Documentos de Académico
Documentos de Profesional
Documentos de Cultura
1973,23,865-870
1. Introdnction
The object of this study was to investigate the possibility of extracting titanium
dioxide (TiO,), via fused salt solvents, from two sources, viz. ilmenite (FeTi03) and
a complex titaniferous slag produced as a by-product of iron extraction from New
Zealand beach sands.
Studies on the solubility of TiOz in a variety of fused salts have established that
fused alkali metal borate melts' and cryoliteZare potentially useful solvents. Borate
melts are superior from the point of view of the generally greater solubility of TiO,
at a particular temperature. However, whereas TiO, is recrystallised from cryolite
solution, solutions of TiO, in fused borates yield on cooling either TiOz or complex
alkali metal titanates, or both.' The product depends on the Lux-Flood basicity of the
solvent, which in turn depends on the alkali metal cation, and on the mol ratio
MzO : Bz03(M = alkali metal) in the borate melt. In general terms, recrystallisation
of TiO, rather than crystallisation of a complex titanate is favoured in lithium borates
with a high proportion of B2O3.
In the present study, fused lithium diborate (Li,O. 2Bz0,) and lithium tetraborate
(Li,O. 4B203) have been used to dissolve ilmenite and slag. Ilmenite was also dissolved
in potassium tetraborate, and slag in sodium diborate, to examine the effect of chang-
ing the alkali metal cation. Phases crystallised from these solutions on slow cooling
have been separated from the borate matrices and (except in one case) identified.
2. Experimental
British Drug Houses AnalaR grade NazB4O7.10Hz0 and standard grade
Li,B,O,. 5Hz0 were used without further purification. LizO.4BZO3and Kz0.4Bz03
865
866 A. J. Ensteal and D.J. Udy
Compound W-%
CaO 11.0
SiOz 1.3
Ti02 30.5
A1203 20.0
MgO 13.2
v205 2.4
MnO
FeO - 3.3
10
Solidified mixtures were extracted with boiling 9 mol dm- sulphuric acid. The
residues, after filtration, were washed with water and dried in a vacuum oven prior to
chemical and X-ray powder diffraction analysis.
For chemical analysis, samples were brought into solution by fusion with a c.
100-fold excess of K,0.2Bz03 in a Pt+5% Au crucible, at 1273 K. The solidified
mass, cooled to room temperature, was dissolved in hot 0.5 mol dm-3 sulphuric acid.
Titanium(1v) and Fe(i1I) were analysed colorimetrically4using a Cecil CE303 spectro-
photometer, and lithium was determined by flame photometry with a Pye Unicam
SPWA spectrophotometer.
X-Ray powder diffraction patterns were obtained with a Guinier focussing camera
using CuK, radiation, and magnetic susceptibilities were determined by the Gouy
method using HgCo(SCN)4 as the calibrant. Densities were determined pycnometri-
cally with water as the immersant.
Extradon of Ti02 from slag 867
The products, denoted C1 and C2, crystallised from ilmenite +Liz0.2Bz03 and
slag+ Li,O .2Bz03 respectively, were apparently single homogeneous phases except
for a trace (probably of the order 1 to 2 weight %) of TiOz in the ilmenite product.
Interplanar spacings derived from X-ray powder difhaction patterns of C1 and C2 are
listed in Table 3. C1 and C2 are essentially isomorphous: their reflections are charac-
teristic of the pseudobrookite (Fe,TiOs) st ru c t ~re.~ The compounds FezMgTi3010
(Kennedyite),6 CoTi,O, and MgTizOS7 also have pseudobrookite structure.
The diffraction patterns of C1 and C2 were indexed on the basis of orthorhombic unit
cells, and the cell dimensions of both compounds were refined using the computer
program CELFIT:" Table 4 lists the refined parameters. Apart from two lines
(attributable to the most intense reflections of TiO,) in the diffraction pattern for the
ilmenite product, every clearly defined line in the patterns for C1 and C2 could be
indexed on the basis of a single set (for each compound) of lattice parameters. Within
the limits of detection of powder diffraction, therefore, the compounds were essentially
pure, except for a trace of TiOz mixed with one of them.
Qualitative analysis by emission spectrography of C1 and C2, indicated Li, Fe and
Ti as the only metallic elements present in significant quantity. Densities and quanti-
tative chemical analyses for the two compounds are given in Table 5 , together with
calculated analyses for LiFeZ.,Ti3O9 and LiZFe3Ti2.509.The agreement between
observed and calculated analyses is generally acceptable, except for lithium. In both
compounds Fe is believed to be present as F~(II), but the oxidation state is not known
with certainty. In view of this uncertainty, and the discrepanciesin the lithium analyses,
868 A. J. East& and D. J. Udy
the molecular formulae proposed for C1 and C2 must be regarded as tentative. The
compound crystallised from ilmenite+ K 2 0 .4B203has not yet been identified.
A notable property of the two compounds is their resistance to attack by strong
mineral acids including concentrated aqueous HF, in addition to boiling 9 mol dm-3
H2S04. The existence of these compounds has not been previously reported. In fact,
only two lithium ferrotitanates appear to have been reported in the literature, viz.
Li2FeTi049and LiFeTi0410*l 1 both of which are cubic.
remainder in a low spin state. This situation would give rise to a pefrof the order
3.5 pB [for Fe as Fe(n)]. We are unable at present to decide in favour of either of these
possibilities.
F ~ T ~ O J + L ~ Z O . ~product
B Z O J (Cl) 3.932 2 433.7b 32.95 31.22 0.41 3.50
LiFe2.sTi30g 3.938C 2 434.3 32.15' 33.09' 1.60" -
Slag+LizO .2BZO3(C2) 8.02 4 436.6b 36.74 25.80 0.47 3.54
Li2Fe3Tiz.sOg 8.18' 4 445.2 37.64' 26.W 3.12' -
* Assumed.
Calculated from the measured density and the assumed value of Z.
'Calculated.
4. Conclnsions
Extraction of Ti02from ilmenite can be accomplished in essentially a one-step process,
by dissolution of the mineral in alkali borate melts of low basicity. By manipulation
of the solvent basicity, it is feasible that reasonably high yields of Ti02 may be
attainable. However, in view of the variable composition of naturally occurring
ilmenites, extraction of Ti02 by this method may not be successful for samples from
other sources.
The compounds LiFe2.5Ti30gand Li2FeJTi2.509produced from ilmenite and
titaniferous slag respectively, have a rather simple formal relationship to ilmenite.
The ilmenite product is essentially a titanium-enriched ilmenite in which of the 6
Fe(I1) ions of 3 molecules of FeTi03 are replaced by 1 Li+ ion. The slag product is an
iron-enriched ilmenite in which & of the Ti(rv) ions are replaced by 2 Li+ ions.
Acknowledgements
We are indebted to New Zealand Steel Ltd. for a research fellowship, and to the New
Zealand Universities Research Grants Committee for equipment grants.
References
1. Easteal, A. J.; Udy, D. J. J. Mut. Sci. 1973, 8, 1171.
2. Madhavan, T. P.; Matiasovsky, K.; Danek, V. Chem. zvesti. 1971,25, 253.
3. New Zealand Steel Ltd. Private communication.
870 A. J. Eesdeal and D. J. Udy