United States Patent (19) [11] 3,849,114

Yoshida et al.
(45) Nov. 19, 1974
54 PROCESS FOR PRODUCING HIGH 2,999,748 9/1961 Basen.................................... 75.15 X
CARBON FERROCHROME 3,661,555 5/1972 Kusama et al............................ 75/3
75 inventors: Toyozi Yoshida; Kazuhisa 3,759,695 9/1973 Downing............................... 75/3 X
Ushiyama; Minoru Yamanaka, all of
Tokuyama, Japan Primary Examiner-A. B. Curtis
73 Assignees: Showa Denko Kabushiki Kaisha; Attorney, Agent, or Firm-Sherman & Shalloway
Shunan Denko Kabushiki Kaisha,
both of Tokyo, Japan
57 ABSTRACT
22 Filed: Sept. 14, 1973
21 Appl. No. 397,359 A process for producing high carbon ferrochrome
which consists of feeding continuously to an electric
furance a charge mixture consisting of sintered pellets
52 U.S. C. ...................................................... 75/3 containing substantially no free carbon, which pellets
51) int. Cl........................... C22b 1/14, C21b 1108 have been obtained by the partial reductive calcina
(58) Field of Search....................................... 75/3, 5 tion of chrome ores, and a carbonaceous material of
particle size 20 - 100 mm; and submitting this charge
56) References Cited mixture to a continuous submerged arc smelting oper
UNITED STATES PATENTS ation.
2,883,278 4/1959 Douglas.................................... 75/5 2 Claims, No Drawings
 3,849,114
1. 2
PROCESS FOR PRODUCING HGH CARBON extensive researches. In consequence, we found that by
FERROCHROME following the method of the present invention to be
fully described hereinafter it was possible to produce
This invention relates to a process for producing high high carbon ferrochrome smoothly and continuously
carbon ferrochrome and, in particular, to a process for with small consumption of electric power, good effi
producing commercially advantageously high carbon ciency and high productivity. A primary object of this
ferrochrome from sintered pellets obtained by the re invention is therefore to provide a commercially useful
ductive calcination of chrome ores. process for the production of high carbon ferrochrome.
High carbon ferrochrome is usually produced by re Other objects and advantages of the invention will be
ducing chrome ores with carbon in an electric furnace. 0 come apparent from the following description.
This method has the shortcomings that a great amount
of electric power is consumed and that the productivity The foregoing objects of the present invention are
per electric furnace is low, since a prolonged period of achieved by a process for producing high carbon ferro
smelting time is required in the electric furnace. For 15 chrome which comprises feeding continuously to an
improving on these shortcomings, there has been pro electric-arc furnace sintered pellets obtained by the re
posed a method which comprises first preparing par ductive calcination of chrome ore and in which of the
tially reduced pellets by reducing the chrome ore with total content of oxygen combined with the iron and
carbon, using a heat source other than electricity, and chromium about 80 - 50 mol percent have been re
thereafter smelting these pellets finally in an electric 20 moved by reduction and the reduced iron and chro
furnace to complete the reduction and obtain the in mium are in the form of acid-soluble state, about 20 -
tended high carbon ferrochrome. According to this 50 mol percent, without having been removed and the
method, since a part of the heat energy required for the unreduced iron and chromium remain in the form of
reduction of the chrome ore is met by heat produced acid-insoluble oxides, and substantially no free carbon
by a source other than electricity, i.e., heat obtained by 25 is contained, and a granular carbonaceous reducing
burning of fuels, the consumption of electric power is material of particle sizes not greater than 100 mm, at
reduced to that extent. In addition, since the chrome least 70 percent by weight thereof being of sizes in the
ore has already been partially reduced, the time re range of about 20 - 100 mm, this carbonaceous mate
quired for the reduction in the electric furnace is re rial being fed in an amount equal to 0.7 - 1.4 times the
duced. stoichiometric amount required to reduce the oxides of
30 iron and chromium
A method of preparing pellets by partially reducing and remaining in said pellets to FeCa
chrome ores with a heat source other than electricity CrCs, respectively, and thereafter submitting the
is disclosed in U.S. Pat. No. 2,883,278. For ensuring charge in the electric-arc furnace continuously to sub
that the desired high carbon ferrochrome is formed by merged electric-arc smelting to form the high carbon
ferrochrome.
the further reduction of the so prepared pellets by their 35 -------
smelting in the electric furnace, these pellets contain a The sintered pellets are those in which about 80 - 50
substantial amount of free carbon. That the pellets con mol percent of the total amount oxygen combined with
tain free carbon required for completion of their reduc the two components iron and chromium in the chro
tion appears to be exceedingly rational. However, we mium ore have been removed by reductive calcination
found that these pellets had the following drawbacks. 40
and the reduced iron and chromium are in the form of
The first drawback of these pellets containing a sub acid-soluble state. By the expression "acid-soluble
stantial amount of free carbon was their low mechani form' is meant the components are soluble in an aque
cal strength. They tended to powder during the course ous sulfuric acid solution, practically all being in the
of their handling, transportation and feeding to the form of the carbides of iron and chromium. On the
electric furnace, as well as to powder readily in the 45
electric furnace. The second drawback of these pellets other hand, about 20 - 50 mol percent oxygen com
was that the continuous operation of their smelting in bined with the two components, not being removed as
the electric furnace could not be carried out smoothly yet, and the iron and chromium remain in the acid
insoluble state, i.e., in the form of the oxides of iron and
without the use of an additional supply of a carbona 50 chromium. Aside from the aforesaid iron and chro
ceous material. In fact, it was found that during the op mium components, the pellets also contain the oxides
eration the pellets would melt excessively and migrate of magnesium, aluminum and silicon as well as other
to the slag layer before their reduction had been suffi incidental impurities that are present in chrome ores.
ciently accomplished to lower the temperature of the Practically all of the carbon is present as the aforemen
slag raising the viscosity thereof, with the consequence 55 tioned carbides of iron and chromium, and there is con
that the continuous operation had to be stopped. While tained substantially no free carbon. By the expression
the reason therefor is not yet fully clear, it is conceiv “there is contained substantially no free carbon' is
ably due to the fact that since the melting speed of the meant that the content of the free carbon does not ex
pellets is greater than that of the ore, the pellets be ceed about 1.5 weight percent based on the weight of
come melted and flow down into the already formed 60
slag layer before the reaction between the free carbon
contained and the oxides of iron and chromium pro The acid-soluble and acid-insoluble iron and chro
ceeds sufficiently to result in the free carbon and the mium components present in the pellets can be quanti
oxides becoming separately dispersed in the slag layer, tatively determined by chemical analysis. Since the
with the consequence that the reaction between the 65 acid-insoluble oxides of iron and chromium can be ex
two components do not proceed sufficiently. pressed as Cr2O3 and Fe0, the mol percent of oxygen
With a view to overcoming the drawbacks of the in the form of these oxides remaining in the pellets can
prior art such as hereinabove described, we engaged in be determined as follows:
 3,849,114.
3 4.
Mol percent of the oxygen feeding the aforementioned pellets, along with the car
Insoluble Cr (percent) 3. bonaceous material and, if necessary, a slag former
52.0 x) such as lime or silica, to the top of a slag layer formed
, (Insoluble
-- Fe percent)
mamma-------www.
atop an underlying metal product layer formed at the
--- 55.85 X 100
5 furnace bottom. In the meantime, a part of the metal
product formed and a part of the slag formed are con
(Total Cr52.01(percent) x3)
2 tinuously or, more preferably, intermittently withdrawn
out of the furnace. In this case, a proper balance must
+(Total Fe55.85(percent) be maintained between the melting speed of the fed
O pellets inside the furnace and the speed at which the
wherein 52.01 is the atomic weight of Cr, and 55.85 is pellets are reduced by their reaction with the carbona
the atomic weight of Fe. ceous material. That is, those pellets which are rela
The foregoing equation can also be said to express tively meltable must not melt and flow down into the
the rate of nonreduction of the chrome ore. slag layer before they are reduced. This control is
The reductive calcination of the chrome ore to such 15 achieved by the carbonaceous material that is fed.
an extent that the oxygen combined with Cr and Fe Hence, a certain amount of the carbonaceous material
contained in the pellets are less than 20 mol percent, fed must always be maintained at the top surface of the
involves technical difficulties when carried out on a slag layer. For this purpose, the granular size of the car
commercial scale. On the other hand, pellets whose bonaceous material must not be too large nor too small.
content of the aforesaid oxygen exceeds 50 mol per If the size of the carbonaceous material is too large,
cent are submitted subsequently to the smelting step, their reactivity with the pellets suffer, whereas if the
the consumption of electric power and the smelting size of the carbonaceous material is too small, the parti
time are inevitably increased, and hence the expected cles of the carbonaceous material migrate into the slag
objects cannot be attained. Of further importance is layer and become suspended therein, thus losing their
that the pellets contain substantially no free carbon. As 25 reactivity, In addition, the size of the carbonaceous ma
previously noted, pellets containing a substantial terial affects the electrical resistance inside the fur
amount of free carbon tend to disintegrate. Hence, they nace. Generally speaking, when pellets that are already
are not only inconvenient to handle but also unsuitable partly reduced are used as in this invention, the amount
for carrying out their smooth continuous smelting in an 30
of the carbonaceous material used is lesser than in the
electric-arc furnace. This is also shown by the hereinaf case of the conventional methods of reducing chrome
ter given comparison examples. '- : ore in an electric furnace. Hence, the electrical resis
According to the present invention, pellets contain tance inside the electric furnace is increased to cause
ing 20 - 50 mol percent of oxygen combined with Cr greater difficulty in supplying a proper amount of elec
and Fe, along with a carbonaceous material in an tricity. This increase in electrical resistance can be
amount sufficient for removing the residual oxygen off, checked by enlarging the particle size of the carbona
are continuously fed to an electric-arc furnace, where ceous material that is fed. However, if the size is too
they are submitted to the submerged electric-arc re large, this also is undesirable, since there is a decrease
ducing operation. The major portion of the carbona in the reactivity of the carbonaceous material with the
ceous material fed is consumed in the reduction of the
40
pellets. After having conducted numerous experiments
oxides of Cr and Fe to the carbide form, whereas the in consideration of the various foregoing factors, it was
minor portion of the carbonaceous material is con found that the upper limit of the size of the carbona
sumed in reducing a part as well as a small amount of ceous material was about 100 mm and the optimum
the silica that is present in the pellets and the slag for range of the size was about 20 - 100 mm. While the
mer used or migrates into the slag to become lost as a : 45 presence of a small amount of those having a size less
result of being burned in the furnace. These various than 20 mm can be tolerated, at least 70 percent by
factors are taken into consideration in determining the Weight based on the total amount of the carbonaceous
proper amount of the carbonaceous material to be fed, material used must be particles having sizes in the
suitably used being an amount equal to 0.7 - 1.4 times range of 20 - 100 mm. Preferred examples of the car
the stoichiometric amount required for reducing the bonaceous materials that can be used include coal
oxides of iron and chromium contained in the pellets to 50 coke, petroleum coke and anthracite.
the FeC and CrCl forms. The stoichiometric amount Since a considerably large amount of the iron and
is based on the following reaction equations. chromium components which remain in the form of ox
7 Fe0 + 10C - FeC + 7CO ides are contained in the pellets used in this invention,
55 the smelting must be carried out by means of the sub
7CrO +27C -> 2Cr,C + 21CO merged arc method. And by operating thus, the smooth
The amount of such a carbonaceous material is de continuous operation becomes possible. The electric
pendent upon the content of the oxides of Cr and Fe in furnace used is preferably of the covered and sealed
the pellets, it being in the range of about 35 - 1 15 kg type for maintenance of a satisfactory working environ
per 1,000 kg of the pellets. 60 ment and for preventing of air pollution.
In addition to maintaining the amount of the carbo -----The pellets to be used in the present invention may
naceous material within the above range, it was found be those prepared by any method, so long as they pos
that the granular size of the carbonaceous material was sess the hereinbefore-described composition. One of
also a very important factor in carrying out the smooth the preferred methods of preparation of these pellets is
continuous operation of the reduction step with good 65 disclosed in U.S. Pat. No. 3,661,555, the assignee of
efficiency. The continuous submerged electric-arc which is the same as that of the present invention. A
smelting is carried out in the following manner. The preferred mode of the aforesaid method and its advan
smelting is continuously carried out while continuously tage, when briefly described, are as follows. First, a
 3,849,114
S
------------------ 6
mixture of a finely divided chrome ore and a finely di 1,500°C. is suitably used. Sintered pellets prepared in
vided carbonaceous material are pelletized. In this this manner possess especially desirable properties.
case, the carbonaceous material is contained in the That is to say, since the whole surface of the pellets is
mixture in an amount of 0.7 - 1.2 times the stoichio covered with a thin sintered coating of metal oxides,
metric amount required for reducing the oxides of 5 the pellets are resistant to oxidation. Hence, there is
chromium and iron contained in the chrome ore to the practically no fear of the reduction product that is pres
CrCa and FeCa forms. The so obtained green pellets ent inside the pellet becoming oxidized again even
are then calcined in a rotary kiln at 1,200 - 1,500°C., though contact is had with air. Further, the crushing
thus forming sintered pellets in which about 80 - 50 strength is also great by reason of this coating. Thus,
mol percent of the total content of the oxygen com 10 owing to the possession of these properties, these pel
bined with chromium and iron components is removed lets can be stored without oxidation being set up. Fur
and said two components are in the form acid-soluble thermore, they do not become crushed or powdered
state, about 20 - 50 mol percent of oxygen is not re during the course of their handling, transportation and
moved and said two components remain in the form of use. In those case where the production of ferrochrome
acid-insoluble oxides, and the resulting sintered pellets 15 by means of smalting in an electric furnace is to be car
contain substantially no free carbon. ried out in the same plant where the foregoing sintered
In the above-described method of preparing the sin pellets are prepared, it is possible to utilize the heat that
tered pellets, the mixture of a finely divided chrome ore is still retained by the pellets by feeding the pellets to
and a finely divided carbonaceous material is prepared the electric furnace immediately after their prepara
preferably by first mixing the starting aggregate materi 20 tion.
als and then comminuting this to a powder of an aver The following examples are given for more fully illus
age particle size of not greater than 40 microns. A part trating the invention. The parts in the examples are on
of the carbonaceous material that is mixed burns in the a weight basis.
Subsequent calcination step. Hence, the total amount EXAMPLE
of the carbonaceous material to be used must be deter 25
mined in consideration of the amount of the carbona The grades (weight percent) of the chrome ores and
ceous material that is burned during the calcination. It carbonaceous materials used were as follows:
has been ascertained that this total amount equals to
0.7 - 1.2 times the stoichiometric amount required for Chrome ore CrO. FeO AlO, MgO SiO,
reducing the oxides of Cr and Fe contained in the 30
chrome ore to the CrC and FeCs forms. Thus, by op Chrome
Orc
A 53.3 3.4 9 9.8 5.
erating as described hereinabove, sintered pellets are do. B 44.7 243 5.8 0.3 3.0
obtained in which about 80 - 50 mol percent of the do. C 49.9 8.3 2.0 5. 3.0
total amount of the oxygen combined with chromium Carbonaceous Fixed Particle
and iron components is removed, while about 20 - 50 35 material carbon Volatiles Ash content size (mm)
mol percent thereof is not removed and the two com
ponents remain in the form of oxides. Coke
do.
A
B
86.8
86.0
2,
1.7
10.2
11.5
maximum 5
0 - 20
The granulation of the foregoing mixture of a finely do. C 87. .5 10.8 20-00
divided chrome ore and a finely divided carbonaceous 40
material can be conveniently carried out using a suit
able granulator such as a pan pelletizer, a drum type 180 Parts of chrome ore A, 600 parts of chrome ore
granulator or a pressured granulator after adding a B, 220 parts of chrome ore C and 220 parts of coke A
small quantity of water glass or a temporary binder were mixed and thereafter comminuted to obtain a
such as water and bentonite to the mixture. The size of
45
powder having a particle size in which 90 percent pass
resulting pellets is preferably 15 - 35 mm. through a No. 150 Tyler mesh. This was followed by
The green pellets, after drying, are submitted to cal adding about 3 percent of bentonite and about 13 per
cination. Usable as the calcination furnace are the ro cent of water to this powder and pelletizing the mixture
tary kiln, shaft kiln and the like. Of these, most pre with a pan pelletizer to obtain green pellets having par
ferred is the rotary kiln wherein the calcination of the 50 ticle sizes of about 20 - 25 mm. The so obtained green
green pellets are carried out while tumbling the pellets pellets were then dried and preheated in a grate type
therein. Heat is provided by the combustion gas of fuel kiln and thereafter fed to a rotary kiln where they were
oil and other conventional fuels. As a result of the com calcined. The maximum temperature was about
bustion gas, the atmosphere inside the rotary kiln be 1,450°C. The resulting sintered pellets had the follow
comes partially oxidized, with the consequence that a 5S
ing analysis (weight percent).

Total Cr 32.64 Acid-soluble Cr 9.2 Acid-insoluble Cr 13.52

Total Fe 17,61 Acid-soluble Fe 15.8 Acid-insoluble Fe, 1.80
Total C 3.43 Free C 0.08

part of the carbonaceous material burns. And in conse The oxygen combined with Cr and Fe corresponds to
quence of the tumbling of the pellets, a thin sintered 33.6 mol percent of the total amount of oxygen present
coating of metal oxides is formed uniformly over the 65 in the starting chromium ore.
whole of the surface of the pellets, and there takes Smelting in electric furnace
place a partial reduction of the oxides of Cr and Fe in One thousand parts of the hereinabove-described sin
side the pellet. A calcination temperature of 1,200 tered pellets (while still in their red-heat state immedi
 3,849,114
7 8
ately after their preparation), 10 parts of coke B, 70 thorough reduction had taken place. Hence, con
parts of coke C (equal to 1.1 times the stoichiometric tinuous operation was not possible.
amount), 60 parts of silica and 100 parts of lime stone Comparison 3: In this experiment the pellets used
were continuously fed to an electric furnace (18,000 were those in which the residual amount of the ox
KVA, three-phase, closed type), and the continuous ides of Cr and Fe was too great. While it was possi.
submerged arc smelting of the pellets was carried out ble to carry out the continuous operation, the
to obtain a high carbon ferrochrome having the follow power consumption was too great. Hence, this
ing analysis (weight perent). would be a disadvantage in operating on a commer
cial scale.
O
We claim: T
C Si Fe and blance
1. A process for producing high carbon ferrochrome
which comprises feeding continuously to an electric
56.7 84.4 1.2 0.020 33.6 arc furnace a charge mixture consisting of sintered pel
15 lets obtained by the reductive calcination of chrome
ores, said pellets being those in which about 80 - 50
It was possible to operate the continuous submerged. mol percent of the total content of the oxygen com
arc smelting stably, and the power consumption per ton bined with iron and chromium components has been
of the product was 1,920 KWH. removed and the two components are in the acid
Examples and Comparison Examples 20 soluble from and about 20 - 50 mol percent, without
The experiments were carried out as in Example 1, having been removed and the two components remain
except that sintered pellets of various types were used, in the form of acid-insoluble oxides, and containing
and the amounts of the carbonaceous material were substantially no free carbon, and a granular carbona
varied. The results obtained are shown in the following ceous reducing material of particle sizes not greater
table, along with the results of Example 1. than 100 mm, at least 70 percent by weight thereof

Grade of sin Amount of coke used

tered pellets (kg/per ton of pellets)
Ratic of Times the Power
co- stoichio- consumption
Experiment version Free C metric (KWH/per
to
No. (%) (%) Coke B Coke C aOut of metal)
Example 33.6 O. O 70 l, 1920
do. 2 45.2 1.3 15 75 0.9 2180
do. 3 27.3 0.4 O 60 O 1740
Com
parison 33.6 0.1 80 O . 2190
do. 2 3.2 40 O O O m
do. 3 58.5 1,2 30 90 0.9 260

Note:- being of sizes in the range of about 20 - 100 mm, said

Example 1 - 3: Instances where the requirements of carbonaceous material being fed in an amount equal to
the present invention have been met. Stable and 0.7 - 1.4 times the stoichiometric amount required to
smooth continuous operation was possible and the reduce the oxides of iron and chromium remaining in
power consumption was also small. 45 said pellets to FeCa and CrC, respectively; and there
Comparison 1: This experiment illustrates the in after submitting said charge mixture in said electric-arc
stance where the size of the carbonaceous material furnace continuously to a submerged electric-arc
was too small. Migration of the carbonaceous ma smelting operation to form the high carbon ferro
terial to the slag layer took place before the carbo chrome.
naceous material had thoroughly reacted with the 50
pellets, thus causing difficulty in carrying out the 2. The process of claim 1 wherein said sintered pel
continuous operation. lets are obtained by pelletizing a mixture of a finely di
Comparison 2: In this experiment the carbonaceous vided chrome ore and a finely divided carbonaceous
material was not used, but the pellets used were material, the content of the latter in said mixture equal
those containing free carbon in an amount suffi 55 ling an amount 0.7 - 1.2 times the stoichiometric
amount required for reducing the oxides of chromium
cient to reduce the amounts of the residual oxides and iron to the CrCa and FeCa forms, and thereafter
of Cr and Fe. Disintegration and powdering of the calcining the resulting green pellets at 1,200 -
pellets took place during the operation. Further, 1,500°C. in a rotary k kiln.
the pellets migrated to the slag layer before their ck k k sk
60

65