See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/225835979

Mechanism of Titanium Sponge Formation in the Kroll Reduction Reactor

Article  in  Metallurgical and Materials Transactions B · February 2004

DOI: 10.1007/s11663-004-0097-2

CITATIONS READS

28 463

4 authors, including:

Ch. R. V. S. Nagesh N. B. Ballal

Defence Research and Development Organisation Indian Institute of Technology Bombay
10 PUBLICATIONS   60 CITATIONS    48 PUBLICATIONS   589 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

development of electrochemical process for titanium extraction View project

Development of 2D BF model View project

All content following this page was uploaded by Ch. R. V. S. Nagesh on 26 November 2014.

The user has requested enhancement of the downloaded file.

03_01-52B-C.qxd 6/1/04 8:14 PM Page 65

Mechanism of Titanium Sponge Formation in the Kroll

Reduction Reactor
CH.R.V.S. NAGESH, CH. SRIDHAR RAO, N.B. BALLAL, and P. KRISHNA RAO

The Kroll process of magnesium reduction of titanium tetrachloride is used the world over the production
of titanium metal in the form of sponge. Although the process has been in practice for the last five
decades, there is no clear understanding of the reaction mechanism and sponge formation. The present
study involved reduction experiments in a 2000 kg titanium sponge–capacity prototype reactor to
develop a better understanding of TiCl4 reduction of magnesium with respect to the process parameters.
Experiments were also conducted in two smaller experimental reactors to study the temperature evolution
during the process as a function of the TiCl4 feed rate. Based on the results of all these experiments,
a model has been proposed for the mechanism of sponge formation in the Kroll process.

I. INTRODUCTION were also carried out in two smaller experimental crucibles

IN the Kroll process, titanium tetrachloride (TiCl4) is
reduced with magnesium at high temperature in a closed
reactor under an inert gas atmosphere.[1] The process has
been widely used over the last 50 years for the commercial
production of titanium metal. Many variations of the mag-
nesiothermic reduction have been attempted, as reported in
the literature.[2–6] With increasing usage of titanium in non-
aerospace applications, there have been continuing efforts
to decrease the energy consumption in the process and the
cost of the metal.
The Kroll reduction reaction
TiCl4 (g)
2 Mg (l)  Ti (s)
2MgCl2 (l)
H1000K  412 kJ/mole
is a complex heterogeneous exothermic reaction with the pos-
sibility of the formation of lower-valence titanium chlorides
(TiCl2 and TiCl3) as reaction intermediates. The smooth
running of the reduction process, titanium yield, quality of
the sponge, and magnesium utilization are all highly dependent
on the control of the temperature, the reaction rate, and the
formation of lower chlorides. In spite of the many studies
reported on the process,[7–12] there is no consensus on the
mechanism of sponge formation and the reaction model. In
the present work, Kroll reduction experiments were conducted
in a prototype reactor and in small experimental crucibles to
develop a better understanding of the reduction process.
II. EXPERIMENTAL WORK
Reduction experiments were carried out in a prototype
Kroll reactor with a capacity to produce 2000 kg of titanium
sponge per batch, at three different TiCl4 feed rates. Studies
CH.R.V.S. NAGESH, Scientist “E,” is with the Defence Metallurgical
Research Laboratory, Kanchanbagh, Hyderabad, A.P. India 500058. Contact
e-mail: nagesh_chrvs@rediffmail.com CH. SRIDHAR RAO, formerly
Scientist “F,” Defence Metallurgical Research Laboratory, is retired.
N.B. BALLAL and P. KRISHNA RAO, Professors, are with the Department
of Metal Engineering and Materials Science, Indian Institute of Technology,
Bombay, Powai, Mumbai, India 400076.
Manuscript submitted January 30, 2001.
to know the variation of temperatures at different locations
in the bath during the magnesiothermic reduction of TiCl4.
A. Experiments in the 2000 kg Prototype Reactor
The reactor consisted of a carbon steel crucible, 1210 mm
in internal diameter and 3050 mm in height, placed inside
a stainless steel retort, measuring 1360 mm in internal
diameter and 3500 mm in height (Figure 1). The crucible
had a detachable, perforated bottom plate with a number
of holes, 40 to 50 mm in diameter. The lid of the retort
had nozzles for feeding TiCl4, admitting argon, and for
pressure control. A drain pipe with a valve at the bottom
of the retort was used for periodic draining of molten MgCl2
during the course of the reduction experiment. The retort
was placed inside a seven-zone, vertical, pit-type electrical
resistance furnace. A network of radial nozzles was pro-
vided in the furnace, through which cooling air could be
blown onto the outer surface of the retort wall. The retort-
wall temperature was controlled by controlling the
temperature of each zone of the furnace independently and
by blowing cooling air as required. The retort-wall tem-
perature was measured at five locations along its height
using chromel-alumel thermocouples.
Production of 2000 kg of titanium sponge requires reduc-
tion of about 8000 kg of TiCl4. Based on preliminary
experiments, it was established that 40 to 45 pct excess
magnesium is necessary over the stoichiometric require-
ment, for maximum yield of titanium. After loading the
required quantity of pickled solid magnesium into the cru-
cible, the lid of the retort was closed. After evacuating the
retort and backfilling with argon, an argon flow rate of
0.2 L/min into the retort was maintained. The magnesium
was heated to 800 °C under a slight positive pressure of
argon, and the TiCl4 feed was started at a low rate of 40 to
60 kg/h. After about 5 to 10 minutes, the TiCl4 feed rate
was increased to the predetermined value. Because of the
perforated bottom of the crucible, liquid magnesium also
filled the annular space between the crucible and the retort.
The liquid MgCl2 produced as a result of the reduction
reaction, which is denser than liquid magnesium, was tapped
from the retort several times during the experiment as per
a predetermined schedule. The first tapping was done after

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 35B, FEBRUARY 2004—65

03_01-52B-C.qxd 6/1/04 8:14 PM Page 66
feeding 2000 kg of TiCl4 into the reactor. Thereafter, tapping
was done after feeding of every additional 500 kg of TiCl4.
After each tapping, the level of the liquid-magnesium surface
fell by 125 to 185 mm. In spite of this, the mean level of
liquid magnesium gradually rose during the experimental
run, due to the accumulation of titanium sponge inside the
crucible.
Due to the high exothermicity of the reaction of the reduc-
tion of TiCl4 by magnesium, the temperature of the retort
wall increased. The retort-wall temperature was maintained
within the range of 830 °C to 880 °C by blowing air onto
the retort wall wherever its temperature reached 880 °C. The
pressure inside the retort was maintained within the range
of 1.1 to 1.25, throughout the experiment, with the help of
a bleeder valve on the retort lid. During the course of the
experiment, periodic bleed-off was observed. The process
was terminated when the frequency of bleed-offs suddenly
increased from once every few hours to once every
30 to 40 minutes. At the end of the experiment, final tap-
ping of the MgCl2 along with the unreacted liquid magnesium
was carried out, and the furnace was switched off and the
reactor cooled to room temperature.
Fig. 1—Schematic diagram of prototype reactor (capacity: 2000-kg Ti per
batch).
66—VOLUME 35B, FEBRUARY 2004
Three experiments were carried out at three different TiCl4
feed rates, namely, 120, 200, and 300 kg/hm2 of crucible
cross-sectional area. The highest feed rate of 300 kg/hm2
of crucible area, however, could not be maintained beyond
12 hours, after which the experiment was continued at a
reduced TiCl4 feed rate of 120 kg/h·m2.
In a separate experiment, temperatures inside the crucible
were measured at three different points along the axis, viz.,
near the initial liquid-magnesium surface and at 200 and
400 mm above this level. During this experiment, TiCl4 was
fed at a rate of 120 and 200 kg/hm2 of crucible area.
B. Studies in Experimental Reactors
The experimental crucible 1 was 1100 mm in internal
diameter, 25 mm in thickness, and 1000 mm high. Crucible
2 was 1305 mm in internal diameter, 12 mm in thickness,
and 625 mm high. These crucibles were placed inside the
retort of the Kroll reactor on supports, so that they were
located in the middle of the retort. The gap between the
retort and the crucible was 105 mm in the case of crucible
1 and 15 mm in the case of crucible 2. Both crucibles had
a closed bottom. Consequently, the liquid magnesium and
MgCl2 were contained entirely within the crucible, and the
annular space between the crucible and the retort was filled
with argon and not liquid magnesium, unlike in the proto-
type reactor.
Four thermowells were inserted through the lid of the retort
at different locations along the radius. Four chromel-alumel
thermocouples were inserted into each of the thermowells,
so that their ends were at different heights (Figure 2). This
enabled continuous measurement of temperatures at four
different levels at each of the four radial locations. In
crucible 2, all the four radial locations were within the
crucible, whereas in crucible 1, which was of a smaller
diameter, only three of the radial locations were inside the
crucible and the outermost location was in the annular space
between the crucible and the retort.
Fig. 2—Schematic diagram showing temperature measurement points in
the experimental crucibles (crucible 2 shown dotted).
METALLURGICAL AND MATERIALS TRANSACTIONS B
03_01-52B-C.qxd 6/1/04 8:14 PM Page 67
The experimental procedure using these crucibles was
similar to that used in the 2000 kg prototype reactor. After
loading the required weight of pickled magnesium into the
crucible (500 kg in crucible 1 and 300 kg in crucible 2),
the lid of the retort was closed, the retort was evacuated and
backfilled with argon, and argon flow into the retort was
started. The magnesium was heated to 800 °C, and the TiCl4
feed was started.
Two experiments were carried out in each crucible. In
each experiment, three different TiCl4 feed rates were used.
The TiCl4 feed rates used in crucible 1 were 60, 120, and
200 kg/hm2 of cross-sectional area of the crucible, and in
crucible 2, the feed rates were 120, 200, and 300 kg/hm2.
Reduction at each feed rate was carried out for 45 to 60
minutes. Between any two feed rates, the TiCl4 feed was
stopped and the reaction mass was soaked at 800 °C for
1 hour before starting the TiCl4 feed at the next-higher rate,
to avoid interference between temperature evolutions dur-
ing the two stages. The total TiCl4 feed was approximately
450 kg in crucible 1 and 750 kg in crucible 2. During
the entire experiment, the temperature of the retort was
maintained in the range of 800 °C to 830 °C by blowing air
whenever the temperature exceeded 830 °C.
III. RESULTS AND DISCUSSION
A. Reduction Experiments in the 2000 kg Prototype
Reactor
After the reduction experiment, when the retort was cooled
to room temperature and its lid was opened, copious fumes
evolved due to the reaction of residual titanium chlorides
with atmospheric air. The crucible was filled with titanium
sponge up to a height of about 150 to 200 mm below the
estimated final liquid-magnesium surface level (Figure 1).
Adherent to the crucible wall was a 150- to 200-mm-thick
layer of sponge up to the height of the final liquid-magnesium
surface. A thin deposit of titanium and magnesium powders
was found on the crucible wall just above the sponge mass.
Deposits of lower chlorides of titanium could be seen on the
top part of the crucible wall and on the retort lid. After
ejection of the Ti sponge cake from the crucible, using a
hydraulic press, a 10- to 20-mm-thick deposit of sponge
could be seen still adhering to the wall, between the initial
and final liquid-magnesium surface levels. There was no
Table I. Summary of Material Balance for Reduction Experiments in 2000 kg/Batch Prototype Reactor
Parameter 1 2
TiCl4 feed rate: actual, kg/h 138  10
specific, kg/hm2 120
Magnesium charge, kg pct excess 2880
(based on 8000-kg TiCl4) 43
Total TiCl4 fed, kg 8040
Reaction time, h 53
Titanium sponge obtained, kg 1990
TiCl4 utilization, pct 98
Mg utilization, pct
(for sponge formation) 72
METALLURGICAL AND MATERIALS TRANSACTIONS B
evidence of sponge sticking on the crucible wall either below
the initial liquid-magnesium surface level or above the final
liquid-magnesium surface level. These observations indicate
that titanium sponge formation occurs mainly on the cru-
cible wall, close to the liquid-magnesium surface. Another
notable feature was the absence of any particles of titanium
sponge in the retort below the perforated bottom plate of the
crucible or in the nozzle at the bottom of the retort, used for
tapping the molten MgCl2. The tapped MgCl2 also did not
contain any particles of titanium.
A summary of the material balance for the reduction experi-
ments at the three TiCl4 feed rates is presented in Table I.
The degrees of utilization of TiCl4 and magnesium were
determined from the weight of the titanium sponge produced.
The reduction process was terminated when the bleed-off
valve in the retort lid started releasing pressure at frequent
intervals, indicating rapid pressure buildup. A typical pressure
profile during a reduction experiment is shown in Figure 3.
The periodic pressure buildup is primarily due to the acc-
umulation of unutilized TiCl4 vapor. Since the maximum
possible increase in pressure inside the retort due to the argon
input (0.2 L/min) can only be around 0.02 atm/h, assuming
the average bulk gas temperature inside the retort to be
600 °C, this cannot be the cause of frequent bleed-offs toward
the end of the experiment. A rapid rise in reactor pressure
may be caused either by the accumulation of unutilized TiCl4
vapor due to a decrease in the rate of the reduction reaction,
or due to the occurrence of reactions leading to the formation
of a gaseous product such as TiCl3. During each bleed, a
maximum of about 0.90 kg of TiCl4 was bled. Therefore, its
effect on the material balance is negligible. In experiment 1
(TiCl4 feed rate of 120 kg/hm2 of crucible area), the bleed-
off started only after about 32 hours of reduction, at a freq-
uency of about once every 4 to 6 hours. After about 52 hours
of reduction, the bleed-off frequency suddenly increased to
once every 30 to 40 minutes, after which the process was
terminated. In experiment 2 (TiCl4 feed rate of 200 kg/hm2
of crucible area) bleed-off started right from the beginning
at a low frequency (once every 4 to 5 hours) and acceler-
ated to once every 30 to 40 minutes after 34 hours of
reduction. In experiment 3, the high TiCl4 feed rate of
300 kg/hm2 could be sustained only for about 12 hours,
because of the occurrence of frequent bleed-offs. The process
was subsequently continued at a lower TiCl4 feed rate of
120 kg/hm2 for the next 24 hours. The process was finally
Experiment
3
345  10 (for 12 h)
230  10 138 (for the remaining 24 h)
200 300 and 120
2950 2986
46 48
7900 7650
33 36
1890 1770
95 92
68 65
VOLUME 35B, FEBRUARY 2004—67
03_01-52B-C.qxd 6/1/04 8:14 PM Page 68
Fig. 3—Pressure inside the prototype reactor (experiment 2, TiCl4 feed rate 200 kg/hm2).
terminated when even this feed rate could not be sustained.
In this case, a total of only 7650 kg of TiCl4 could be fed
into the reactor.
It can be seen from Table I that the overall TiCl4 utilization
decreased from 98 pct at a feed rate of 120 kg/hm2 of cru-
cible area to 95 pct at a feed rate of 200 kg/hm2. In the third
experiment, in which the TiCl4 feed rate was 300 kg/hm2
during the first 12 hours, the overall TiCl4 utilization was even
lower at 92 pct, although the feed rate was decreased to just
120 kg/hm2 during the remaining 24 hours of operation.
Retort-Wall Temperature Profiles
Titanium forms three stable chlorides: TiCl4, TiCl3, and
TiCl2. The reduction of TiCl4 by magnesium can be repre-
sented as a stepwise reaction:
TiCl4 → TiCl3 → TiCl2 → Ti
Since all the three reactions are highly exothermic, meas-
urement of the retort-wall temperature was considered helpful
in determining the location of intense reduction reactions
taking place within the reactor. Five thermocouples, TR1
through TR5, were used to measure the temperatures of the
outer surface of the retort wall at intervals of above 690 mm
along its height (Figure 1). The lowest thermocouple, TR5,
was near the bottom of the retort, and was about 380 mm
below the perforated bottom plate of the crucible. The
thermocouple TR4 was about 310 mm above the perforated
68—VOLUME 35B, FEBRUARY 2004
bottom of the crucible. Thermocouple TR1 was at the top
of the uppermost zone of the furnace and about 450 mm
below the top of the crucible.
The retort-wall temperature was always maintained
between 830 °C and 880 °C. When the temperature in any
zone went up above 880 °C, air cooling was started in that
particular zone. When the temperature dropped below 830 °C,
the air cooling was stopped in that zone.
The estimated level of the initial liquid-magnesium sur-
face was between the thermocouples TR3 and TR4. The
mean level of the liquid-magnesium surface progressively
rose, although the actual level dropped by about 125 to
185 mm after each MgCl2 tap and then rose again due
to the accumulation of the reaction products. At the end of
the experiment, the estimated level of the liquid-magnesium
surface was close to the level of thermocouple TR2. (Liquid
levels could be estimated by considering entrapment of
liquids by 35 pct of sponge volume.)
The start of the reaction was characterized by a sharp
rise in the temperatures indicated by thermocouples TR3 and
TR4. As the reaction progressed, the high-temperature zone
progressively moved up. Gradually, the temperature measured
by thermocouple TR2 increased and went above the tempera-
ture of TR3 during later stages of the experiments. At this
stage, there was some increase in the temperature indicated
by thermocouple TR1 as well. The highest temperature was
always close to the estimated liquid-magnesium surface level,
METALLURGICAL AND MATERIALS TRANSACTIONS B
03_01-52B-C.qxd 6/1/04 8:14 PM Page 69
indicating that the exothermic heat is largely liberated close
to the gas/liquid interface. Temperatures much below the
liquid-magnesium surface level (at TR5 and, in the later
stages, also at TR4) remained low, indicating that no import-
ant exothermic reactions occurred below the liquid-magnesium
surface.
The general trend of variation of temperatures at all the
three TiCl4 feed rates was similar. However, at higher TiCl4
feed rates, there was a faster increase in temperature of the
retort wall, needing more frequent air blowing, indicative of
an increased rate of heat generation inside the reactor. With
increasing TiCl4 feed rates, there was a faster increase in
temperature of the retort wall, needing more frequent air
blowing, indicative of an increased rate of heat generation
inside the reactor. With increasing TiCl4 feed rate, there was
also a more rapid increase in the temperatures at the higher
levels (thermocouples TR2 and TR1), leading to a narrowing
of the difference between these temperatures and the tem-
perature of thermocouple TR3, when the estimated level of
the liquid-magnesium surface was still well below the level
of TR3. This was especially noticeable at the highest feed
rate of 300 kg/hm2 of crucible area. This may be an indi-
cation of the increased occurrence of gas-phase reactions at
higher TiCl4 feed rates.
Another feature was the higher temperatures recorded
by the thermocouples TR4 and TR5 in the experiments
with higher TiCl4 feed rates as compared to the values
at a TiCl 4 feed rate of 120 kg/hm2 of crucible area.
(Thermocouple TR5 and, at later stages, even TR4 were
below the level of the liquid-magnesium surface.) This
indicates either the occurrence of some reactions inside the
bath (such as the reduction of TiCl2 dissolved in MgCl2
droplets settling down) or the presence of a more energetic
flow of the liquid-magnesium bath leading to the down-
ward flow of hot magnesium liquid from the surface along
the crucible wall.
In a separate experiment in the 2000 kg prototype reactor,
temperatures were measured on the liquid-magnesium surface
at the center of the crucible. The temperature on the surface
of the liquid magnesium was substantially higher than the
retort-wall temperature, indicative of the release of exother-
mic heat of the reduction reaction here. The temperature
of the liquid-magnesium surface was higher at higher TiCl4
feed rates. For example, the temperatures were around
1020 °C and 1100 °C, respectively, at TiCl4 feed rates of
120 and 200 kg/hm2.
B. Temperature evolution in the experimental crucibles
Temperature evolution was studied at three different TiCl4
feed rates in the two experimental crucibles. The experiments
were repeated under identical conditions, and it was found
that the evolution of the temperature profile was reproducible.
Before the start of the introduction of TiCl4, all 16 thermo-
couples indicated temperatures of 780 °C to 810 °C, and
the thermocouple at level 1 (Figure 2) corresponded to the
initial level of the liquid-magnesium surface.
C. Crucible 1
The experiment started with a TiCl4 feed rate of 60 kg/hm2
of crucible area. Immediately, the temperatures at level 1,
METALLURGICAL AND MATERIALS TRANSACTIONS B
which corresponded to the initial liquid-magnesium level, rose
sharply, indicating that reactions occur mainly at the liquid-
magnesium surface. The temperatures at level 1 were the high-
est near the wall and near the center of the crucible (930 °C
to 940 °C), with a dip in the midradius position (900 °C).
There was a progressive increase in temperatures with time
at the other levels, which were all above the level of the liquid-
magnesium surface. At levels 2 through 4, the temperature
was always highest near the crucible wall and lowest near the
center. Figure 4(a) shows the temperature distribution at
various locations at the end of this stage of the experiment.
Before the start of the second stage of reaction with a feed
rate of 120 kg/hm2, the temperatures at all 16 locations were
in the range of 817 °C to 835 °C. As soon as the TiCl4 feed
was started, the temperatures at level 1 started increasing
rapidly, especially near the crucible wall and the center, and
reached values of over 1050 °C. In the midradius position,
the temperature was much lower at 900 °C to 925 °C. In this
stage also, the temperatures at the other levels gradually
increased with time. At the end of this stage, the temperatures
at levels 1 and 2 were comparable (Figure 4(b)), and the liquid-
magnesium surface was estimated to be close to level 2.
In the third stage, again, on starting the TiCl4 feed at
200 kg/hm2 of crucible area, the temperature at all levels
started increasing. But in this case, the temperatures were the
highest at level 2, particularly near the center and midradius
positions of the crucible (1100 °C to 1150 °C). The temper-
ature distribution at the end of this stage is given in Figure
4(c). The absence of high temperatures near the crucible wall
at level 2 may possibly be due to the growth of titanium
sponge on the wall at the liquid-magnesium surface, with
consequent shifting of the reaction zone inward. During this
stage, the temperatures at level 1 were relatively low. By this
time, the liquid-magnesium surface was well above level 1.
An attempt to continue the experiment with an increased
feed rate of 250 kg/hm2 resulted in increased crucible-wall
temperatures and frequent pressure buildup inside the reactor.
After the end of the experiment, titanium sponge could be
seen deposited on the crucible wall and on the thermowell
pipes. Fluffy deposits seen on the crucible rim and retort
wall were found to be of the lower chlorides of titanium.
D. Crucible 2
As mentioned earlier, crucible 2 was of a larger diameter
than crucible 1 and, consequently, the thermocouples at the
radial location D were also inside the crucible, unlike in
crucible 1. Experiments were conducted at TiCl4 feed rates
of 120, 200, and 300 kg/hm2 of crucible area. Before the
start of each stage of the experiment, the temperature inside
the crucible was around 820 °C near the crucible wall and
730 °C to 750 °C at the center.
On starting the experiment with a feed rate of 120 kg/hm2,
the temperature rise was most rapid at level 1, corresponding
to the initial liquid-magnesium surface level, indicating that
the reactions occur mainly on the surface of liquid magnesium.
The temperatures at this level were higher near the crucible
wall (locations D and C) and in the center (location A), with a
dip at an intermediate location (B), reaching values of 1000 °C
1040 °C, 970 °C to 980 °C, and 930 °C to 940 °C, respectively
(Figure 5(a)). The temperatures at level 2 rose gradually to
950 °C to 970 °C near the wall (location D) and 930 °C to
VOLUME 35B, FEBRUARY 2004—69
03_01-52B-C.qxd 6/1/04 8:14 PM Page 70
Fig. 4—(a) Measured temperature profiles in crucible 1, stage 1, 55 min
after the start (feed rate 60 kg/hm2). (b) Measured temperature profiles in
crucible 1, stage 2, 55 min after the start (feed rate 200 kg/hm2). (c) Mea-
sured temperature profiles in crucible 1, stage 3, 48 min after the start (feed
rate 200 kg/hm2).
940 °C at the center (location A), with a dip at the intermediate
location (B). Temperatures at level 3 rose more slowly and
did not show a dip at the intermediate location. Temperatures
at level 4 remained almost unchanged throughout.
During the second stage of the experiment (TiCl4 feed rate
of 200 kg/hm2), the temperatures were higher at location C
than near the wall and decreased gradually toward the center.
The temperatures were, in general, higher than in the first
stage. The highest temperatures were initially at level 2 and,
70—VOLUME 35B, FEBRUARY 2004
(a)
(b)
Fig. 5—(a) Measured temperature profiles in crucible 2, stage 1, 56 min
after the start (feed rate 120 kg/hm2). (b) Measured temperature profiles
in crucible 2, stage 2, 48 min after the start (feed rate 200 kg/hm2).
toward the end of this stage, the temperatures at levels 2 and
3 were comparable and level 1 had the lowest temperatures
(Figure 5(b)), indicating that the liquid-magnesium surface
was by then well above level 1 and was probably even slightly
above level 2.
In the third stage of the experiment (TiCl4 feed rate of
300 kg/hm2), the temperature at level 2 (except near the
crucible wall) and at level 3 rapidly rose to high values. At
the start of the third stage, the liquid-magnesium surface
was estimated to be between levels 2 and 3. The temper-
atures at level 2, position C and at level 3, position D reached
values as high as 1200 °C. Temperatures at other locations
at level 3 and at all locations at level 4 also increased. Subse-
quently, all the temperatures decreased gradually, with
continuous buildup of pressure in the reactor and frequent
bleeding, which is indicative of a rapid decrease in the
reaction rate. All through this stage, the temperatures at level
1 remained low, indicating that this was well below the level
at which reactions occurred.
At the end of the experiment, when the crucible was taken
out, a wide but thin annular layer of titanium sponge was
seen adhering to the crucible wall at the level corresponding
to the final liquid-magnesium surface level (Figure 6). Sponge
deposit was also seen on the thermowell pipes and the steel
METALLURGICAL AND MATERIALS TRANSACTIONS B
03_01-52B-C.qxd 6/1/04 8:14 PM Page 71
guide strip, indicating that the steel wall can act as a substrate
on which titanium sponge can grow preferentially.
E. Reaction Mechanism and Sponge Formation
The experiments carried out in the 2000 kg prototype
reactor and in the experimental crucibles have led to the fol-
lowing observations.
1. When the lid of the prototype reactor was opened after
the completion of the experiment, the titanium sponge
was found in the form of an aggregate builtup on the per-
forated bottom of the crucible and filled the crucible
almost up to the final liquid-magnesium surface level. In
addition, an annular deposit of titanium sponge growing
from the crucible wall toward the center was seen at the
final liquid-magnesium level. Sponge growth was also
seen on the lower ends of the thermowells, which were
below the final liquid-magnesium surface.
2. Although the bottom plate of the crucible had 40 to 50-mm
diameter holes in it, no sponge mass or particles were found
below the bottom plate, in the MgCl2 drained from the
bottom of the retort, or in the drain pipe used for this purpose.
3. There was no sponge growth on the wall of the crucible
above the final level of liquid magnesium or on the lid.
4. Small amounts of fluffy deposits of titanium and magnes-
ium powders and of lower chlorides of titanium could
be seen on the crucible wall above the final liquid-
magnesium level. These deposits were more noticeable in
high-TiCl4-feed-rate experiments.
5. After extraction of the sponge cake from the crucible by
pushing it out in a press, the surface of the crucible below
the initial liquid-magnesium level was seen to be smooth
and clean, with no sign of any sponge-deposit formation.
On the other hand, a thin irregular (discontinuous) layer of
sponge adherent to the crucible surface was seen between
the initial and final levels of the liquid-magnesium surface.
6. During the reduction process in the experimental crucibles,
the temperatures was high on the liquid-magnesium
surface. The temperature on the magnesium surface was
highest near the crucible wall (or just next to the sponge
deposit on the crucible wall at later periods of the experi-
ment) and at the center, with a dip at intermediate radial
Fig. 6—Reaction mass in crucible 2 at the end of experiment.
METALLURGICAL AND MATERIALS TRANSACTIONS B
locations. The temperatures on the liquid-magnesium
surface increased with increasing TiCl4 feed rate. The tem-
perature was as high as 1080 °C at a TiCl4 feed rate of
120 kg/hm2. At an intermediate location between the wall
and the center, the temperature remained relatively low
and constant (900 °C to 930 °C) through the experiment.
7. The temperature below the liquid-magnesium surface
decreased rapidly with increasing distance from the sur-
face. Similarly, the temperature in the gas phase above
the liquid-magnesium surface was low.
8. Frequent bleeds were seen toward the end of the process,
indicating rapid pressure buildup. At high TiCl4 feed rates,
the retort-wall temperature above the liquid-magnesium
surface and the gas temperatures were found to increase.
This was also accompanied by rapid pressure buildup
inside the reactor leading to frequent bleeds.
In the magnesiothermic reduction of titanium tetrachloride,
various reactions are possible between the compounds of
titanium and magnesium, as listed in Table II. Under the
conditions prevailing in the reactor, magnesium can be
present in both the liquid and the gas phases (boiling point
of 1110 °C), titanium can be present in the solid phase,
MgCl2 can be present as the liquid, TiCl3 can be present in
the gas phase and TiCl2 can be present as the solid or the
liquid (melting point 1030 °C). Magnesium monochloride
gas (MgCl) can be present only at very high temperatures.
MgCl2 dissolves TiCl2 and magnesium. The solubility of
magnesium in molten magnesium chloride is 0.25 to 0.4 pct
in the temperature range of 800 °C to 1200 °C.[13] TiCl2
has a large solubility in liquid MgCl2. For example, at
900 °C, about 40 pct TiCl2 is soluble in MgCl2.
The reaction TiCl4 (g)
2Mg (l)  Ti (s)
2 MgCl2 (l)
(reaction 1 in Table II) is highly improbable kinetically,
since it is a four-phase reaction and the four phases meet at
a point. If magnesium is dissolved in MgCl2, the reaction
becomes a three-phase reaction. Even then, it can only take
place along the line of three-phase contact and, therefore, it
is not kinetically probable. The reduction of TiCl4 with mag-
nesium in the gas phase to form titanium (reaction 7) is also
not possible, since it is a three-phase reaction. Therefore,
the reduction to titanium has to take place in stages through
two or more than two phase reactions.
The equilibrium compositions of the species in the Ti-Mg-
Cl system in the temperature range of 723 °C to 1223 °C
(1000 to 1500 K) were computed using high-temperature
phase-simulation software.[14] The computations were done
at different initial concentrations of TiCl4 and Mg and at
atmospheric pressure without involving solubilities of the
species. At the stoichiometric weight ratio (TiCl4/Mg) of 4:1,
it is found that the system contains four moles of Ti (s) and
8.2 moles of MgCl2 (l). However, at the conditions of mag-
nesium depletion represented by the ratio 8:1, the system
possesses significant concentrations of TiCl2 (g) and TiCl3 (g),
the proportions of which vary depending on the tempera-
ture. This indicates that when the magnesium surface is
heated to high temperature during the reduction, magnesium
vaporizes and makes the gas phase richer in Mg (g). If
the magnesium concentration in the gas phase increases to
the stoichiometric ratio, the reactions may end up in titanium
powder formation; otherwise, the system posses stable titan-
ium lower chlorides as the reaction products.
VOLUME 35B, FEBRUARY 2004—71
03_01-52B-C.qxd 6/1/04 8:14 PM Page 72

Table II. Possible Reactions in Magnesio-Thermic Reduction of TiCl4

Number of Phases in the Reaction

In the Case of When Magnesium
Individual Pure and TiCl2 Dissolve
Reaction Reaction Species in MgCl2
1 TiCl4 (g)
Mg (l)  Ti (s)
MgCl2 (l) 4 3
2 TiCl4 (g)
Mg (l)  TiCl3 (g)
MgCl2 (l) 3 2
3 TiCl4 (g)
Mg (l)  TiCl2 (l)
MgCl2 (l) 4 2
4 TiCl3 (g)
Mg (l)  Ti (s)
MgCl2 (l) 4 3
5 TiCl3 (g)
Mg (l)  TiCl2 (l)
MgCl2 (l) 4 2
6 TiCl2 (l)
Mg (l)  Ti (s)
MgCl2 (l) 4 2
7 TiCl4 (g)
Mg (g)  Ti (s)
MgCl2 (l) 3 3
8 TiCl4 (g)
Mg (g)  TiCl3 (g)
MgCl2 (l) 2 2
9 TiCl4 (g)
Mg (g)  TiCl2 (l)
MgCl2 (l) 3 2
10 TiCl3 (g)
Mg (g)  TiCl2 (l)
MgCl2 (l) 3 2
11 TiCl3 (g)
Mg (g)  Ti (s)
MgCl2 (l) 3 3
12 TiCl2 (l)
Mg (g)  Ti (s)
MgCl2 (l) 4 3
13 TiCl4 (g)
TiCl2 (l)  TiCl3(g) 2 2
14 TiCl4 (g)
Ti (s)  TiCl3 (g) 2 2
15 TiCl3 (g)
Ti (s)  TiCl2 (l) 3 3
16 TiCl4 (g)
Ti (s)  TiCl2 (l) 3 3

When the solubility of TiCl2 and Mg in MgCl2 is considered,

the reactions giving TiCl3 (reactions 2, 8, and 13) and the
reactions giving TiCl2 (reactions 3, 5, 9, and 10) become
probable from the kinetic point of view, as they involve only
two phases. Therefore, the major paths for titanium reduction
could be the following:
2 TiCl4 (g)
Mg (in MgCl2) (a)
[17]
 2 TiCl3 (g)
MgCl2 (l)
TiCl4/TiCl3 (in gas phase)
Mg (in MgCl2) or Mg (g)
[18]
 TiCl2 (in MgCl2)
MgCl2 (l)
TiCl2 (in MgCl2)
Mg (in MgCl2)
[19]
 Ti (s)
MgCl2 (l)
The sponge formation can then be explained as follows. (b)
As TiCl4 is fed into the reactor containing molten magnes-
ium, it vaporizes and is transported to the liquid-magnesium
surface. Reaction of TiCl4 (g) with magnesium liquid gives
rise to the formation of tiny droplets consisting of MgCl2
(reaction 2) or a solution of MgCl2/TiCl2 (reaction 3). Further
significant reduction of TiCl4 can only take place by the
dissolution of magnesium in the salt droplets and its trans-
port to the salt/gas interface and by reduction reaction 18
(Figure 7(a)). The reaction along the line of contact of the three
phases should be much less significant. The formation of titan- (c)
ium from TiCl2/MgCl2 salt does not need the presence of the
gas phase and can take place at any location where the supply Fig. 7—(a) through (c) Proposed reaction mechanism for sponge forma-
of magnesium can be ensured. At the liquid-magnesium/salt tion in Kroll reactor.
interface, the formation of titanium sponge again involves three
phase reactions. Kinetically, therefore, titanium forms when magnesium chloride/reactor wall, as proposed by Okabe
the MgCl2 droplet reaches a surface where the nucleation and Waseda,[15] according to which the physical contact of
and growth of titanium sponge is favored. Sponge formation magnesium and TiCl2 is not necessary.
proceeds by the dissolution of magnesium in the salt, its Since it was observed in the experiments that there were
diffusion through the salt, and the chemical reaction 19 at no sponge pieces below the perforated bottom plate of the
the crucible wall or the titanium surface (Figures 7(b) and reactor, which has holes of about 40 to 50 mm in size, it
(c)). This sponge-formation reaction can also take place by appears that the sponge grows to large lumps before it breaks
an electrochemical mechanism of charge transfer through off and settles on the perforated bottom plate. Since sponge

72—VOLUME 35B, FEBRUARY 2004 METALLURGICAL AND MATERIALS TRANSACTIONS B

03_01-52B-C.qxd 6/1/04 8:14 PM Page 73
lumps of 50 mm in size are not likely to form and stay on
the liquid-magnesium surface, sponge formation should be
taking place at the crucible inner wall.
Initially, TiCl4 is reduced to TiCl2 and MgCl2 at the liquid-
magnesium surface, forming tiny droplets, as explained earlier.
These droplets may be continuously swept toward the crucible
wall due to convection currents set up by the buoyancy and
surface-tension forces. These droplets can then be further
reduced to titanium at the crucible wall where sponge has
already formed. The reduction of TiCl4 to TiCl2 can also
continue to take place on the liquid-magnesium surface near
the wall/sponge deposit at the gas-droplet interface, which also
involves the release of exothermic heat. Thus, it is possible
that the occurrence of both the reactions (viz., reactions 18 and
(a)
(c)
Fig. 8—Schematic diagram of proposed titanium sponge block formation: (a) initial, (b) 25 pct reduction, (c) 75 pct reduction, and (d) final.
METALLURGICAL AND MATERIALS TRANSACTIONS B
19) can cause increased heat release near the wall/sponge
deposit. This can explain the observed high temperatures on
the magnesium surface near the crucible wall/sponge deposit.
The observed low magnesium surface temperatures at higher
feed rates can be explained by the fact that the reaction rates
are lowered (as discussed in the latter part of this discussion)
due to the reduced magnesium cross-sectional area caused by
sintering of sponge mass at the crucible wall/sponge deposit.
As the sponge layer at the crucible wall widens, the surface
area available for TiCl4 reduction progressively decreases.
This can result in decreased consumption of TiCl4 and pres-
sure buildup. On the other hand, pieces of sponge periodi-
cally break off and settle down, exposing a fresh surface of
magnesium (Figure 8). During the initial period of reaction,
(b)
(d)
VOLUME 35B, FEBRUARY 2004—73
 03_01-52B-C.qxd 6/1/04 8:14 PM Page 74
the break-off of pieces is delayed, leading to noticeable pres-
sure buildup and frequent bleed-offs. This may be followed
by a large piece becoming loose and settling down, which
could be caused by a lowering of the liquid level due to a
MgCl2 tap. The reaction rate may then remain high for some
time, before another buildup. This may explain the erratic
behavior observed in the reactors, where periods of relatively
constant pressure are interspersed with periods of frequent
bleed-offs.
Toward the end of the process, the level of accumulated
sponge fills the crucible up to the level of the liquid-
magnesium surface. The availability of liquid magnesium
for TiCl4 reduction, therefore, becomes seriously limited,
leading to frequent bleed-offs and forcing the termination
of the experiment. Since the titanium sponge is porous,
part of the magnesium is trapped in the pores and is not
available for reaction. This leads to the lower utilization of
magnesium, as generally observed.
It should be noted that at temperatures of 1100 °C to
1200 °C, as observed in the experiments at high feed rates,
the titanium sponge layer formed at the magnesium surface
may sinter, increasing its strength. Therefore, small pieces
which are left on the wall where layers of sponge break can
continue to sinter, becoming stronger. Slowly, therefore, a
strong layer of sponge can build up behind the advancing layer
of freshly formed sponge. Eventually, this strong layer, which
does not break, can cover a sufficient area to permanently
hamper the reaction rate. This may explain the inability to
maintain the reaction rate even at a feed rate of 120 kg/hm2,
after some period at a 300 kg/hm2 TiCl4 feed rate in exper-
iment 3 in the 2000 kg/batch reactor. The temperatures must
have been higher during the initial period of high TiCl4 feed
rate, resulting in a strong layer of titanium sponge being
formed, decreasing the surface area drastically.
One of the interesting features of the temperatures distrib-
ution at the liquid-magnesium surface is the low and rel-
atively steady value of temperature around the midradius
position during most of the experimental duration, in spite
of the temperatures at the wall and center increasing with
time. This cannot be explained only on the basis of excess
heat generation near the crucible wall due to sponge forma-
tion. A possible explanation is the flow of cold liquid from
the bulk of the magnesium bath toward the surface around
the midradius position. Such a flow can be caused by a
double-toroid flow pattern.
IV. CONCLUSIONS
Experiments were conducted in a prototype 2000 kg batch
reactor and in two smaller experimental crucibles to under-
stand the processes taking place inside a Kroll reactor. Based
on extensive measurements made during these experiments,
74—VOLUME 35B, FEBRUARY 2004
View publication stats
a mechanism for the formation of titanium sponge by the
magnesiothermic reduction of TiCl4 has been proposed.
TiCl4 vapor becomes reduced to titanium in two import-
ant stages. At the liquid-magnesium surface, TiCl4 becomes
reduced to give TiCl2 (l) and MgCl2 (l), which are miscible
in each other. The solubility of Mg in the chloride solution
permits this reaction to proceed at a reasonable rate. TiCl2
in the solution is reduced by dissolved magnesium in the
region where the liquid-magnesium surface meets the cru-
cible wall. Thin sheets of titanium sponge so formed can
grow into lumps and periodically break off and settle down
in the liquid magnesium. The reactions being exothermic,
excessive rates of TiCl4 feed rate can result in high tempera-
tures and magnesium evaporation leading to gas-phase
reduction, giving titanium powder deposits on the crucible
walls and frequent bleed-offs.
ACKNOWLEDGMENTS
The authors are thankful to the Defense Research and
Development Organization (DRDO), Department of Atomic
Energy (DAE), and Department of Science & Technology
(DST) for the financial support for this work.
REFERENCES
1. W.J. Kroll: Trans. Electrochem. Soc., 1940, vol. 78, pp. 35-47.
2. H. Kametani and Y. Kurihara: in Titanium 95 Science and Technology,
P.A. Blenkinsop, W.J. Evans, and H.M. Flower, eds., The Institute of
Materials, London, 1996, vol. 3, pp. 2602-09.
3. G.R.B. Elliot: JOM, 1998, vol. 50 (9), pp. 48-49.
4. H.Y. Sohn: JOM, 1998, vol. 50 (9), pp. 50-51.
5. T.N. Deura and K. Ono: Metall. Mater. Trans. B, 1999, vol. 30B,
pp. 403-10.
6. R.O. Suzuki, T.N. Harada, T. Matsunaga, T.N. Deura, and K. Ono:
Metall. Mater. Trans. B, 1999, vol. 30B, pp. 403-10.
7. F.S. Wartman, D.H. Baker, J.R. Nettle, and V.F. Homme: J. Elec-
trochem. Soc., 1954, vol. 101, pp. 507-13.
8. A.N. Petrunko, N.V. Galitsky, N.A. Pampooshko, S.I. Denisov, and
A.E. Andeev: in Titanium and Titanium Alloys—Scientific and Tech-
nological Aspects, J.C. Williams and A.E. Belov, eds., Plenum Press,
New York, NY, 1982, vol. 1, pp. 101-06.
9. F.F. Lukashenko, N.K. Zinovieva, V.P. Tereckin, and P. Feofanov:
Trans. Titani. Ego Splavy, SSSR, 1961, vol. 99 (6), pp. 14-20.
10. V.D. Savin: Izv Vyssh. ucheb Zaved., Tsvet Met., 1970, vol. 13 (5),
pp. 63-68.
11. S.V. Ogurtsov: in Titanium and Titanium Alloys—Scientific and Tech-
nological Aspects, J.C. Williams and A.E. Belov, eds., Plenum Press,
New York, NY, 1982, vol. 1, pp. 41-61.
12. V.A. Reznichenko: in Titanium and Titanium Alloys—Scientific and
Technological Aspects, J.C. Williams and A.E. Belov, eds., Plenum
Press, New York, NY, 1982, vol. 1, pp. 63-77.
13. V.A. Garmata: The Metallurgy of Titanium, Translation Division,
Wright Patterson Air Force Base, OH, 1970, pp. 250-86.
14. Astra.4/pc, Bauman Moscow State Technical University, Moscow, 1996.
15. H.T. Okabe and Y. Waseda: JOM, 1997, vol. 49 (6), pp. 28-32.
METALLURGICAL AND MATERIALS TRANSACTIONS B