Microstructural Studies and Carbochlorination Kinetics of

Xenotime Ore
MARCO A. GIMENES and HERENILTON P. OLIVEIRA

In this work, a systematic study of the reaction between xenotime, chlorine, and carbon has been
performed. The kinetics of carbochlorination of xenotime raw material (rare-earth elements in phos-
phate form, REPO4) has been studied over a temperature range from 600 C to 950 C. The influences
of temperature, partial pressure of chlorine, carbon content, and particle size on the rate of conversion
of xenotime to RECl3 were investigated. The results showed that the process follows the unreacted
coreshrinking model with formation of a porous product layer. Powder X-ray diffraction (XRD)
corroborated this model, showing clearly the patterns related to the formation of yttrium oxychloride
(YOCl), indicating that the reaction mechanism involves the presence of an intermediate step before
the formation of lanthanide chloride. A global rate equation which includes these parameters has
been developed:

9057
1 (1 X )1/3 kappt 2.8 104 d 00.4 PCl
0.9
2
exp t
T

I. INTRODUCTION medium.[3,4] Moreover, direct chlorination makes possible

RARE-EARTH elements (lanthanides) are more abun-
dant in the earths crust than their name suggests, and more
than 250 kinds of minerals exist, however, not as individual
compounds. Among the minerals, only a few are very
important for the rare-earth industry, such as, especially,
fluorocarbonates (bastnasite), phosphates (xenotime and
monazite), oxides (euxenite), and silicates (gadolinite).[1] In
addition, rare-earth minerals can be classified into two
groups on the basis of their composition: (1) bastnasite and
monazite, which have a high proportion of the cerium sub-
group of the lanthanide elements, and (2) xenotime, which
contains approximately 60 pct of the yttrium subgroup.[1] In
recent years, rare-earth elements have been used in high-
technology materials like permanent magnets, electronic
components, catalysts, phosphors, and hydrogen-storage
alloys. So, their demand has been increasing every year,
mainly due to the search for high-purity individual ele-
ments.[1,2] Wet decomposition of rare-earth ores (alkaline
and acid processes) into soluble form in water or acid
involves several operations and introduces impurities,
resulting in more laborious separation/purification opera-
tions. The chlorination process is a potential dry method of
production of rare-earth elements which allows the isolation
of metals from ores and concentrates, refining metals and
recovering metals from slags, besides having application in
advanced ceramics areas. Certain advantages in relation to
other decomposition processes have arisen: phosphorous
may be eliminated and the chlorides of rare earths can be
obtained in one operation, and impurities can be eliminated
with the formation of volatile chlorides; this procedure
makes possible the isolation of chlorides using a nonaqueous
MARCO A. GIMENES, Graduate Student, and HERENILTON P.
OLIVEIRA, Assistant Professor, are with the Department of Chemistry,
FFCLRP, University of Sao Paulo, CEP 14040-901, Ribeirao Preto, SP,
Brazil, herepo@ffclrp.usp.br.
Manuscript submitted November 27, 2000.
the mutual separation of rare-earth chloride mixtures using
chemical-vapor transport (CVT) mediated by the formation
of volatile complexes with KCl and AlCl3.[4,5] Although
there are many studies concerning the chlorination of rare-
earth elements with different purposes, few studies have been
devoted to the kinetics, mechanism, and structural changes in
the reaction of rare-earth minerals and chlorinating agents.
In this work, we focused our investigation on the reaction
between xenotime (REPO4) and chlorine in the presence of
carbon, as well as the microstructural changes occurring
during the reaction.
II. EXPERIMENTAL SECTION
A. Materials and Sample Preparation
The xenotime ore used in this work was ground and
classified into various size fractions from 500 to 62 m,
and it was not submitted to any previous treatment. The
composition of the xenotime obtained by energy-dispersive
X-ray, given as a pct of the rare-earth RE element, is 26.0
pct Y, 30.8 pct P, 24.6 pct Dy, 7.6 pct Er, and 11.0 pct
Yb. Powder X-ray diffraction (XRD) of the ore showed
the typical profile of yttrium orthophosphate (Figure 1(a)).
Agglomerates containing xenotime (particle diameters
between 62 and 45 m) and coal (particle diameters smaller
than 75 m and 97 pct purity) used in this work were
prepared by a pelletizing technique. A binding agent was
required, and an aqueous solution of sugar (1:1 mass/mass)
was used for this purpose. The mixture of xenotime and
coal (in several proportions) was placed inside a drum and
rotated at 100 rpm with a 45 deg angle to the horizontal.
The binding agent was introduced by spraying the sugar
solution until nearly spherical particles formed. The agglom-
erates (pellets) were dried at 80 C for about 24 hours in
air and classified by particle size. The carbon:xenotime ore
ratio was evaluated by heating the samples in air at 900 C
for 2 hours and weighing the residue, assuming that it was
only ore.

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 32B, DECEMBER 20011007


Fig. 1Powder X-ray diffraction patterns of (a) xenotime ore, (b) unreacted
pellets, and (c) pellets after 40 min of chlorination.
The chlorine gas and nitrogen gas used were 99.9 pct
grade. The chlorine gas was dried by passing it through a
column with CaCl2 before mixing it in a required proportion
with nitrogen gas.
B. Apparatus and Procedure
The experimental apparatus included a quartz tube
(24 mm i.d. 850 mm length) inside a horizontal tubular
electric furnace (35 mm i.d. 500 mm length) with a
programmable controller and a gas flow system. Calibrated
rotameters were used to meter the gas flow. The temperature
of the furnace was controlled within 2 C. The pellets
(0.200 g) were put in an alumina boat and then placed in
the quartz tube.
The furnace was heated while passing nitrogen gas
through the reactor to remove oxygen; when the required
temperature was achieved, chlorine or the N2/Cl2 mixture
was introduced. The product stream issuing from the reaction
system was scrubbed by passing it through a sodium hydrox-
ide solution (20 pct mass/volume), 4 mol L1 HCl, and water
before its exhaustion. After the reaction, the system was
purged with nitrogen until room temperature was reached.
After reaction, the residue in the alumina boat was leached
with 2 mol L1 HCl, filtered, rinsed with deionized water,
and dried at 80 C. Later, the excess carbon in the residue
was burnt off in a muffle furnace at 900 C, and the unreacted
xenotime ore was weighed to the obtain the degree of conver-
sion (X ). Pellets were prepared in a pelletizing machine
from Tecnal Industry (TECNALEquipamentos para
Laboratorio Ltda, Sao Paulo, Brazil). The powder X-ray
data were recorded on a SIEMENS D5005 diffractometer
(Siemens AG, Munich, FRG) using a graphite monochroma-
tor and Cu K emission line (1.541 A, 40 kV, and 40 mA).
The samples were placed on a glass plate and the data were
collected at room temperature over the range of 2 deg
2 65 deg, with a step of 0.020 deg. Scanning electron
microscopy (SEM) studies were done on a ZEISS (Carl
Zeiss, Mikroskopie, Gottingen, FRG) DSM 940 microscope,
operating at 20 kV. Specific surface-area (BET) data were
1008VOLUME 32B, DECEMBER 2001
Fig. 2Influence of the amount of carbon added (carbon:ore ratio) on the
fraction of xenotime ore chlorinated. Reactions performed under 1173 K,
1.0 L/min, PCl2 of 50 kPa, 40 min, and 125 to 250 m particle diameter.
obtained using a Quantachrome NOVA 1200 Gas Sorption
Analyzer (Quantachrome Corporation, Boynton Beach, FL).
III. RESULTS AND DISCUSSION
A. Chlorination of Carbon/Xenotime Pellets
1. Influence of carbon content
Analysis of the kinetic data with respect to the carbon
concentration was based on the carbon:ore ratio (mass/mass),
which covered a range between about 0.1 and 1.6. The effects
of the amount of carbon on the reacted fraction are shown
in Figure 2. Note that there is an increase of the fraction of
ore chlorinated as the carbon:ore ratio was increased from
0.1 to 0.6. However, at higher carbon:ore ratios, there was
a decrease in the fraction chlorinated, suggesting that the
carbon and xenotime were not intimately mixed. In fact,
when the pellets were prepared, it was necessary to add an
excess of binding agent in order to obtain particles with a
regular shape. In addition, this effect is reproducible and
may be attributed to the existence of an optimum ratio of
ore and carbon in the original mix, yielding an improved
contact resulting in a high chlorination rate.[6] Another point,
probably, is that after drying the pellets, the binder clogged
the pores or interfered with the chlorination by forming a
kind of film between the coal and ore agglomerates. Note,
if we assume that the global reaction could be written as
REPO4 3C 3 Cl2 RECl3 POCl3 3CO [1]
that the carbon:ore ratio (mass/mass) required by the reaction
stoichiometry (approximately 0.17) should give a yield of
RECl3 around 25 pct, as shown in Figure 2, so an excess
of carbon is necessary. This fact could be related to the lack
of contact between the ore and carbon particles, arising,
presumably, by segregation of the pellets during production.
The experiments to determine the effect of carbon content
on the rate constant (shown in Figure 2, insert) were per-
formed under the following conditions, which were kept
constant in all experiments: temperature of 1173 K, gas flow
rate of 1.0 L/min, chlorine partial pressure of 50 kPa, particle
METALLURGICAL AND MATERIALS TRANSACTIONS B

(a)
(b)
(c)
Fig. 3Micrographs of surface structure of pellets chlorinated (873 K, 1.0
L/min, PCl2 of 50 kPa, and 1.3 carbon:ore ratio) for (a) 20 min, (b) 40 min,
and (c) 40 min.
size range of 125 to 250 m, and reaction time of 30 minutes.
In addition, the results presented subsequently were based
on the data corresponding to a low content of carbon, in
order to avoid the effects of contact and segregation of
METALLURGICAL AND MATERIALS TRANSACTIONS B
Fig. 4Influence of specific surface area on the fraction of xenotime
ore chlorinated.
the particles, as discussed previously. The results shown in
Figure 2 indicate that the amount of carbon has a significant
effect on the chlorination rate. Considering these aspects,
the experiments to determine the kinetics parameters were
performed with an excess of carbon: a 1.3 carbon:ore ratio.
However, a more fundamental study of the reaction mecha-
nism for this system is under way, as well as of the effect
of a binding agent on the rate, including the morphologi-
cal aspects.
2. Microstructural studies
Studies were performed in order to evaluate the micro-
structural changes in carbon/xenotime agglomerates during
the chlorination reaction using SEM and powder XRD.
Figure 1(a) shows the typical powder XRD pattern of xeno-
time ore. Figure 1(b) shows the profile of an unreacted pellet,
where the main reflections of the yttrium phosphate could
be observed. Note that the coal and the residual sugar had
little influence on the diffractogram profile in relation to the
pure ore. A powder XRD pattern of the pellets immediately
after they had reacted with chlorine at 1173 K for 40 minutes,
with a gas flow rate of 1.0 L/min and without any later
treatment, is shown in Figure 1(c). This diffractogram shows
the peaks attributed to the yttrium oxychloride (YOCl)
phase: 13.6 deg/001, 26.9 deg/101, 31.9 deg/110, 35.8 deg/
102, 48.4 deg/201, (2/hkl). Other reflections suggested the
presence of another crystalline phase in a minor quantity,
which, unfortunately, we were not able to identify.
Changes in the particles morphology during the chlorina-
tion of pellets are shown in Figures 3(a) through (c). Figure
3(a) shows the surface of pellets before the reaction, in which
their morphology is coherent with the formation process, i.e.,
constituted by agglomerates. In addition, we observed that
the agglomerates were not homogeneous in shape and size
and had some cavities that, presumably, extended into the
interior of the agglomerate. A comparison with pellets before
the reaction shows that after the chlorination (Figure 3(b)),
the individual particles were smaller in size, became more
irregular, and developed cracks. We can note the formation
of holes related to the evolution of gaseous products (Figure
3(c)), indicating an increase of porosity which allows trans-
port of gaseous species and suggesting that the ore has
undergone a strong chemical attack by Cl2. Specific surface-
area data from initial pellets and after 20 and 40 minutes of
VOLUME 32B, DECEMBER 20011009
 (a)

(b)
Fig. 5Micrographs of surface of chlorinated pellets (1173 K, 1.0 L/min, PCl2 of 50 kPa, 1.3 carbon:ore ratio, and 40 min) with specific surface area of
(a) 0.23 m2g1 and (b) 1.3 m2g1.

chlorination (873 K, 1.0 L/min, PCl2 of 50 Kpa, and a 1.3

carbon:ore ratio) corroborated the increase of porosity: 0.40,
0.53, and 0.65 m2/g, respectively. In order to investigate the
influence of a specific surface area on the fraction of ore
chlorinated, we performed some experiments in which the
carbon:ore ratio (mass/mass) was kept constant (0.6). More-
over, the amount of binder agent was varied and the specific
surface-area values referred to the entire pellet. Figure 4
indicates that high values of the fraction of ore chlorinated
were found for samples with a high specific surface area.
We also verified microstructural changes with the presence
of holes for samples with different surface areas, as shown
in Figure 5. These previous results confirm the importance
of the preparation of pellets, since different pelletizing condi-
tions could cause different distances between the ore and
carbon surfaces, as well as variations in porosity which
would affect the rates of conversion.
3. Influence of gas flow rate Fig. 6Effect of gas flow on the chlorination of xenotime.
In order to minimize the reactant-gas starvation and
boundary-layer mass-transfer effects on the rate of reaction,
we determined the gas flow rate in which these effects could
be considered negligible. Figure 6 summarizes the results because the process is dependent on the rate at which the
plotted against the gas flow rate. Below 0.75 L/min gas flow gas molecules diffuse through the boundary layer sur-
values, the chlorination rate increased with the flow rate rounding the solid. For higher values, we did not observe

1010VOLUME 32B, DECEMBER 2001 METALLURGICAL AND MATERIALS TRANSACTIONS B

significant changes of the fraction of xenotime/carbon chlori-
nated, indicating that the lack of dependence on the gas flow
rate can rule out the diffusion-layer control. Thus, in order
to determine kinetics parameters, experiments were per-
formed at 1.0 L/min.
If we assume that there is a sharp interface between the
reactant and product solids and based on previous informa-
tion of structural and morphological changes, we can sup-
pose that the reaction follows a topochemical process with
the formation of a solid porous product.[7] Moreover, the rate
of a reaction that is chemically controlled can be described
according the following expression for spherical particles:[8]
1 (1 X )1/3 kapptt [2]
where
X fractional conversion (ratio of the weight of the (a)
reacted fraction to the initial weight),
t chlorination time (minutes), and
kappt overall rate constant.
In this case, we considered that kappt is composed of the
following parameters: the initial particle diameter (d0), par-
tial pressure of chlorine (PCl2 ), and activation energy (Ea ).
Thus a general form of the rate expression for kappt can be
written as

RT
Ea
kappt k0d b0PCl
c
2
exp [3]

where k0, b, c, and Ea are experimental constants.

4. Effect of partial pressure of reagent
Experiments at four different partial pressures of Cl2 in
N2 were carried out in order to study the effect of reagent
concentration on the rate, as shown in Figure 7(a). The
temperature (1173 K), gas flow rate (1.0 L/min), carbon:ore
ratio (1.3) and particle size (125 to 250 m) were kept
constant in all experiments. It was found that the partial
pressure of the reagent has a significant effect on the chlori-
nation rate. By plotting ln kapp (from the data of Figure 7)
vs ln PCl2, we determined the reaction order with respect to
Cl2 (c 0.9), as shown in Figure 7(b). In this case, the
reaction rate is almost directly proportional to the partial
pressure of chlorine gas.
5. Effect of particle size
The chlorination of the carbon:ore agglomerates curves
of different initial particle sizes varying from 75 to 125 m
to 500 to 600 m are shown in Figure 8(a). An increase of
the conversion was observed with the decrease of the particle
size. The plot of the apparent rate constant (ln kappt) against
the initial particle size (ln d0), shown in Figure 8(b), gave
a slope of 0.4 (b) suggesting a moderate dependence of
the reaction rate on the particle size. It is important to note
that all the data sets appear to have curvature. Although the
model does not fit the data well (the average correlation
coefficient is 0.943), we can assume that this approach does
not affect the qualitative discussion and conclusions. More
work is underway to clarify the apparent nonlinearity of
1 (1 X )1/3 vs t against the initial particle-size curves.
6. Effect of temperature
In order to study the effect of temperature on the chlorina-
tion rate, experiments were performed in isothermal condi-
tions in the temperature range from 873 to 1223 K, working
(b)
Fig. 7(a) Influence of partial pressure on the reaction rate of pellets with
Cl2 and (b) plot of ln kappt vs ln PCl2.
with a chlorine partial pressure of 50 kPa, particle size range
of 125 to 250 m, and gas flow rate of 1.0 L/min. The
fraction chlorinated vs time curves obtained at different tem-
peratures are shown in Figure 9(a). An Arrhenius plot, shown
in detail in Figure 9(b), indicated that the process did not
change its mechanism with the increase of temperature. The
apparent activation energy (Ea) of 75.3 kJ/mol is consistent
with a chemically controlled process.[8]
In the present set of experiments, considering the factors
investigated previously and combining the parameters, we
can express the global rate equation as follows:
1 (1 X )1/3 kapptt [4]
9057
kappt 2.8 104d 00.4PCl
0.9
2
exp [5]
T
where d0 is in microns, PCl2 is in kilo Pascals, T in Kelvin,
t is in minutes, and the constant k0 is in min1 m0.4 kPa0.9.
B. Reaction Mechanism of Xenotime/Carbon Pellets
with Cl2
There are few reports dealing with chlorination of rare-
earth compounds or with carbochlorination of their ores.[3,913]

METALLURGICAL AND MATERIALS TRANSACTIONS B VOLUME 32B, DECEMBER 20011011


(a)
(b)
Fig. 8(a) Influence of particle size on the reaction rate of pellets with
Cl2 and (b) plot of ln kappt vs ln d0.
Hartley and Wylie[3] reported the preparation of lanthanide
chlorides by reacting chlorine with monazite ore at tempera-
tures around 973 K, using carbon and carbon monoxide as
reducing agents. They also investigated the influence of parti-
cle size, gas flow rate, temperature, and carbon content on the
reaction rate and proposed a mechanism for the reaction. In
addition, these authors found the following rate-constant val-
ues: 0.0038 min1 (823 K), 0.0054 min1 (873 K), 0.0082
min1 (923 K), and 0.018 min1 (973 K). Their results are
quite different from our results (listed subsequently) and are
difficult to compare, since experimental conditions such as
the temperature range and pellet preparation procedure were
different.
T(K) 873 1073 1123 1173 1223
k(min1) 0.0004 0.0015 0.0061 0.0065 0.0070
Nevertheless, at first glance, their rate-constant values for
temperatures around 900 to 950 K fell in the same range,
although, for higher temperatures, they found a greater rate
constant. In another work, Hartley[9] suggested that the proc-
ess has three parallel steps (Eqs. [6] through [8]):
1012VOLUME 32B, DECEMBER 2001
(a)
(b)
Fig. 9(a) Effect of temperature on the reaction rate of pellets with Cl2
and (b) Arrhenius plot of rate constants.
REPO4 3C 3Cl2 RECl3 POCl3 3CO [6]
REPO4 4C 3Cl2 RECl3 PCl3 4CO [7]
REPO4 4C 3/2Cl2 RECl3 1/4P4 4CO [8]
Because of the great stability of xenotime ore against
chlorine without a reducing agent, we did not observe any
reaction for temperatures below 1400 K. If we consider that
the chlorination reaction was carried out in just one step, it
could be expressed as
REPO4 3C 3Cl2 RECl3 POCl3 3CO [9]
However, carbochlorination of the xenotime ore produced
yttrium oxychloride in an intermediary step, as shown by
XRD data and supported by the dependence of the reaction
rate on chlorine partial pressure. This step could be written as
2YPO4 2Cl2 2YOCl 1P2O5 1COCl2 [10]
If this step is rate determining, we could infer that the
reaction would occur at the surface of the carbon/ore agglom-
erate. This stage, speculating, could be an induction period
that corresponds to the formation and growth of YOCl phase
and the release of gaseous species, according to specific
surface-area and SEM data. Then, the reaction could be
METALLURGICAL AND MATERIALS TRANSACTIONS B
followed by a fast step related to the production of the
following products (Eq. [11]):
2YOCl 1C 2Cl2 2YCl3 1CO2 [11]
IV. CONCLUSIONS
The formation of YOCl was verified by XRD data. The
release of gaseous species corresponded to the increase of
the porosity of the pellets. The approximate proportionality
of the reaction rate to the partial pressure of chlorine gas
could be attributed to a chemically controlling step at the
surface of agglomerates. In addition, the overall process is
dependent on the initial particle size of the pellets. In the
conditions of this work, the apparent activation energy evi-
denced a chemically controlled process, and the reaction
between xenotime and chlorine follows a topochemical
mechanism. The effects of parameters studied in this system
could be expressed by a global rate expression, as follows:
9057
1 (1 X )1/3 kappt 2.8 104 d 00.4 PCl
0.9
2
exp t 241-46.
T 11. A.W. Henderson, S.L. May, and K.B. Higbie: Ind. Eng. Chem., 1958,
ACKNOWLEDGMENTS
The authors thank FAPESP (97/5779-1) for the finan-
cial support.
METALLURGICAL AND MATERIALS TRANSACTIONS B
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