FIELD OF THE INVENTION
The present invention relates to a method for direct reduction of oxidized chromite ore fines composite
agglomerates in a tunnel kiln using carbonaceous reductant for production of reduced chromite
product/ agglomerates applicable in Ferrochrome or charge chrome production. The invention further
relates to a slag with a novel slag chemistry for reduction of oxidized chromite one fines in the tunnel
kiln. The invention also relates to a method of using carbonaceous layer on the tunnel kiln car surface
for making the reduction process more effective in the tunnel kiln. The invention still further relates to
a novel method of partial recycling of the cooled tunnel kiln exhaust gas into the cooling zone of the
tunnel kiln for quenching/cooling of reduced product/agglomerate to prevent re-oxidation of the
reduced product and discharge the reduced product at temperature less than 500°C temperatures from
the tunnel kiln.
BACKGROUND OF THE INVENTION
Chromite ore is the prime raw material for production of ferrochrome using a submerged arc furnace
(SAF) process. Globally, most of the ferrochrome is produced by submerged arc furnace route except a
small fraction, produced in the DC are furnaces route. The smelting reduction of chromite ores is
carried out in the submerged arc furnaces using coke as the reductant and quartzite as the flux.
Chromite ores in the form of lump are smelted in the SAF directly, whereas the chromite ore fines in
the size range of 0 to 4.0 mm are agglomerated to pellets or briquettes. Chromite ore fines are
conventionally agglomerated to pellets without any prior heat treatment of ore fines. These
agglomerates are then subjected to sintering process in a vertical shaft furnace or a horizontal steel
belt sintering furnace prior to smelting in the submerged arc furnace.
According to the prior art, five primary processes are used for production of ferrochrome. These
processes include conventional process with open or semiclosed submerged arc furnaces, the
conventional process with closed submerged arc furnace, the Outokumpu process, the DC Arc route
and the Premus process. Each of these processes are discussed briefly below.
Conventional Process with Open or Semiclosed Submerged Arc Furnaces
In the conventional process, a mixture of chrome ore, reductants and flux is fed cold with minimum
pre-processing directly into open/semiclosed type submerged arc furnaces. The furnace off-gases are
cleaned in a bag plant before being vented into the atmosphere. The metal and slag are then tapped
from the furnace for further processing. The primary advantage of this process is that it requires lowest
capital investment and is very flexible in terms of raw materials that can be used in the process. The
main disadvantage of this process is that it is increasingly being perceived as being less
environmentally friendly than other available processes and it has the lowest efficiencies.
Conventional process with closed submerged arc furnace:
In conventional process with closed submerged arc furnaces, a mixture of sintered pellets, lumpy
chromite ores, coke as reductant and flux are fed to closed submerged arc furnaces. The furnace off-
gas is cleaned using wet scrubbers in the gas cleaning plant. The metal and slag are then tapped for
further process. The primary advantage of closed submerged arc furnace is that it is energy efficient
process as compared to open or semiclosed furnaces. The main disadvantages of the process are that,
the energy consumptions are still higher up to 4500 kWh/t of metal, requires costly metallurgical coke
and high losses of metal to slag upto 10% by weight.
Outokumpu process
Fine chrome ore is wet milled and then palletized using a binder such as bentonite. The pellets are
then sintered and then air cooled and stockpiled. The pellets together with fluxes may be heated in a
pre-heater located above the furnace bins. Reductants consisting of coke and char, are added to the
(preheated) raw materials and fed into closed submerged arc furnaces. The furnace off-gas is cleaned
in wet scrubbers and used as an energy source in the sintering and preheating processes. The main
advantages of this process is that the sintered pellets and preheating of the charge to the submerged
arc furnaces results in reduced specific energy consumptions and improved chromium recoveries.
DC arc furnace
The furnace uses a single solid carbon electrode and produces a DC arc to an anode in the bottom of
the furnace. The arc is normally an open or semi-submerged one. Raw materials can be charged either
directly into the furnace, or by using a hollow electrode. The primary advantage of this process is that
the process utilizes any of the available raw materials including
100% chromite fines with minimum or no pre-processing, thus eliminating the need for an expensive
agglomeration plant. Inferior grades of reductants like cola and anthracite can be used in this process,
which is also considered an additional advantage of the process.
Premus Technology
Fine chrome ore, bentonite and a reductant such as anthracite fines are dry milled, palletized and
preheated before being fed into rotary kilns where partial pre-reduction of the chromium oxidie and
iron oxides take place. The metallized pellets are then hot charged into closed submerged arc furnaces.
The furnace off-gas is cleaned in ventury scrubber and used throughout the plant as an energy source.
Initial capital costs for this process are high and the level of operational control required to ensure
smooth operation of the process is also very high.
The above processes manly included pre-reduction or preheating of agglomerates in rotary kilns. The
advantage was seen in reducing the cost of electrical energy. Chromium recoveries are improved and
cost smelting is reduced by these pretreatment methods. The steel belt sintering furnace process
developed by Outokumpu offered the reduced energy consumptions and emissions and was
advantageous to harden pellets in order to withstand handling. The preheating of smelting charge by
burning carbon monoxide in shaft furnace up to a temperature of 700°C, removes moisture and
volatiles, which gave major savings in electricity and increased the capacity of the smelting furnaces by
20%. The best metal recoveries were reached with agglomerated chromites from the materials.
Optimal smelting furnace operation was achieved by the right charge mix, depending on the raw
materials. The preheating and pre-reduction methods have improved the performance of SAF process;
however none of it could replace the SAF process completely. It is worthwhile to mention that, most of
these methods for ferrochrome production included the pre-treatment such as preheating or pre-
reduction of the agglomerates obtained either by agglomeration of chromite ores such as for sintering
or composite agglomerates obtained from agglomeration of chromite ores, reductant, flux and binder.
However it should be noted that, none of these processes (pre-heating, pre-reduction) have used the
tunnel kiln reduction process or process based on oxidized chromite ore fines which are obtained
typically by pretreatment of chromite ore fines such as oxidation of chromite ore fines prior to its
agglomeration. The oxidation process of chromite ore fines ensures a uniform degree of oxidation
across the oxidized chromite ore particles which help in enhancing the reduction reactions during
subsequent reduction process of oxidized chromite ore fines.
The prior art technologies are designed for processing of FeO-rich chromite ores for producing the
change chrome with relatively lower chromium content, varying between 50 to 55 percent. On the
other hand, the MgO-rich chromite ores are highly refractory in nature and therefore needs a different
approach. The key problems with SAF process used for production of high carbon ferrochrome are (a)
highly energy intensive process consuming about 2600-4500 kWh/t of FeCr (b) high Metallurgical coke
consumption of 500-700 kg/t (c) requires high quality feed material with Cr2O3 greater than 48 percent
(d) about 10 percent (by weight) Cr2O3 loss in slag (e) large volumes of slag (Slag: Metal ratio in
excess of 1.0) (f) environmental problems with respect to CO2 emissions and slag. Therefore, these
problems needs to be considered while developing a novel technology, which further contemplating use
of low cost materials, efficient and effective use of secondary energy produced, increase in process
efficiency, minimize the operating costs and improve the working environment.
Tunnel kilns are traditionally used for heat treatment of refractory bricks or calcinations of materials.
For example, a calcinations process of chrome ore and lime mixture bricks in the tunnel kiln at 1400°C
is disclosed in GB496890 to produce chromium chemicals such as calcium chromate and calcium
bichromate. The calcium bricks of chrome ore-lime mixture obtained from the tunnel kiln are ground
further and boiled with water in presence of air to remove CO2 and produce calcium carbonate
precipitate and calcium chromate solution. US3295954 discloses a process for alkaline roasting of
chromium ore with Na2O is disclosed wherein molding of ore and soda mixture is heated in tunnel kiln
at 1100°C to obtain improved chromium yield. A method for reduction of chromium ore in tunnel kiln is
disclosed in JP62256938, wherein the lump (molding) of mixture of ore, carbonaceous reducing agent
and binder is provided with a protective film of Cr2O2 SiC and fly ash on the surface for preventing
intrusions of oxidizable combustion gas into the molding during reduction between 1200 to 1500°C to
obtain high chromium reduction. JP62243723 describes a method for reduction of chromite wherein the
mixture of chrome ore, coke reductant and binder (carboxymethyl cellulose) is filled in a ceramic
(aluminous) vessel to form green compact of about 10 to 200mm diameter inside the vessel. The
ceramic vessels are then placed into a tunnel kiln of about 30 to 100 m length for atleast 30 minutes in
a temperature range of 1400 to 1500°C for obtaining about 90% reduction. A new smoke pollution
device for tunnel kiln is disclosed in US5603615, which prevents the discharge of pollutants such as
sulphides, steam and ashes to atmosphere. A tunnel kiln without exterior combustion chamber for
producing coal based direct reduced iron is disclosed in CN1804049. According to the cited invention
the width of the tunnel kiln is enlarged upto more than 10 m and single kiln production capacity up to
0.1mtpa and more than 0.5mtpa using suitable product quality and 1050 to 1300°C baking temperature
can be achieved. CN101497933 discloses a method for rapidly and directly reducing iron/hematite ore
or limonites into ferrous powder. The hematite ore is crushed, washed and subjected to magnetic
separation. The ore is mixed with coal dust, lime and calcium chloride (CaCI2) and binder. The mixture
is pressed into blanks, dried and stacked on cars to send in the tunnel kiln. The blanks are subjected to
water quenching to separate iron powder and slag automatically. CN101113488 discloses a method for
comprehensive utilization of V-Ti-bearing iron ore concentrate to produce iron powder and vanadium
pentaoxide compounds by using tunnel kiln reduction-grinding-separation. High temperature metal
recovery process is disclosed in US2003047035, for particulate metal containing dust such as electric
arc furnace dust wherein metallic values are recovered from the dust using a tunnel kiln. The mixture
of metal containing dust alongwith carbonaceous fines is heated in a moving bed horizontal tunnel
furnace to release volatile and alkali metals in gaseous product principally zinc and iron. The zinc and
iron are separated from gases as the process product. A process and apparatus for producing direct
reduced iron is disclosed in CN114708, wherein oxide of iron as raw material is mixed with bituminite,
lime, coal and nutshell as an additive. The mixture is fed in to a material column reactor which is
passed through externally heated tunnel kiln for 30 to 38 hours at about 950°C. The process is used for
direct reduction of iron-containing raw material in solid state into, metal iron. CN 1142541, discloses a
coal based direct reduction process of iron containing material to produce sponge iron using a tunnel
kiln. The mixture of iron ore, coal is fed to a metallic reactor and claimed in slope-type tunnel kiln to
produce sponge iron in the metallic reactors.
OBJECTS OF THE INVENTION
It is therefore and an object of the present invention to propose a method for direct reduction of
oxidized chromite ore fines (0 to 4.0mm) composite agglomerates in a tunnel kiln to produce reduced
chromite product/agglomerate to use in ferrochrome or charge chrome production.
Another object of the invention is to propose a method for direct reduction of oxidized chromite ore
fines (0 to 4.0mm) composite agglomerates in a tunnel kiln to produce reduced chromite
product/agglomerate to use in ferrochrome or charge chrome production, which uses oxidized chromite
ore fines (0 to 4.0mm) obtained by heat treatment of one of ground run of mine chromite ore (0 to
4.0mm) and a beneficiated product of run of mine chromite ore (0 to 4.0mm).
A further object of the invention is to propose a method for direct reduction of oxidized chromite ore
fines (0 to 4.0mm) composite agglomerates in a tunnel kiln to produce reduced chromite
product/agglomerate to use in ferrochrome or charge chrome production, which uses slag with
improved slag chemistry for reduction of oxidized chromite ore fines.
A still further object of the invention is to propose a method for direct reduction of oxidized chromite
ore fines (0 to 4.0mm) composite agglomerates in a tunnel kiln to produce reduced chromite
product/agglomerate to use in ferrochrome or charge chrome production, in which the reduction
process of composite agglomerates is carried-out in a tunnel kiln, using a carbonaceous agent layer on
the surface of kiln cars in order to maintain a highly reducing atmosphere in the immediate vicinity of
oxidized chromite ore fines composite agglomerates during reduction process in the tunnel kiln.
Yet further object of the invention is to propose a method for direct reduction of oxidized chromite ore
fines (0 to 4.0mm) composite agglomerates in a tunnel kiln to produce reduced chromite
product/agglomerate to use in ferrochrome or charge chrome production, in which a zone wise
temperature profile (distribution) is maintained in the tunnel kiln across its length for efficient reduction
of oxidized chromite ore fines composite agglomerates.
Another object of the present invention is to propose a method for direct reduction of oxidized
chromite ore fines (0 to 4.0mm) composite agglomerates in a tunnel kiln to produce reduced chromite
product/agglomerate to use in ferrochrome or charge chrome production, in which the an improved
tunnel kiln for carrying out an efficient reduction of composite agglomerates made from oxidized
chromite ore fines is used.
SUMMARY OF THE INVENTION
According to the present invention, a method is developed for direct reduction of oxidized chromite ore
fines composite agglomerates in the tunnel kiln using carbonaceous reductant such as coal. The
oxidized chromite ore fines are obtained by heat treatment of the chromite ore fines prior to its
agglomeration. This heat treatment in order to obtain oxidized chromite ore fines, is carried out in a
tunnel kiln or a rotary kiln at temperature of less than 1100°C with residence time in the range of 30 to
300 minutes in presence of air in order to oxidize the FeO present in chrome spinel to Fe-sequioxide
(Fe2O3). The Fe-sequioxide phase formed during oxidation process enables enhancing the subsequent
reduction process of oxidized chromite ore fines composite agglomerates in the tunnel kiln. The
oxidized chromite ore fines in the size range of 0 to 4.0 mm are mixed with carbonaceous reductant,
quartz or quartzite and lime as the slag formers and bentonite as the binder. The reductant, slag
formers and binder are added in predetermined ratio as per the designed slag chemistry to form
composite agglomerates for achieving enhanced reduction of oxidized chromite ore fines and formation
of low temperature slag during reduction. These composite agglomerates are dried and then fed to a
reduction process in the tunnel kiln. In tunnel kiln reduction process, a layer of carbonaceous agent
such as coal is placed on the surface of the kiln cars which allows maintaining a highly reducing
atmosphere in the immediate vicinity of the composite agglomerates subjected to reduction process.
The tunnel kiln used in the present invention is a closed type and air required for the combustion of the
fuel combustion as well as the excess air required for post-combustion of the reaction gas typically CO,
is supplied only in the firing/combustion zone through externally fired burners or additional air input
below the burners. Thus, the operating principle of the tunnel kiln in the present invention is different
than that of the conventional kilns for firing refractory bricks, where additional air is blown inside the
kiln at entry, exit and immediately after the firing zone (i.e. rapid cooling) in order to maintain proper
temperature profile as well as gas flow inside the kiln. One of the important features of the present
invention is that the proposed tunnel kiln makes use of partially cooled tunnel kiln exhaust gas for
cooling/quenching of the reduced product inside the tunnel kiln cooling zone, which achieves the
cooling of the reduced product/agglomerate to less than 500°C by preventing reoxidation of the
reduced product. This feature eliminates the need of quenching the reduced product in water outside
the tunnel kiln and also prevents the disintegration of reduced product which usually occurs in water
quenching process. The reduced product/agglomerates obtained from the tunnel kiln reduction process
have high metallization of iron and chromium. These reduced chromite agglomerates can be used in
ferrochrome or change chrome production at a lower energy consumption in ferrochrome or charge
chrome production, and further improves the productivity of the submerged arc furnaces.
The present invention results in production of reduced chromite product/ gglomerates with a high
degree of iron and chromium metallization which can reduce the energy and coke consumption in
ferrochrome or charge chrome production. The reduced chromite agglomerates are obtained by
reduction of oxidized chromite ore fines composite agglomerates in a tunnel kiln.
According to the invention, the heat treatment of ground run of mine chromite ore fines is carried out
in a tunnel kiln or a rotary kiln in presence of air and typically at temperature upto 1100°C to 30 to 300
minutes duration in order to break the chrome spinel in chromite ore fine particles due to oxidation and
conversion of FeO present in chrome spinel to Fe-sequioxide lamellae on the surface of chromite ore
particles.
According to the invention, an improved slag chemistry is obtained by using proper mixture ratio of
carbonaceous reductant, slag formers such as quartz or quartzite and calcined lime or hydrated lime in
order to form low temperature slag for enhancing the reduction of oxidized chromite ore fines in tunnel
kiln. The agglomerates made from proper mixture ratio of oxidized chromite ore fines, slag formers
such as quartz or quartzite and lime alongwith bentonite binder are termed as composite
agglomerates.
According to the invention, the tunnel kiln has a length of about 20m which is much less as compared
to conventional refractory bricks application kiln which are usually greater than about 30m long. The
new design of the kiln uses partially cooled tunnel kiln exhaust gas for quenching/ cooling of the
reduced agglomerates in the cooling zone of the kiln such that the reduced product/agglomerates are
discharged at less than 500°C temperatures from the tunnel kiln. This feature helps to achieve the
cooling of the reduced product and prevent its re-oxidation. Use of partially cooled tunnel kiln exhaust
gas for cooling also eliminates the need for water quenching of the reduced product outside the
reduction equipment which is usually applied for cooling of direct reduction processes product.
BRIEF DESCRIPTION OF THE ACCOMPANYING DRAWINGS
The invention is explained in greater details wit the accompanying drawings:
Figure 1 shows a typical size analysis of Mgo-rich chromite ore fines obtained either by girding run of
mine chromite ore or by beneficiation of run of mine chromite ore
Figure 2 present a comparison of optical micrograph of chromite ore particles before and after
oxidation in a tunnel kiln or a rotary kiln, the microstructure of chromite ore particles after oxidation
exhibiting an exolved lamellae of Fe-sequioxide developed on the surface of chromite grains due to
oxidation process.
Figure 3 shows a process for reduction of composite agglomerates in the tunnel kiln emphasizing
placing of the carbonaceous layer on the surface of trolley or car, and the physical state of the
composite agglomerates before reduction in the tunnel kiln and after reduction in tunnel kiln.
Figure 4 shows a schematic diagram of tunnel kiln reduction process for reduction of composite
agglomerates made from oxidized chromite ore fines consisting of typical temperature profile and
residence/cycle time of composite chromite agglomerates in the tunnel kiln, which particularly shows
the zone-wise temperature profile in the tunnel kiln across the length of the kiln, the cumulative
residence time of the composite agglomerates placed on the cars for total reduction cycle in the tunnel
kiln.
Figure 5 shows a schematic diagram of a tunnel kiln process showing a method for cooling reduced
product/agglomerate inside a tunnel kiln for prevention of re-oxidation of the reduced product by using
a part of the tunnel kiln exhaust gas cooled to 100 to 200°C before injecting it into the cooling zone of
the tunnel kiln.
Figure 6 shows typical micrographs of reduced product/agglomerates (pellet and briquette which are
typically pillow shape agglomerates) obtained by reduction of composite chromite agglomerates in a
tunnel kiln reduction process, the micrograph exhibiting three phases namely reduced Fe-Cr metal, slag
and partially reduced chromite particles.
Figure 7 shows a size analysis of FeO-rich chromite ore as an additional example of oxidized chromite
ores used for reduction in the tunnel kiln.
Figure 8 shows optical micrograph of oxidized FeO-rich chromite ore particles, the micrograph
exhibiting an exolved Fe2O3 phase on the surface of oxidized FeO-rich chromite ore particle.
Figure 9 shows micrographs of reduced product/agglomerates obtained by reduction of oxidized FeO-
rich chromite ore composite agglomerates in a tunnel kiln showing reduced metal (Fe-Cr metal), slag
and partially reduced chromite partices.
DETAILED DESCRIPTION OF THE INVENTION
Chromite ore fines (0 to 4.0mm) are typically obtained by grinding the run of mine chromite ore to fine
size (less than 4.0mm). The typical particle size analsysis of Mgo-rich ore fines is shown in Figure 1. It
can be seen that, the d80 (80% of particles having average diameter) of chromite particle is in the
range of 80 to 90 urn. The oxidized chromite ore fines used in the present inyention to form composite
agglomerates were obtained by heat treatment of chromite ore fines (0 to 4.0mm) prior to its
agglomeration. This heat treatment in order to obtained oxidized chromite ore fines, is typically carried
out in tunnel kiln or rotary kiln at temperatures of less than 100°C for residence time in the range of 30
to 300 minutes typically in presence of air in order to oxidized the FeO present in chrome spinel to Fe-
sequioxide (Fe2O3). The typical optical micrograph of chromite ore particles before and after oxidation
process is shown in Figure 2. The optical micrograph of chromite ore particles after oxidation process
(Figure 2b) shows the Widmanstatten structure of bright lines on chromite mineral. It can be seen that,
the Fe-sequioxide phase has exolved on the surface of chromite particles. During oxidization reaction,
the FeO present in chrome spinel gets oxidized to Fe2O3 as exolved Fe-sequioxide phase and in turn
cation vacancies are generated in the spinel lattice. In an oxidizing atmosphere, in addition to the
intrinsic driving force for phase transformation, the imposed oxygen chemical potential promotes the
diffusion of Fe2+ ions from the core of chromite grain towards the solid-gas interface on the surface of
the grain. This outward diffusion of Fe2+ cations and oxidization to Fe3+ cations takes place via
following reactions:

Where represents oxygen anions on the cubic closed packed lattice, is cation vacancy, h* is
hole, and e' is electron. Oxidation of chromite ore also results in opening up of the spinel structure. The
optical micrograph of chromite ore particles after oxidation process is shown in Fig. 2b, which shows
the Widmanstatten structure of bright lines on chromite mineral. It can be seen that, the Fe-sequioxide
phase has exolved on the surface on the chromite particles. The EDX analysis of oxidized chromite
particles has indicated that the bright lines are iron rich phases and the matrix is magnesium rich
phase. It can be concluded from above that iron is precipitating from the matrix on {111}
crystallographic planes. The oxidation of chromite resulting in Widmanstatten structure is in accordance
with established theory of oxidation and precipitation of sequioxide phase which states that preferential
crystallographic orientation of Widmanstatten lamellae was along the {111} plane of spinel matrix
phase. The {111} planes of spinel and the {001} planes of sequioxide have a similar close packing
arrangement of oxygen ions, which account for the common orientation of sequioxide lamellae along
the {111} plane of the spinel matrix. Tapered terminals develop at the intersection of two or more
lamellae, which are indicative of a diffusion-controlled process. This newly formed Fe-sequioxide phase
on chromite particles along with the vacancies generated during oxidation improves the reactivity of
chromite ore during reduction. This Fe-sequioxide phase formed during oxidation process helps in
enhancing the subsequent reduction process of oxidized chromite ore fines composite agglomerates in
tunnel kiln. The oxidized chromite ore fines in the size range of 0 to 4.0 m are mixed with powdered
carbonaceous reductant such as coal, powdered quartz or quartzite and powdered lime such as
calcined lime or hydrated lime as slag formers and bentonite as binder. The typical chemical
composition of different raw materials such as coal (reductant), quartz, calined lime or hydrated lime
(slag formers) and bentonite (binder) used in the present invention is shown in Table 1. The reductant,
slag formercs formers and binder are added in predetermined ratio as per the specially designed slag
chemistry to form composite chromite agglomerates for achieving enhanced reduction of oxidized
chromite ore fines and formation of low temperature slag during reduction. The typical chemical
composition of composite agglomerates used in the tunnel kiln reduction process obtained after mixing
and agglomerating predetermined ratio of raw materials in order to achieve special slag chemistry is
also shown in Table 1. The formation of low temperature slag during reduction in tunnel kiln is
achieved with the help of lowering the slag liquids due to use of lime as slag former and also due to
reduction of Fe-sequioxide (Fe2O3) phase in oxidized chromite ore fines formed during oxidation of FeO
at low temperatures. It is worthwhile to mention that, the formation of Fe-sequioxide phase lamellae is
uniform across the chromite grain surface due to selection of finer (0 to 4.0 mm) oxidized chromite ore
fines which ensures that maximum iron present in oxidized ore is available as a separate the FeO has
to come to travel to the particle surface and then reduce while is not an effective reduction process.
Since the iron is present as separate exolved Fe-sequioxide (Fe2O3) phase in oxidized chromite ore
fines, it reduces quickly to FeO at low temperature during reduction. This newly formed FeO acts as
slag forming agent and enhances the diffusion of iron and chromium ions in slag. One of the important
features of the newly formed FeO is that it further reduces to Fe3C (iron carbides) at low temperatures
and the carbon present in iron carbides helps in reduction of chromium oxides thus further enhancing
the reduction process. The composite agglomerates obtained from mixing and agglomerating the
oxidized chromite ore fines, slag formers and binder can promote formation of spherical pellets or
briguettes or lump or any other form of agglomerates. These composite agglomerates are then
subjected drying process for 30 to 120 minutes in the temperature range of 100°C to 200°C. The
drying process is carried out in continuously moving steel grate belt dryer which typically uses hot air
from hot air generator as drying medium. The dried composite chromite agglomerates are then fed to
reduction process in tunnel kiln. In tunnel kiln reduction process, a layer of carbonaceous agent such
as coal is placed on the surface of the kiln cars which helps in maintaining highly reducing atmosphere
in the immediate vicinity of the composite agglomerates subjected to reduction process. Figure 3a
shows the method of placing the carbonaceous layer on the surface of tunnel kiln car and Table 1
shows typical chemical composition of the carbonaceous layer agent such as coal. The carbonaceous
layer is sprayed/placed on the cars or surface of the trolley such that each car/trolley have atleast 100
g or upto 5000 g of additional coal on each car/trolley surface apart from coal present in the dried
composite agglomerates. The dried composite agglomerates are then laid on the carbonaceous layer
on the surface of car/trolley such that a typical thickness of agglomerate layer is about 30 to 40mm on
the carbonaceous layer is ensured. The feeding of composite agglomerates on the surface of car or
trolley is carried out using a vibrating hopper feeder arrangement supported with a leveler which
ensures the desired thickness of composite agglomerates layer on the surface of each car. The
composite agglomerates laid on a typically trolley of tunnel kiln car before subjecting to reduction
process is shown in Figure 3b. The tunnel kiln used in the present invention is closed type and air
required for fuel combustion as well as excess air required for post-combustion of reaction gas typically
CO, is supplied only in the firing/combustion zone through externally fired burners or additional air
input below the burners. Thus, the operating principle of the tunnel kiln in present invention is different
unlike the conventional refractory brick application kilns where additional air is blown inside at entry,
exit and immediately after the firing zone (i.e. raid cooling of product) in order to maintain proper
temperature profile as well as gas flow inside the kiln.
The tunnel kiln used in the present invention has four major temperature zones across the length of
tunnel kiln. These temperature zones starting from entry are drying, preheating, firing and cooling
zone. The schematic of typical tunnel kiln reduction process used in the present invention is shown in
figure 4. The typical temperatures maintained in the four zones of tunnel kiln during reduction process
are, less than or equal to 800°C in drying zone, less than 1000°C in drying zone, less than 1000°C in
preheating, less than or equal to 1500°C in firing zone and less than or equal to 500°C in cooling zone.
It is worthwhile to mention here that, the temperature in different zones or temperature distribution
across the tunnel kiln length are only indicative and slight variations (±200°C) in temperatures can
occur across the length of tunnel kiln. The tunnel kiln cars having composite agglomerates placed on it,
travels through all the four temperature zones of tunnel kiln such that the total residence/ cycle time
(in to out) of composite agglomerates is maintained typically of about 75 minutes within kiln however
this residence or cycle time may not be sacrosanct and can vary depending on the properties of the
composite agglomerates subjected to reduction process using the disclosed method in present
invention. The indicative cumulative residence time or cycle time distribution for composite
agglomerates within kiln is also shown in Figure 4. The reduced product or agglomerates are
discharged from tunnel kiln without its re-oxidation at temperatures less than 500°C while exiting from
tunnel kiln. This fairly rapid quenching or cooling of the reduced product without re-oxidation is
achieved using partially cooled tunnel kiln exhaust gas for rapid quenching or cooling of the reduced
product in the cooling zone of tunnel kiln. One of the important features of the present invention is that
the proposed tunnel kiln makes use of part of tunnel kiln exhaust gas which is cooled to about 100 to
200°C in gas cooling unit outside tunnel kiln. Figure 5 shows the schematic of typical tunnel kiln
arrangement used for achieving the cooling of the reduced product or agglomerate to less than 500°C
while exit from tunnel kiln. The tunnel kiln exhaust gas consists of CO2 and N2 (nitrogen) as a major
constituent since most of the CO generated during reduction reactions is burned inside the firing or
combustion zone to convert to CO2 by use of excess air. Therefore, the tunnel kiln exhaust gas
containing CO2 and N2 as major gas components is partly diverted to a gas cooling unit for cooling the
tunnel kiln exhaust gas to about 100 to 200°C. This cooled gas is injected into cooling zone of tunnel
furnace for rapid quenching or cooling of the reduced product/agglomerate arriving from the
firing/reduction zone of tunnel kiln. The rapid quenching of the reduced product using the cooled
tunnel kiln exhaust gas prevents the re-oxidation of the reduced product and also ensures rapid cooling
of the reduced product to less than 500°C. The reduced product is cooled to less than 500°C within
the cooling zone and cars are taken out of the kiln since the reduced chromite product or agglomerates
does not re-oxidize due to exposure to atmospheric air at temperature below 500°C. This feature
eliminates the need of quenching the reduced product in water outside the tunnel kiln and also
prevents the disintegration of reduced product which usually occurs in water quenching process used in
direct reduction processes. The reduced product or agglomerates typically obtained after reduction of
composite agglomerates are shown in Figure 3b. The reduced product/agglomerates are then removed
from the tunnel kiln cars using a physical scrapper or pneumatic hammer for further use of the reduced
product in ferrochrome or charge chrome production. The reduced product/agglomerates obtained
from tunnel kiln reduction process have high metallization of iron and chromium. The typical chemical
composition of reduced product or agglomerates is given in Table 2. The % iron metallization (i.e. ratio
of metallic iron to total iron in reduced agglomerate) in reduced product is upto 90% and % chromium
metallization (i.e. ratio of metallic chromium to total chromium in reduced agglomerate) in reduced
product obtained from the tunnel kiln is as high as 75%. Figure 6 shows the typical micrographs of
reduced pellets and reduced briquettes obtained by reduction of composite pellets or briquettes in
tunnel kiln. The micrographs shows three phases namely reduced Fe-Cr metal, slag and partially
reduced chromite particles in the reduced agglomerates. These reduced chromite agglomerates can be
used in ferrochrome or charge production which can result in low energy consumption in ferrochrome
or charge chrome production and also improves the productivity of the submerged arc furnaces due to
presence of highly metalized iron and chromium in it. The reduced chromite agglomerates can be used
in ferrochrome/charge chrome production. The use of reduced agglomerates obtained in the present
method, in ferrochrome production by submerged arc furnace process can result in low energy
consumption in ferrochrome/charge chrome production and also improves the productivity of the
submerged arc furnace. The reduced agglomerates obtained in present invention, can further result in
increased chromium content in the ferrochrome/charge chrome product due to its effective smelting
properties in submerged arc furnace. Therefore, a new method of direct reduction of oxidized chromite
ore fines in tunnel kiln is developed in the present invention. As a additional example of the tunnel kiln
reduction process, oxidized Feo-rich chromite ore (0 to 4.0mm) having typical size analysis as shown in
Figure 7 and chemical composition as given in Table 3 was also subjected to reduction process in
tunnel kiln as described above. The optical micrograph of oxidized FeO-rich chromite ore used in the
present invention is shown in Figure 8. It can be seen that, the FeO present in chrome spinel was
oxidized to Fe2O3 as exolved Fe-sequioxide phase which improves the reactivity of ore in subsequent
reduction processes. Typical micrographs of reduced product/ agglomerates obtained by reduction of
oxidized FeO-rich chromite ore composite agglomerates obtained by reduction of oxidized FeO-rich
chromite ore composite agglomerates in tunnel kiln are shown in Figure 9 showing three phases
namely reduced metal (Fe-Cr Metal), slag and partially reduced chromite particles. The reduction
process of oxidized South African chromite ore composite agglomerates in tunnel kiln was highly
effective, and high degree of iron and chromium metallization is achieved in reduction process.
WE CLAIM
1. A method for direct reduction of oxidized chromite ore fines (0 to 4.0 mm) composite
agglomerates in a tunnel kiln to produce one of a reduced and agglomerates for use in
ferrochrome or charge chrome production; comprising:
Implementing a direct reduction or solid state reduction of oxidized chromite ore fines in a
tunnel kiln using carbonaceous reductant such as coal, anthracite or charcoal.
2. The method as claimed in claim 1, wherein the oxidized chromite ore fines are having particles
size range from 0 to 4.0 mm and having 80% of particles having average diameter less than 90
µm.
3. The method as claimed in claim 1, wherein the oxidized chromite ore fines have Cr2O3 content
in the range of 25 to 55% (by weight) and Fe(t) in the range of 10 to 25% (by weight).
4. The method as claimed in claim 1, wherein the oxidized chromite ore fines are obtained by heat
treatment of chromite ore fines in tunnel kiln or rotary kiln at temperature of less than 1100°C
and for residence time up to 300 minutes typically in presence of air.
5. The method as claimed in claim 1, wherein the chromite ore fines may be obtained by grinding
the run of mine chromite ore/lumps or a product of beneficiation of run of mine chromite ore
for use in ferrochrome or charge chrome production.
6. The method as claimed in claim 4, wherein the oxidized chromite ore fines has Fe-sequioxide
phase lamellae on atleast one of the chromite particles which is iron rich phase in the
microstructure of oxidized chromite particle.
7. The method as claimed in claim 1, wherein the composite agglomerates are obtained by mixing
and agglomerating the mixture of oxidized chromite ore fines, reductant, slag formers and
binders in predetermined ratio as per the special slag chemistry to form into composite
agglomerate.
8. The method as claimed in claim 7, wherein the reductant is carbonaceous agents such as
powered coal, powdered coke, anthracite or charcoal and slag formers are powdered quartz or
quartzite and powdered lime can be calcined lime or hydrated lime.
9. The method as claimed in claim 8, wherein the reductant carbonaceous agent has fixed carbon
typically in the range of 60 to 87% by weight and volatiles matter in the range of 5 to 45% by
weight.
10. The method as claimed in claim 7, wherein the binder is of organic or inorganic base for
example bentonite, dextrose, lingo sulphonate, molasses or dextrin.
11. The method as claimed in claim 7, wherein the slag chemistry is characterized by chemical
composition of the slag forming components in composite agglomerates such as SiO2 typically in
the range of 5.0 to 25.0% by weight, Al2O in the range of 3.0 to 20.0% by weight, MgO in the
range of 5.0 to 15.0% by weight and CaO in the range of 2.0 to 15.0% by weight.
12. The method as claimed in claim 7, wherein the composite agglomerates have shape selected
from a group consisting of a spherical pellet a briquette a lump, and other form of agglomerates
comprising atleast oxidized chromite ore fines as one of its constituent item.
13. The method as claimed in claim 1, wherein the reduction process of composite agglomerates is
carried out in a tunnel kiln having length of about 20m.
14. The method as claimed in claim 1, wherein the tunnel kiln reduction process is characterized by
subjecting the composite agglomerates to reduction process by placing them on carbonates
layer on the surface of tunnel kiln cars or trolleys.
15. The method as claimed in claim 13, wherein the carbonaceous layer placed on the tunnel kiln
cars or trolleys is of carbonaceous agent such as coal, char, anthracite, coke or charcoal.
16. The method as claimed in claim 15, wherein at least additional 100 g or upto 500 g of
carbonaceous agent is sprayed or laid on each of the tunnel kiln car or one the trolley surface.
17. The method as claimed in claim 15, wherein the carbonaceous layer placed on the tunnel kiln
car or trolleys creates a highly reducing atmosphere in the adjacent vicinity of the composite
agglomerates during reduction in the tunnel kiln.
18. The method as claimed in claim 14, wherein the composite agglomerates are placed on
carbonaceous agent layer on the tunnel kiln car/trolleys forms a layer with 30 to 40 mm
thickness.
19. The methods as claimed in claim 13, wherein the reduction process of composite agglomerates
is carried out by subjecting the composite agglomerates placed on the tunnel kiln cars to a
temperature profile inside the tunnel kiln for a predetermined residence or cycle time.
20. The method as claimed in claim 18, wherein the tunnel kiln has a plurality of temperature zones
across its total length which start from the entry of the kiln, and comprises a drying zone, a
preheating zone, a firing or reduction or combustion zone, and a cooling zone.
21. The method as claimed in claim 18, wherein the temperature profile inside the tunnel kiln is
characterized by about less than or equal to 800°C temperature in the drying zone, less than
1000°C in the preheating zone, less than or equal to 1500°C in the firing or reduction or
combustion zone and less than or equal to 500°C in the cooling zone.
22. The method as claimed in claim 18, wherein the predetermined residence or cycle time
constitutes the total time of composite agglomerates spent across total length of the tunnel kiln
which is typically less than 80 minutes.
23. The method as claimed in claim 1, wherein the tunnel kiln is of enabled to carry out an efficient
reduction of the composite agglomerates and prevent re-oxidation of the reduced product or
agglomerates.
24. The method as claimed in claim 23, wherein the tunnel kiln is characterized by use of a part of
the tunnel kiln exhaust gas which is cooled and injected to the cooling zone of the tunnel kiln.
25. The method as claimed in claim 24, wherein the tunnel kiln is of closed type and air required for
combustion of fuel including excess air required for combustion of fuel including excess air
required for post-combustion of reaction gases (typically CO) enters only in the firing or
reduction or combustion zone.
26. The method as claimed in claim 24, wherein the tunnel kiln exhaust gas consists of CO2
(carbon dioxide) and N2 (nitrogen) gas as its major constituents.
27. The method as claimed in claim 25, wherein the major constituents of the tunnel kiln exhaust
gas such as CO2 is a result of fuel combustion using air including post-combustion of reduction
reaction gas such as CO using excess air.
28. The method as claimed in claim 26, wherein the post-combustion is obtained in the firing zone
by injecting excess air either through burner or additional input in firing zone.
29. The method as claimed in claim 24. wherein the part of the tunnel kiln exhaust gas is cooled in
external gas cooling unit.
30. The method as claimed in claim 24, wherein the cooled tunnel kiln exhaust gas is injected at
the beginning of the cooling zone or at the end of the firing zone along the length of the tunnel
kiln in order to quench or cool the reduced product to less than 500°C.
31. The method as claimed in claim 24, wherein the cooling zone is characterized by zone having
temperature less than 500°C towards the exist end of tunnel kiln.
32. The method as claimed in claim 1, wherein the reduced product or agglomerates is obtained at
a temperature of less than 500°C on the tunnel kiln cars after reduction of the composite
agglomerates in new design of tunnel kiln.
33. The method as claimed in claim 1, wherein the reduced product or agglomerate is characterized
by presence of reduced metal (Fe-Cr metal) metallic phase in atleast one of the reduced
agglomerates.
34. The method as claimed in claim 1, wherein the reduced product or agglomerate typically have
multi-phases comprising a reduced metal (Fe-Cr metal) phase, a slag phase and a partially
reduced chromite particles.
35. The method as claimed in claim 1, wherein the reduced product is characterized by percent
chromium (Cr) metallization in the range of 15.0 to 75.0% by weight and percent iron (Fe)
metallization in the range of 40.0 to 90.0% by weight in the reduced product or agglomerate.
36. The method as claimed in claim 1, wherein the reduced product or agglomerates are removed
from tunnel kiln car and used in ferrochrome production or charge chrome production or in any
other application where smelting of reduced product or agglomerates is carried out in a vessel.
37. The method as claimed in claim 36, wherein the reduced product or agglomerates are removed
by using one of a physical scrapper and a pneumatic hammer.
38. The method as claimed in claim 36, wherein the product ferrochrome is of high carbon
ferrochrome production or low carbon ferrochrome production.
39. The method as claimed in claim 36, wherein the charge chrome production is characterized by
production an alloy of Fe and Cr which typically contains chromium in the range of 45.0 to
60.0% by weight.
21
Table 1 Typical chemical composition of raw materials for reduction process
Table 2 Typical chemical composition of reduced agglomerates obtained from tunnel kiln
reduction process
Table 3 Typical chemical composition of South African chromite ore

This invention relates to a method for direct reduction of oxidized chromite ore fines (0 to 4.0 mm)
composite agglomerates in a tunnel kiln to produce one of a reduced and agglomerates for use in
ferrochrome or charge chrome production; comprising implementing a direct reduction or solid
state reduction of oxidized chromite ore fines in a tunnel kiln using carbonaceous reductant such as
coal, anthracite or charcoal.