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IN THE KROLL-PROCESS
Abstract
Behaviour of oxygen in Kroll-process was investigated at a plant scale with
the use of stable isotope 18o. It was shown that the percent of the oxygen,
from each source, passing into titanium sponge from oxygenous compounds is
approximately the following for each of raw materials: titanium tetrachlori-
de-BO, magnesium-30, circulating condensate-40. More than 13,73 of oxygen
entering reactor with all the sources is removed with discharged magnesium
chloride, mainly in the first half of the process. Absorption of water va-
pour and oxygen by the surface of titanium sponge while block dressing ·
leads to increase of titanium hardness by 2-10 HB.
Introduction ·
Oxygen is known to be one of the most harmful impurities decreasing the qua-
lity of titanium sponge and articles made of it. Interaction between titani-
um and oxygen or oxygenous impurities is determined by high chemical affi-
nity of titanium for oxygen .. Thermodynamic calculations show high probabili-
ty.of the reactions between titanium or magnesium oxides and titanium with
formation of solid solutions of oxygen in titanium, containing up to 0,1 3
of oxygen. According to material balance of main impurities in Kroll-proces~
30-40 3 of the oxygen sources are unaccounted for. We have investigated be-
haviour of ox1gen during all the stages of Kroll-process at a plant scale.
In order to differentiate the role of each source of oxygen stable isotope
18o in the form of gas or water was used.
Experimental Procedures
Oxygen isotope in the form of heavyoxygen water was introduced into titanium
tetrachloride and metallic magnesium by bubbling or dispersed inside the
reactor containing circulating condensate. To determine the extent of conta-
mination of titanium sponge by oxygen while processing sponge block into fi-
nal product we have investigated interaction of vaporous H2 18o or gaseous
180 with metallic titanium having oxidized ("passive") and unoxidized ("ac-
2
tive") surface. To control behaviour of oxygen, samples of raw titanium
tetrachloride and metallic magnesitim, titanium sponge, discharged magnesium
chloride and reaction mass were taken. Samples were analysed for total and
Tilanium '92
. Science and Technology
Edited by F.H. Fraes and I. Caplan
The Mine<als, Marais & Materials Sociely, 1993
2,423
stable isotope 180 content. From results obtained the quantities of absorbed
oxygen were calculated. The sensitivity of 18o analysis was 5•10-6 3.
Results
0xygen from Titanium Tetrachloride
Studies of behaviour of oxygenb_introduced with titanium tetrachloride, show
that an increased content of 1"0 has been observed in local samples from up-
per and lower parts of titanium spoqge block and the lowest content - in the
centre of the block (Figure 1,A). 160 content in discharged magnesium chlo-
ride is approximately invariant in first discharges and decreases sharply
after the eighth discharge (Figure 2).
(A)
2,0
0
i,O ~o to 15 20
DISCHARGE NlJw1BER
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The balance of 1Bo in reduction products shows that 'major part of oxygen
from titanium t~trachloride, contained in the form of ox~chloride; passes
into titanium sponge (Table I). Moreover up to 60 °/o of 1.°0 pass into the
central part of block and nearly 12 °lo - into garnissage. About 14 % of oxy-
gen is removed with discharging magnesium chloride. Some part of 1So passes
into metallic magnesium and magnesium chloride remaining in the reaction
mass and then passing to circulating condensate.
Table I Distribution .of 180 in the products of magnesiumthermic reduction
of titanium tetrachloride
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Table II Content of l80•105 %,in magnesium bath before and in the cource of
process
20 0,4 6, 1
50 0,4 4, 1
75 0,5 2,8
100 0,5 7,8
125 1' 1 11,8
Discussion
Perming magnesium chloride and structure of titanium sponge block play sig-
nificant role in distribution of 1 ~0 in reduction products. Oxide compounds
from raw metallic magnesium at the initial stages of the process react with
the first portions of titanium sponge and precipitate on the bottom (in the
form of ground film and first layer of bottom part) and on the walls (in the
2.426
form of garnis~e) of reactor. When next portions of titanium tetrachloride
are charged, the bottom depositions are stirred up because of the increased
temperature gradient and physical disturbances. As a result oxide compounds
are transported to the central zone. by circulating flows of melt, provoding
contamination of the central part of titanium sponge block. The major part
of oxide compounds from magnesium is removed with discharged salt at the
initial stages of the process. But then the forming block of titanium sponge
overlaps all the cross-section of the reactor and acts as a filter. From
this time 180 content in discharged magnesium chloride decreases sharply.
Oxygenous compounds continuously entering the reactor as a part of raw tita-
nium tetrachloride preferably contaminate the titanium sponge and partly '
pass into magnesium chloride and metallic magnesium. During the circulation
in reduction apparatus, magnesium chloride washs titanium sponge block, wets
oxide compounds and removes them from the central zone of reactor. So upper
part of the block and garnissage, in contact with surplus magnesium chloride
less than central part of the block, contain more oxygen. At the initial
stages of process oxygenous compounds, unabsorbed by titanium sponge, are
just completely removed from reactor with discharged salt. As mentioned
above, after eighth discharge forming block of titanium sponge overlaps all
the cross-section of the reactor and prevents removal of oxygenous compounds
with discharged magnesium chloride. As a result, lower layers of titanium
sponge block are contaminated with 180. So the main sources of oxygen conta-
mination of titanium s'ponge in Kroll-process are raw titanium tetrachloride
(up to 80 %of the 180 TiCl4 in the fonn of oxichloride pass into sponge)
and to a lesser extent-metallic magnesium and circulating condensate (from
30 to 40 %of oxide compounds pass into the sponge). Irrespective of source
of oxygenous impurities, their behaviour in the Kroll-process may be consi-
dered approximately identical. The positive role of magnesium chloride is
worthy of note, removing more than 15 %of oxygen, entering reactor from all
the sources. Contact of produced titanium sponge with humid air as well as
with oxygen of air while block dressing leads to absorption of both water
vapour and oxygen by sponge surface up to several molecular layers. As a re-
sult final titanium hardness may increase by 2-10 HB.
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