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A fundamental study was conducted on a new process for producing vanadium (V) metal by the preform reduction process (PRP) based on
metallothermic reduction of vanadium pentoxide (V2 O5 ). Feed preforms with good mechanical strength even at elevated temperatures were
prepared by adding either CaO or MgO to V2 O5 feed powder because V2 O5 has a low melting point of 963 K; thus complex oxides (Cax Vy Oz ,
Mgx Vy Oz ) with high melting point at more than 1273 K were obtained. Reduction experiments were conducted by using either Ca or Mg vapor
at 1273 K for 6 h. V metal with a purity of more than 99% was successfully obtained when using Mg as a reductant. The feasibility of producing
V metal by the PRP will be discussed on the basis of fundamental experiments. [doi:10.2320/matertrans.M2010027]
(Received January 26, 2010; Accepted March 16, 2010; Published April 28, 2010)
Keywords: vanadium, reduction process, metallothermic reduction
-200
2 CaO
a + O2 = Ti
-1200 2C gO
O =2M -8
g + 2
2M
-1400
300 500 700 900 1100 1300 V
-10
0.5 1.0 1.5 2.0
Temperature, T / K
Reciprocal temperature, 1000 T -1 / K-1
Fig. 1 Ellingham diagram of some selected oxides.24)
Fig. 2 Vapor pressure of some selected elements as a function of reciprocal
temperature.24)
of this process are its effective control of purity and
morphology and its ability to flexibly scale the reduction
process. Contamination into the product can be easily atures at above melting point of V2 O5 . In order to solve this
avoided because the feed material in the self-supporting problem, V2 O5 was mixed with flux such as magnesium
preform does not have physical contact with the reaction oxide (MgO) or calcium oxide (CaO) and calcined to
container or the reductant. Highly flexible scalability is synthesize complex vanadium oxides. In Fig. 3, equilibrium
achieved as it is possible to simultaneously treat multiple phase diagrams of V2 O5 -MgO and V2 O5 -CaO quasi binary
pieces of preforms in a single reduction chamber. Further- systems are shown.26,27) It is expected that Mg2 V2 O7 and
more, the amount of molten salt (or flux) used in this process Ca2 V2 O7 maintain enough mechanical strength even at the
is smaller than that used in other processes. reduction temperature (Tred. ¼ 1273 K) because these com-
pounds have high melting points.
3. Thermodynamic Analysis
4. Experimental
A reductant suitable for the PRP and the optimum
reduction temperature were studied from the thermodynamic A flowchart of the production of V metal by the PRP
view-point. Calcium (Ca) or magnesium (Mg) was selected employed in this study is shown in Fig. 4. The PRP of V2 O5
as a suitable reductant for the V2 O5 reduction by considering using Ca or Mg vapor as a reductant consisted of four major
the Gibbs energies for the formation of oxides shown in steps: preform fabrication, calcination, reduction by reduc-
Fig. 1.24) For reducing V2 O5 by the PRP, the reductant metal tant vapor, and sample recovery by acid leaching. Firstly, the
has to be supplied in a vapor form. The vapor pressure of feed preform was fabricated from a slurry made of V2 O5
some selected elements as a function of temperature is powder (99.9% purity), CaO or MgO powder as a flux, and a
illustrated in Fig. 2.24) In order to have an efficient supply of a collodion solution (5 mass% nitrocellulose in ethanol and
reducing agent in the gas phase, it is desirable that the vapor ether) as a binder. The experimental conditions for preparing
pressure of the reducing agent is higher than 104 atm at the the feed preform using the Ca or Mg vapor were determined.
reduction temperature.25) In this study, 1273 K was selected The viscosity of the slurry was controlled by varying the
as the reduction temperature because their vapor pressures amount of the flux and binder. The cationic molar ratio,
are higher than 103 atm, which is high enough for sufficient RCat./V , listed in Table 1 is defined as RCat./V ¼ NCat. =NV ,
gas supply of the reducing agents. where NCat. and NV are the mole amounts of the cation in
The melting point of V2 O5 is 963 K, which is lower than the flux and V, respectively. Plate-shaped preforms with a
the reduction temperature. This low melting point causes thickness of 3–10 mm were prepared by casting the ob-
difficulty in the fabrication of a suitable feed preform for the tained slurry into a stainless steel mold. Secondly, the cast
PRP. The preforms fabricated only from V2 O5 and a binder preforms were heated and calcined in air for 2 h at calcined
cannot retain their mechanical shapes at elevated temper- temperatures.
1104 A. Miyauchi and T. H. Okabe
Feed preform
900
Mg3V2O8 + MgO
Mg2V2O7 + Mg3V2O8
Calcination
Mg2V2O7 + L
L 742°C
Reductant (Ca or Mg) Reduction
Mg2V2O7
MgV2O6
S L
Isopropanol, solution
Mg2V6O17 + L
Acetone
V2O5 + Mg2V6O17
Vacuum drying
500
0 20 40 60 80
V2O5 (MgO) V metal powder
MgO content, x MgO (mol%)
Fig. 4 Flowchart of the production of V metal by PRP in this study.
(b)
1400 1380°C
Figure 5(a) is a schematic illustration of the experimental
apparatus used for the calcination step. In this calcination
step, the binder and water in the feed preforms were removed,
Temperature, T’ / °C
800 778°C
thick-walled stainless steel vessel, and the reductant solid
Ca2V2O7
CaV2O6
Table 2 Experimental conditions for the reduction experiments, and representative analytical results of vanadium powder obtained after
reduction.
Thermocouple
5. Results and Discussion
(a) Melted preform (a) Exp. A-6 (Flux: MgO, aR Cat. / V = 1.5)
20 30 40 50 60 70 80
Angle, 2 θ (degree)
(d) Exp. A-8 (Flux: CaO, aR Cat. / V = 1.5)
Fig. 6 Photograph of the obtained samples in the alumina crucible after the
CaO JCPDS # 77-2010
Intensity, I (a.u.)
calcination experiment, (a) Exp. A-1 (Flux: MgO, RCat./V ¼ 1:0, Tcal. ¼
1173 K), (b) Exp. A-6 (Flux: MgO, RCat./V ¼ 1:5, Tcal. ¼ 873 ! 1173 K). Ca2V2O7 JCPDS # 72-2312
Intensity, I (a.u.)
30 40 50 60 70 80 30 40 50 60 70 80
Angle, 2 θ (degree) Angle, 2 θ (degree)
(d) After leaching (d) After leaching
30 40 50 60 70 80 30 40 50 60 70 80
Angle, 2 θ (degree) Angle, 2 θ (degree)
Fig. 8 Photograph and XRD pattern of the obtained sample (Exp. A-6-1), Fig. 9 Photograph and XRD pattern of the obtained sample (Exp. A-8-2),
(a) and (c): After the reduction process (R: Mg, Flux: MgO, Tred. ¼ (a) and (c): After the reduction process, (R: Ca, Flux: CaO, Tred. ¼ 1273 K,
1273 K, t00 red. ¼ 6 h), (b) and (d): After the leaching process (50% t00 red. ¼ 6 h), (b) and (d): After the leaching process (50% CH3 COOH aq.
CH3 COOH aq. (t00 lea. ¼ 12 h), 20% HCl aq. (t00 lea. ¼ 1 h)). (t00 lea. ¼ 12 h), 20% HCl aq. (t00 lea. ¼ 1 h)).
oxides (i.e. CaV2 O4 ) formed in the preform are chemically leaching. All of Ca2 V2 O7 was reduced to CaV2 O4 with the
stable and it becomes difficult to reduce by Mg vapor. The Ca vapor after reduction, that is, the oxidation state of V
details are unclear at this stage. changed from +v to +iii. However, metallic V was not
produced in the experimental conditions employed in this
5.3 Calciothermic reduction (Exp. A-6-2 and Exp. A- study. In the same way, V metal was not produced in Exp. A-
8-2, reductant: Ca) 6-2, in which MgO was used as a flux; rough black powder
Figure 9 presents the appearance and the representative obtained after leaching was identified as Mg1:5 VO4 (i.e.
XRD patterns of the samples obtained after each step in Mg3 V2 O8 ) by XRD analysis. The XRF analysis revealed the
Exp. A-8-2 with CaO flux. When Ca was employed as the purity of the obtained powder in the Exp. A-8-2 and Exp. A-
reductant, black solid in the form of flake was obtained after 6-2 to be higher than 85 mass% V. It is assumed that a part of
1108 A. Miyauchi and T. H. Okabe
the surface of the obtained powder was reduced to metallic V. also due to Mr. T. Oi for providing technical assistance in
At this stage, the reason for the unsuccessful results of producing the metal powder.
calciothermic reduction is not clear. The difference between
the results obtained using the Mg and Ca reductants are REFERENCES
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