

furnace
A. A. HEJJA,* Dipl. Ing. (Budapest) (Visitor)
D. D. HOWAT,** B.Sc. (Glas.), Ph. D., F.I.M. (Fellow)
P. R. JOCHENS,* Pr.Eng., M.Se. (Eng.) Rand, Ph.D., A.I.M. (Member)

SYNOPSIS
The iron charged to the basic oxygen furnace at the steel plant of Highveld Steel and Vanadium Corporation has a
relatively high sulphur content. Considerable emphasis is therefore placed on the reactivity of the lime. An in-
vestigation of the lime used at the steel plant showed that its reactivity had deteriorated considerably both during
transport from the supplier (Northern Lime Company) and during storage and handling at the steel plant. The
deterioration on the steel plant is the more severe, and is due to hydration and carbonation. Rapid deterioration is a
characteristic of highly reactive lime when exposed to the atmosphere.
Plant tests showed that the desulphurization efficiency decreases with a decrease in the reactivity of the lime.
The addition of slag rich in manganous oxide to the furnace considerably improved the efficiency of desulphurization
that can be achieved with limes of lower reactivity and with lime that has deteriorated. A decrease in particle size of
lime of lower reactivity greatly increased the desulphurization efficiency.
Less lime of higher reactivity is required for the same degree of desulphurization to be achieved. Lime of higher
reactivity gives rise to slags with lower ferrous oxide contents and hence the steel yield is increased.

SINOPSIS
Die yster wat gebruik word in die basiese suurstofhoogoond by die staalinstallasie van "Highveld Steel & Van-
adium Corporation" het 'n relatiewe hoe swawel-inhoud. Gevolglik word daar bale klem gele op die reaktiwiteit
van die kalk. 'n Ondersoek het getoon dat die kalk wat gebruik word, se reaktiwiteit aansienlik verswak met die
vervoer vanaf die verskaffer (Northern Lime Company) en ook as gevolg van die opberging en hanteering by die
staalinstallasie. Die verswakking by die staalinstallasie was egter die meeste en dit was as gevolg van hidratering en
karbonering. Een van die eienskappe van hoe reaktiewe kalk is dat dit vinnig verswak as dit aan die atmosfeer
blootgestel word.
Toetse by die installasie het getoon dat die ontswawelingsvermoe verminder as daar 'n afname in die reaktiwiteit
van die kalk is. Die byvoeging van slak wat ryk is aan mangaanhoudendeoksied in die hoogoond het 'n verbetering
getoon in die ontswawelingsvermoe wanneer kalk met 'n laer reaktiwiteit en kalk wat reeds verswak het, gebruik
word. Met die verkleining in korrelgrootte van die kalk wat 'n laer reaktiwiteit het, het die ontswawelingsvermoe
grootliks verbeter.
Minder kalk met 'n hoer reaktiwiteit is nodig om dieselfde graad van ontswaweling te bewerkstellig. As kalk met
'n hoer reaktiwiteit gebruik word word slak met 'n laer ysteroksiedinhoud verkry en sodoende word die opbrengs
verhoog.

INTRODUCTION
In the production of vanadium-rich
pig iron and titaniferous slag from the
titaniferous magnetites of the Bush-
veld Igneous Complex, the ore is
pre-reduced in rotary kilns before
being charged to electric smelting
furnaces. The hot metal is then
transferred to a shaking ladle in
which, by suitable additions, top
oxygen blowing concentrates the
vanadium in the slag. This partially
blown hot metal is converted to
steel in a basic oxygen furnace
(B.O. F.) and is subsequently trans-
ferred to a continuous casting plant.
Because of its high titanium dioxide
content (about 30 per cent), the slag
*Pyrometallurgical Research Group. Nat-
ionallnstitute for Metallurgy
**Professor and Head. Department of Metal-
lurgy. University of the Witwatersrand
(This paper is based on a thesis submitted to
the University of the Witwatersrand)
produced in the electric smelting
furnaces is of Iow basicity and hence
the sulphur capacity is also Iow, and
rather high sulphur levels can there-
fore be expected in the hot metal.
The silicon and manganese con-
tents of the partially blown metal
charged to the B.O.F. are very Iow.
In addition, considerable fluctuations
occur in its carbon content, which is
generally lower than that of typical
iron produced in a blast furnace.
Ferrosilicon has therefore to be
added to the B.O.F. so that the
desired quantity of scrap can be
charged to the furnace.
The production of steel of Iow
sulphur content (less than 0,04 or
0,05 per cent, depending on grade)
presents difficulties under these con-
ditions. It is believed that lime, as
the most important slag-forming
agent, plays a very important role in
steel production and that its role
depends on its reactivity. This re-
activity is a function of the degree of
burning, being higher for 'soft burnt'
than for normally burnt lime. It is
generally accepted that lime of high
reactivity dissolves more easily and
rapidly, thus promoting the for-
mation, at the start of the blowing
period, of a slag relatively high in
calcium oxide, which assists in rapid
desulphurization and dephosphori-
zation. A further advantage of highly
reactive lime is that its consumption
is lower and the slag is decreased,
resulting in smaller losses of ferrous
oxide in the slag and higher yields of
steel. Also, early dissolution of the
lime means that refractory attack is
reduced.
DETERIORATION OF REACTIVITY
OF LIME
The lime that is specifically burnt
for use in the B.O.F. at Highveld

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY MARCH 1973 249
 Steel and Vanadium, when dispatched
from the Northern Lime Company's
plant at Lime Acres, Cape Province,
is generally of high reactivity. How-
ever, because of the considerable
distance (some 800 km) between the
lime producer and the steel plant,
and the time taken for the journey,
the lime can deteriorate in the
railway trucks, although these are
covered with tarpaulins. Also as a
result of this long rail haulage, con-
siderable bunker capacity for lime
has to be provided at the steel plant
to ensure a continuous supply, and
lime can be stored there for several
days before use. Further deterio-
ration of reactivity can occur during
this period. Before the effects of
lime reactivity on desulphurization
in the B.O.F. could be studied, the
deterioration of reactivity during
railage and storage had to be in-
vestigated.
Measurement of the reactivity
The two tests most commonly used
in determinations of the reactivity
of lime are the coarse-grain titration
and the slaking test. In the titration
test, the rate at which 50 g of lime
between 10 and I mm (between
inch and 16 mesh) in particle size
dissolves in 2 litres of water at
40°C is measured by the continuous
neutralization of the resultant solu-
tion with hydrochloric acid. An in the rail trucks at 10 cm intervals
essential condition of the titration from the surface, three samples
is that the solution should always being taken from each 10 cm level.
remain alkaline (above a pH value of The results are presented in Table I.
8) to ensure that only dissolved As can be clearly seen, the reactivity
calcium hydroxide is neutralized and of lime in the upper layers had
that solid calcium oxide is unaffected. deteriorated considerably, and this
In the DIN slaking test (similar in deterioration increased with time, as
principle to the Beachville and Ameri- shown by the first three trucks,
can reactivity tests), 150 g of lime which were sampled twice, i.e., on
between 5 and I mm (between 4 and arrival at the steel plant and after
16 mesh) in particle size is placed in having stood on the rail siding for a
600 ml water at 20°c. The reactivity week. If this deterioration of the
is obtained from a measure of the upper layers is expressed as de-
time required for the solution to terioration of the total contents of
reach a predetermined temperature. the truck, the decrease in reactivity
The reactivity values quoted in this of the lime during rail haulage varies
paper were determined from slaking from 4,0 to 20,0 per cent. It should be
tests by use of the formula pointed out that the weather con-
240 ditions were dry and windy.
R ~
-- X 10,
t
where Deterioration of reactivity during
storage and handling in the steel plant
R=reactivity of lime, and
t =time in seconds for a tempera-
In a determination of the extent
of the deterioration occurring on the
ture of 60°C to be reached.
steel plant, a programme of sampling
Experiments had indicated that the
was conducted during August and
slaking test was more suitable than
September, 1970. The results are
the titration test for rapid quality
shown in Table 11, which, for com-
control in a plant, and both the lime
parison, also indicates the deteriora-
producer and the steel plant employ
tion attributable to transport by
this technique.
i rail. It can be seen that the re-
Deterioration of reactivity during activity values of the lime were
transport drastically reduced as a result of
During August 1970, the lime that storage in the bunkers and handling
arrived at the steel plant was sampled on the steel plant.

TABLE I
REACTIVITY OF LIME AT VARIOUS DEPTHS IN RAIL TRUCKS, AS SAMPLED AT WITBANK

Date - August, 1970 Truck Reactivities at various levels from the surface Average Decrease in reactivity
number of the consignment in the truck, RDIN reactivity due to deterioration
Arrival at Sampling of of upper layers
Witbank of truck 0 to 10 cm 10 to 20 cm 20 to 30 cm 30 to 40 cm consignment %
RDIN

19th 20th 151146 39 91 107 120 100 8,5

26th 151146 11 37 69 118 97 17,9
19th 20th 112801 120 126 133 145 139 4,0
26th 112801 25 45 67 130 10S 19,5
16th 17th 186875 39 51 115 120 106 11,6
24th 186875 13 63 83 120 102 15,0
16th 17th 163248 100 105 141 141 134 5,0
16th 17th 162139 40 100 120 149 126 11,6
19th 20th 67728 44 77 100 150 126 16,0
3rd 7th 115211 52 80 90 120 93 10,5
3rd 11th 134987 5 26 120 126 105 16,5
3rd 14th 113605 5 14 56 104 86 20,S
14th 137311 9 68 75 120 101 15,8
14th 122557 13 68 96 109 95 12,1
15th 17th 150774 17 52 105 110 96 12,5
11th 17th 115346 2,5 30 45 86 67 18,5
12th 21st 153745 4 44 65 80 69 13,6
11th 21st 162491 4 12 14 15 14 9,5
12th 21st 151782 7 63 70 127 106 16,4
11th 21st 163973 10 120 142 150 142 5,5
31st 31st 150144 68 77 104 114 106 7,3
31st 31st 222671 52 89 133 133 105 7,4
31st 31st 138933 31 63 83 100 89 11,0

250 MARCH 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 TABLE 11 suits, which are shown in Fig. I, are
DETERIORATION OF THE REACTIVITY OF LIME IN THE RAIL TRUCK AND AT THE similar to those obtained by Ander-
STEEL PLANT
son and Vernon1.
Reactivity of lime (DIN)
EFFECT OF REACTIVITY OF
Date Sample taken below Estimated bulk As fed to B.O.F. LIME ON DESULPHURIZATION
upper deteriorated reactivity of converter
levels in truck truck load As indicated earlier, the partially
6th August
blown metal fed to the B.O.F. is
102 to 115 88 to 100 48
relatively high in sulphur but Iow in
7th August 38 silicon and manganese and exhibits
8th August 20
10th August 15
considerable fIuctuations in carbon
11th August 106 93 27 content. Although lime of high re-
12th August 48 activity is dispatched from the lime
13th August 36,21
producer, the lime fed to the furnace
14th August 15 is generally of Iow reactivity because
15th August 10 of deterioration during railage and
16th August 122 108 13
17th August 23 storage. Because these factors made
the attainment of the required
18th August 22
19th August 115 100 14
sulphur levels in the steel rather
difficult, the practice of adding a slag
20th August 12 high in manganous oxide (derived
21st August 73 64 18
from an adjoining ferroalloy pro-
23rd August 12,9 ducer), which would induce early
24th August 132 115 8 and rapid slag formation, was intro-
25th August 13 duced. The effect of the reactivity of
26th August 20 lime on desulphurization and of the
27th August 120 104 33, 34, 37
28th August 43,44,38 slag addition was evaluated in an
extended test campaign.
29th August 31
31st August 128 II1 13 Operating practice in the basic
1st September 28 oxygen furnace
2nd September 21,22 Of the two B.O.F. vessels, only one
3rd September 116 101 12 is in operation while the other is
4th September 11 being reconditioned. The water-
cooled lances have three 0,0286 m
Discussion
3,5 70
Of the deterioration of reactivity
occurring during railage and during
storage and handling at the steel
3,0 60
plant, the latter is the greater. It ;f!.
was shown that considerable at- UJ-
trition of the lime occurred during --'
D..
~2.5 50
storage and handling at the steel «
plant, this disruption of the particles VI

producing an increased rate of de- ~N

terioration because new surfaces 0 2,0 1.0
u
became exposed to the atmosphere. z
0
The degree of deterioration was z 0
«
shown to be related to the increase 0
1,5 30 >--
N t-
in hydrate and carbonate content of :I:
>
the lime, the hydrate content being z' c~ t-
U
the more important factor. Hence, 0
;:: I,D 20
the deterioration can be correlated z
l:> ~~10
with loss on ignition values. As con-
firmation of this contention, samples z
0 0,5
of lime supplied by the Northern VI
VI
Lime Co. were exposed to atmos- 0
--'
pheric conditions as a single layer of 0
0
lumps. At selected time intervals, 0 2 3 I. 5 6
the increase in carbon dioxide and EXPOSURE TIME, h
water content and the loss on
Fig. I-Change in the composition and reactivity of lime on exposure to the
ignition were determined. The re- atmosphere

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY MARCH 1973 251
(I t in) de laval type of nozzles in-
clined at 10° to the vertical and iU
c: ...
operate at a pressure of 1,034 to 0 0 ~ ~ ~ '" '"
CXI"
M
CXI
I-
1,172 MPa (150 to 170 Ib/in2), with '~N>..
maximum oxygen flow rates of 2,83 '~g-
..:,,!!
m3/s (6000 ft3/min). a.v
c:
"'~
.,gCl> ... ~
The major proportion of steel z a. ~ 0
produced is in the 0,15 to 0,25 per 0 Cl> """ ~:$ ~ MM
.,..... -0
M
0 0 C
cent carbon range, and the desired i= 1-;
« ...
production technique is the 'catch N
~
carbon' practice. To permit this 0
:r: "'_iU
practice, a thermally balanced charge c.. 2o~
V> CXI -0
is required. Early slag formation and 0 .,gt;E -0 1'1-0
:r: a.CI>c: ~ ~ ~ 00V> -0
0
the correct total oxygen input are c.. 8t;~ 0 0 "
00 0
w ..:00
essential, and lance height and flow- 0 c..v:<;
rate are adjusted for slag condition- 0
z
ing. «
The B.O.F. is charged with 4,5 to z ~,,~ c:
9 t (5 to 10 sh. ton) of scrap, followed
0 ~
~t:~~o ~~~~~g~~~~~~~~~~
i=
by 54,5 to 59 t (60 to 65 sh. ton) of « iU
> "'~c,,:<;i ~~~~~~~~~~~~~~~~
N 0 ~ ...; ;'O~
partially blown hot metal. The con- ~ E
::> Cl> ><
verter is turned into the vertical :r:
c.. V> '- ---I
position, the lance is lowered to the !:
-'::> '0
Cl> c: 'e
required height above the metal V> ...
surface, and blowing is commenced.
w
0 Cl::
'"
~~ ~ V>"'~~V>V>~O"V>V>""CXI"~N
u.. """
0 C
CXI-oON"""'--O"'N""-oCXIV>~
~~~~~~~~~O~NOONO
The ferrosilicon addition and the 0 1-;
...
u.:
first lime addition are then made. V>
u
6
ai
The lime is charged in separate i=
w 0
...
batches of 454 to 794 kg (I 000 to z
;;2 iU
... "Cl>
I 750 Ib). - c: 0 ~ ~~~~~~~~~~;~~~~~ ~
The amount of lime to be added is
=
W Z
0 0
';:; I- ..:
"'>..
N v v'"
based principally on the ferrosilicon ~ « 'i: c: Cl>
« >- Cl> '-Cl>
addition and a basicity ratio (calcium I- U ..:'0
'" ~
~~ c:
oxide to silica) in the slag of 3,5 to Z Cl> ... ~ u..
W
Cl>
'" ~ 0 '"
4,0. At the first 'turn-down', the U 0'"
~ ~~~~~~~~~"~~~~~~ U'"
u::: """
0 C -...0
bath temperature is measured and, u..
W 1-;...
after a sample has been analysed, W M
M
blowing conditions are adjusted for :r: 0
I- 0
...
carbon elimination or sulphur re- 0 c:
Z 0
moval. The required temperature « V>'~ 0
~;; ,0 ~V>"""CXlv>""-o-"""'OOCXIN""
~~O~CXlCXI~CXI~CXlCXlO~CXlO~
and composition should be attained W qq~qqqqqqqq~qq~q
at the second turn-down. If the metal
1: ,-... Cl>
.=g
c: ~
0000000000000000 "c:
::::i '"
Cl>
has had to be overblown so that 0 '-0
sulphur contents will be sufficiently
0 v
c:
0
>-
I-
-...'-0
-----
Iow, recarburization is achieved by :;: c: ..:
the addition of anthracite to the steel 0 ,~
i= ........
ladle. A short, second reblow is often u ~ '-1>0
~'O O'~ ... """""""""0""-0"""" -0
.,.
«W ---1'1-0-""--
~~~N~~~~~~*+-+-+-~~ 0
required for the adjustment of final Cl:: «"c:'"
1: 0
...
steel composition. W
:r: ....
M
Plant test I- . 0
Z "Cl> u.. ;z ...
The tests were so planned that W
W
Cl>
E ~~B6 . 0 ~~~~~~~~~"'~~~~='" -;;;
'"
information would be obtained on the ~ '" a:I <>::
"5 ..:
v
relation of desulphurization and I-
W
-0 l>O'i: .
a:I >..
... ""Cl>
-;;;o,!:!
other metallurgical factors to lime ';; c:'"
Z ';:; iU "51:.!!
with Iow, intermediate, and high 0 v ~ ;z ,- v
++++
'0'0 'f
reactivity when a slag rich in man- i=
«
Cl>
'"
Cl:: ~~~~ a. 0 ~~~~~~~~~CXI~~~~~"
<>::
!: 0"""
C:C:a.
ganous oxide had been added and -'W 0 '" 1: ,Q
Cl:: -,~ Cl>
when it was absent. Also, since lime 0"
"V
c:" '"
,Q~]
that has been burnt to possess a
high reactivity but that has de- 'O...~ "'0'-
cl ~'i: -N"""""-o"CXI~O-N"""""-o ~~'O
teriorated is generally charged to Z"'~
------- Cl>Cl>
'"
ot:E
the B.O.F., this lime was treated as a Z.=:J
+-* ++
252 MARCH 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 during the first blowing period.
Fig. 3 shows the effect of lime
1.Rat! of desulphuriza t ion to 1st turn-down. reactivity on dephosphorization. As
2.Desulphurizat ion efficiency to 1st turn-down. for desulphurization, the trend is
3. Desulphurization efficiency for the total rather pronounced up to the first
blowing period.
60 turn-down, whereas, for the whole
blowing period, the reactivity has
0 D
'70
very little effect on the removal of
50
x phosphorus from the metal. It may
0
"if!. be noted that because of the very
"if!.1'~
Iow phosphorus content of the iron,
>'
u
z
0
z dephosphorization has never been a
w 1.0 0 serious problem in Highveld's B.O.F.
U I-
<{
u:: operation.
u. N
w 0 0::
0
::::> Slag formation
z 30 3
0 iE Fig. 4 illustrates the fields of the
~ ...J
<{ ::::> Highveld B.O.F. slags in the (CaO+
V1
!:::! w MgO+MnO) - FeO - Si02 pseudo-
0:: 0
::::>
:I: 20 ternary diagram for two lime re-
u.
a.. 0 activity ranges, viz., 88 to 115 RDlN,
...J
::::> w (field 2) and 30 to 35 RDlN, (field I).
V1
w
0
~
0::
The slags were analysed after com-
10
pletion of the blowing period. As can
be concluded from the graph, as
lime reactivity decreases, the field of
.0 0 slag formation definitely moves up
0 20 .1.0 60 Ba 100 towards the heterogeneous phase
LIME REACTIVITY, R DIN boundary, which was drawn accord-
Fig. 2-Desulphurization efficiency and rate of desulphurization as functions of ing to Bardenheuer et al.2 for three
lime reactivity different temperatures. As the re-
activity decreases, the rate of dis-
separate type from the above three reactivity of the lime, but the trend solution of lime in the slag also de-
types. The results in Table IIIare the is for lower reactivity values to be creases and the slag gradually be-
average results of each test series associated with lower final desul- comes saturated with calcium ortho-
which consisted of from 25 to 300 phurization values. silicate. This will result, in addition
heats. The results of these tests in In those tests in which no additions to the presence of undissolved lime,
which additions of slag rich in of slag rich in manganous oxide were in the precipitation of solid di-
manganous oxide were made are made, it can be seen that, provided calcium silicate, the formation of
plotted in Figs. 2 and 3. the initial reactivity of the lime and which may be further increased by
Discussion the reactivity when charged to the relatively Iow temperatures at the
Fig. 2 clearly shows that, in the B.O.F. is high, good desulphurization start of the blowing period or by
presence of slag rich in manganous is obtained in the first blowing local areas of Iow temperatures
oxide, as the reactivity of the lime is period. Lime of intermediate re- caused by charging of large amounts
decreased, the desulphurization effi- activity and lime that had de- of cold lime.
ciency up to the first turn-down also teriorated from a high reactivity did In Fig. 5, total desulphurization
decreases. The reactivity value not exhibit good desulphurization efficiencies are plotted against the
plotted is that measured on arrival at capacity.When reactivity values were ferrous oxide contents of the slag
the steel plant. The rate of de- Iow, it was not practically possible for the above lime reactivities. For
sulphurization up to the first turn- to conduct a test series consisting of the lime of lower reactivity, the
down decreases similarly, although many blows because the first blow sulphur transfer to the slag first
this value incorporates the effect of resulted in very poor desulphuri- decreases with increase in ferrous
variation in time during the first zation efficiency. oxide, reaches a minimum value, and
blowing period. Very little de- Series 15 and 16 were cond ucted then increases again with further
sulphurization is obtained when with lime of reduced particle size - increase in ferrous oxide content.
'dead-burnt' lime is used. Interest- between 0,019 and 0,006 4 m (be- This behaviour accords with the
ingly enough, lime of high reactivity tween i and tin) - instead of the findings of Bardenheuer and Ober-
that has deteriorated behaves effect- material generally used, which was hauser3. Fig. 5 also indicates that, for
ively like lime that has not de- between 0,038 and 0,019 m (be- the same degree of desulphurization,
teriorated. tween I! and i in). Even with 'dead- lime of lower reactivity is associated
The final desulphurization value burnt' lime of very Iow reactivity, with higher losses of ferrous oxide
obtained is far less affected by the good desulphurization was achieved in the slag.

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY MARCH 1973 253
 1.Field of BOF slags obtained with lime of medium retlrtivity ROIN = 32
2.l=ield of BOF slags obtained with lime of high reactiviiy ROIN = 97

3CaO.25i02
()" 60

0
.
:f 2 CoO. 5iD2

70
~~
3CaO.5i02
o'
J>

1.Dephosphorization etticiency to 1st turn-dew

2.Dephosphorization efficiency for the total
blowing period.

0
90

Fig. 4-Effect of reactivity of lime on the composition of the slag

D
!! 80 2.
0 0
!:I
ROIN = 32
>-'
u
Z
t:. ROIN = 97
ill 70 fj, I fj,
U 70 I
'LL
LL
,
/
ill 0

Z It:.
Q 60
I-
« 60 t:. 'I
N
~
1, !J. ,'6. j
0 I :
0
~
(f)
0
50 t:. ,/ /0
:x:
CL ~~>' h /8
w SO 0/
8 6/ 6,

/
0 40 u
z
w I / 0
u
30
u.
u. 0
~ !:t./ b"
o~.
:1 0
w 0 !J
z
40
,? A 00 A I
I
.~
/
20
0 " .;; /_9~
~0
0 20 40 60
LIME REACTI VITY, RDIN
80 100 N A / ~
et: /
=> 30 fj, I A
I
Fig. 3-Dephosphorization efficiency as a function of a.. / 0
reactivity of lime -'
=>
(/) /6
W I
0

20
10 20 30 40
FeD CONTENT, %
Fig. 5-Effect offerrous oxide content ofthe slag on the desulphur-
ization efficiency of lime possessing high and medium reactivity

254 MARCH 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 mainly via the slag phase. With the
lime of lower reactivity, gas-phase
t::. ROIN = 50
desulphurization becomes far more
80
0 ROIN = 80 significant. Irrespective of the re-
0
activity of the lime, an increase in the
initial sulphur content of the iron is
70 associated with an increase in the
0
0 proportion of sulphur removed via
0
0 0 the gas phase.
60 0 A
0
o!! 0 00 t::. Lining wear
0
>--
u
0
0 The magnesium oxide content of
0 t::.
0
~ 50 0 0 0 t::.t::. t::. the slag is almost totally derived
U 0 t::.t::. from the attack on the magnesia
u. 0000 00 t::.
u. refractory lining of the vessel, and
w t::.
0 t::.
z 40 0 0 t::. the degree of refractory attack can
0 t::.t::. t::.
0 0 therefore be assessed in terms of the
t::. t::.
~N 0 t::. t::. t::. magnesium oxide in the slag. From
t::.
~
I
30 t::.
t::. t::.
the available plant data, the mag-
Il. nesium oxide content could be corre-
-'=> t::.
lated with the ferrous oxide content
t::.
'"~ 20 and the basicity ratio of the slag:
% (MgO) = 2,69 - 0,179 (CaO to
Si02) + 0,027
10 (% FeO).
0 2 3 4 5 6 7
(CI10) Therefore, to ensure a Iow mag-
SLAG BASICITY
SiO2
nesium oxide content in the slag
Fig. 6-Effect of slag basicity on desulphurization at various reactivities of lime
(i.e., Iow refractory consumption),
the ratio of calcium oxide to silica
Effect of reactivity of lime and slag Gas-phase desulphurization
should be high and the ferrous oxide
basicity on desulphurization efficiency
Based on calculations of sulphur content should be Iow. Since higher
Another effect of the reactivity of balance, an investigation of gas- reactivities of lime will promote
lime is shown in Fig. 6, in which the phase desulphurization was made for quicker slag formation and thus
desulphurization efficiency is plotted lime of three reactivities. The results result in higher slag basicities at the
as a function of slag basicity. In the are summarized in Fig. 7. It is ap- early stages of the blow, thereby
period of this test series, the average parent that the use of the two restricting the level of ferrous oxide
reactivity of the lime supplied was highly reactive limes results in very in the slag, the beneficial effect of
83. However, at times the values similar desulphurization character- lime of higher reactivity becomes
were lower, i.e., 50 to 65. It can be istics, viz., desulphurization occurs apparent. This confirms the findings
concluded from Fig. 6 that lime of
higher reactivity gives rise to better
desulphurization efficiency at all slag
basicities, an increase in slag basicity 100 0
being accompanied by an increase in w'
desulphurization efficiency. Behrens '"
<{
I
Il.
et al.4 obtained similar results for <:>"
<{ 20 CJ
CJ 80
the relations between sulphur dis- -'w '"
<{w

"'>
wO
<:>i;
w::;:
tribution and slag basicity, from Iw0::
which they concluded that, for I~ 40 ~
~O:: 60 zO::
identical slag basicities, the sulphur ~O::
-=>
DI => CJI
distribution is better in heats using wll.
wll.
[IJ-, >-'
soft-burnt lime than in heats using
:5~ 40 60 ~~
hard-burnt lime. Linear regression w-'
analysis between desulphurization '"
[IJ-'
<{~
O::<{
O::~
0::0 =>~
efficiency and basicity of the slag for =>~ 80 I u.
Iu. 20
the two types of lime gave the ~o
~O
~o!!
following expressions: => 0
"'....
% 7Js = 20,33 (CaO/Si02) - 14,5 0 .0.04 0.06 0.08 010 0.12
100
for the higher-grade lime,
INITIAL SULPHUR CONTENT, 0'0
and
% 7Js = 12,86 (CaO/Si02) - 11,0 Fig. 7-Desulphurization in the slag and gas phase as a function of
for the lower-grade lime. sulphur load at various reactivities of lime

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY MARCH 1973 255
 1.

60
3.

4. 46 so

3.0 44 ~ 40
>-'
M u 0
0 z I-
w
Z
><
2.8 ~ 1.2 ~ 30 2, QM
M u..
E
......
>
u..
w ~6
~
01 I- z
2 N-
0::: ><
U)
0 ~ o C
> 2.6 ~ 40 ~ 20 IO" 'E
CL l
I- ~ N J Z-
U) ~5
0::: 2,
Z
W
0
I-
Z
~
I -1 ~O
00
'~
2.4 ~
«
38 CL
~
J
10
I.,
u..Z
00:::
I

J
;::) CL U)
W~
CL w 1-1-
CD
« 0 «-$!
0 ~
2.2 36 0 1.-
0 20 L.O 60 80 100
LIME REACTIVITY) ROIN
Fig. a-Relation between desulphurization and lime characteristics at various
reactivities of lime

of Krieck5 and Limes6, who emphasize laboratory and desulphurization effi- four groups of limes when slag rich in
the importance of the role played by ciency in the B.O.F. The latter was manganous oxide was added to the
ferrous oxide in lining wear. regarded as the actual measure of B.O.F. and when it was absent indi-
the reactivity of lime under working cated the following:
Reactivities of lime measured in the conditions. Fig. 8 indicates that the (I) Good desulphurization is ob-
laboratory and those evaluated in DIN reactivity test appears to be a tained with lime of high re-
B.O.F. operations satisfactory measure of the reactivity activity, even in the absence of
There has been a great deal of that can be expected from B.O.F. slag rich in manganous oxide.
controversy in the literature about operation. The figure also indicates (2) Lime of medium reactivity can be
how far the reactivity of lime, as that, below a reactivity of about 30 used, but the operation becomes
determined in aqueous media, can be to 35 DIN, there is a noticeable more difficult and the desulphur-
related to its behaviour in the decrease in the desulphurization ization efficiency is reduced,
B.O.F. Gregory et a1.7, for example, efficiency. especially when slag rich in
found that the lime used in a pilot- manganous oxide is not added.
plant converter behaved in a manner CONCLUSIONS (3) Lime of Iow reactivity in the
exactly opposite to that expected The reactivity of lime deteriorates conventional size range is not
from laboratory reactivity tests. considerably both during rail trans- suitable for desulphurization.
This aspect was investigated in port and during storage and handling However, if this lime is added at
the light of the available data from at the steel plant. The deterioration smaller particle size, good de-
Highveld's operation, and the re- on the plant is the more severe and is sulphurization is obtained in the
sults are summarized in Fig. 8. The caused by hydration and carbonation, presence of slag rich in man-
graph shows the relation between the former being predominant. ganous oxide. Smaller particle
reactivity as determined in the Tests conducted on the plant with size was also highly beneficial

256 MARCH 1973 JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY
 in the lime of medium reactivity. slags with higher ferrous oxide mission of the Director General, the
(4) If additions of slag rich in man- contents, and the steel yield is National Institute for Metallurgy,
ganous oxide are made, lime consequently decreased. For the Johan nesbu rg.
that was burnt to possess a high same basicity, sulphur is removed
reactivity but that has deterio- better when lime of high reactivity REFERENCES
rated behaves like a lime of high is used, Le., less lime of high re-
I. ANDERSON, c., and VERNON, I. The quality and
reactivity with respect to its activity is required to achieve the production of lime for basic oxygen steelmaking.
). Iron Steel Inst., 1970. pp. 329-335.
desulphurization potential in the same degree of desulphurization. As 2. BARDENHEUER, F., VOM ENDE H., and OBER-
B.O.F. the reactivity of the lime is decreased, HAUSER, P. G. Lime solution, slag formation and
life of dolomite lining when blowing Iow-phos-
Correlation of the laboratory slak- the proportion of sulphur removed in phorus pig iron in oxygen converter. Stahl und
Eisen, vol. 88. 1968. pp. 128S-1290. (In German).
ing method for the determination of the gas phase is increased. In ad- 3. BARDENHEUER, F., and OBERHAUSER, P.G.
the reactivity of lime with the de- dition, it appears that lime of higher Desulphurisation during the blowing of low-
phosphorus pig iron with pure oxygen as de-
sulphurization efficiency of the lime reactivity is associated with lower pendent on the slag composition. Arch. Eisen-
h'~ttenw., vol. 41. 1970. pp. 221-225. (In German).
in the B.O.F. appears to be valid, rates of lining wear.
4. BEHRENS, K. F., KOENITZER, J., and KOOTZ, T.
except when lime has deteriorated The effect of lime properties on the basic oxygen
ACKNOWLEDGEMENT steelmaking.}. Meto/s, N.Y., Jul. 1965. pp. 776-781.
from a high reactivity value. 5. KRIECK, H. T. S. Recent trends in the application
A comparison of limes of different The close cooperation of the and technology of refractory materials in iron and
steel production. Colloquium on Future Trends
reactivity confirms that a lime of management and staff of the High- and New Developments in Iron and 5teel Pro-
duction, 5. Afr. Inst. Min. Metall., Johannesburg.
Iow reactivity does not dissolve as veld Steel and Vanadium Corporation 17th Mar., 1971.
rapidly or as completely in the slag as (Pty.) Ltd. and The Northern Lime 6. LIMES, R. W. Refractory practice in basic oxygen
furnaces. ). Iron Steel Inst., 1968. pp. 478-484.
a lime of high reactivity. Further, Co. Ltd. is gratefully acknowledged. 7. GREGORY, J. A., et al. Basic oxygen flux: an ex-
amination of water activity and digestion to a
lime of Iow reactivity gives rise to This paper is published by per- slag. }. Iron Stee//nst., 1965. pp. 886-891.

THE SOUTH AFRICAN INSTITUTE OF

MINING AND METALLURGY

COLLOQUIUM ON TRACKLESS MINING

A one-day colloquium is being arranged by the South African Institute of
Mining and Metallurgy on the above subject, to be held on May 16th, 1973, in
Kelvin House.

Papers dealing with their respective trackless-mining methods will be presented

by the following:
Mr C. F. Hews of the International Nickel Co., Canada; Mr A. Winther, of
Kiruna Mine, Sweden; Messrs M. P. Grobler and P. J. Constancon, of Prieska
Copper Mine; Mr S. Watson, of Thabazimbi; Mr Maibaum, of Demag; Mr
Mantell, of Oamites Mine, South West Africa; and Mr J. Hoatson, of Rokana
Division, Nchanga Copper Mines Limited, Zambia.

Members of the Institute who would like to contribute to this Colloquium are
invited to submit their suggestions to the Secretary, South African Institute of Mining
and Metallurgy, as soon as possible.

JOURNAL OF THE SOUTH AFRICAN INSTITUTE OF MINING AND METALLURGY MARCH 1973 257