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Materials Transactions, Vol. 51, No. 6 (2010) pp.

1102 to 1108
#2010 The Japan Institute of Metals

Production of Metallic Vanadium by Preform Reduction Process


Akihiko Miyauchi1; * and Toru H. Okabe2
1
Department of Materials Engineering, Graduate School of Engineering, the University of Tokyo, Tokyo 113-8656, Japan
2
Institute of Industrial Science, the University of Tokyo, Tokyo 153-8505, Japan

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

1. Introduction (Al). In order to produce high-purity V metal, multiple


melting steps by using an electron beam melting process are
Vanadium (V) is a transition-metal element with an atomic necessary for removing the Al. For this reason, the ATR
number of 23. V metal is the 20th most abundant element process is not a suitable production process of high-purity V
among all elements in the earth’s crust. The abundance of V metal. In the past, some researchers attempted to develop
metal is 120 ppm in the earth’s crust, which is significantly an alternative to the ATR process for producing V metal.
larger than the well-used common metals such as nickel (Ni, Metallic V with more than 99% purity was first produced
84 ppm, 23rd rank) and copper (Cu, 60 ppm, 26th rank).1,2) through calciothermic reduction by Marden and Rich.11)
However, V metal belongs to a set of less common metals or They used a mixture of V2 O5 , Ca and CaCl2 at 1173–1223 K.
‘‘rare metals’’ since the production volume of V metal was McKechenie and Seybolt proposed another reaction based on
only 58 kt in 2007 and is far smaller as compared to that of calciothermic reduction with a small amount of flux such
common metals.3) The small production volume of V metal is as CaI2 .12) Gregory researched calciothermic reduction of
partly due to its low concentration in the ore and uneven V2 O3 .13) In order to eliminate oxygen contamination,
distribution of its minerals. The principal V metal minerals chloride metallurgy for producing high purity V metal was
such as titanomagnetite contain only 1–2 mass% of V2 O5 .4) investigated by Campbell et al.14) Preparation of high-purity
The majority of the mineral resources are distributed in three V by the Van Arkel-de Boer process (Iodide disproportio-
countries: China, Russia, and South Africa. naton process) was studied by Carlson et al.15,16) However, an
V metal and its alloys are mainly used as additive elements effective production process suitable for commercial mass
(alloying elements) or as catalysts. In Japan, more than 85% production has not been established at this stage. Therefore,
of V metal is used as an additive in steel products for the development of a simple and efficient production process
improving their tensile strength and heat resistance.5) Special of high-purity V metal is strongly required. In the recent
steel containing V metal is applied in bridges, industrial years, Suzuki et al. investigated electrochemical reduction of
tools, etc. In the field of chemical industries, V compounds V2 O5 or V2 O3 in molten CaCl2 for producing high purity V
are utilized as a desulfurization catalyst in sulfuric acid metal and its alloys,17–19) as well as calciothermic reduction
production processes. Furthermore, vanadium-titanium (V- of V2 O5 and TiO2 for producing V-Ti alloys.20) With these
Ti) alloys are now attracting considerable attention as new backgrounds, the present study aims to develop a new process
electrode materials in hydrogen storage batteries, because V for the effective production of V metal from its oxide by
has high hydrogen storage capacity at ambient temperature utilizing a simple metallothermic reduction.
and moderate pressure.6–8) Considering the expanding market
for hydrogen storage batteries, the demand for V-Ti alloys 2. Preform Reduction Process (PRP)
may be expected to increase in the future.
Currently, V feed for smelting V metal is produced in the As an effective production process of high-purity V metal
form of its oxide (V2 O5 ) as a byproduct of steel slag or as a from V2 O5 , we selected the preform reduction process
residue of oil, and these V2 O5 feeds are mostly used as a (PRP).21–23) Feed preforms are prepared by mixing a starting
starting material for V products. V metal is commercially material oxide feed, flux, and binder solution. After drying,
produced by the aluminothermic reduction (ATR) of the preforms have sufficient mechanical strength to stand
V2 O5 .9,10) Although this process is simple and economical, alone. By utilizing the features of the mechanical structure of
the product is not a high-purity V metal; it is a vanadium- the feed preforms, contamination from the reduction contain-
aluminum (V-Al) alloy containing 20 mass% of aluminum er can be prevented. In the PRP, the oxide in the preforms is
directly reduced to metal by reductant vapor. After reduction,
*Graduate Student, the University of Tokyo the produced metal is recovered by leaching. The advantages
Production of Metallic Vanadium by Preform Reduction Process 1103

Reduction temperature Temperature, T / K


Standard Gibbs energy of formation, ∆G°f / kJ mol -1

0 2000 1000 500

-200

Vapor pressure of element i, log pi / atm


P °Mg = 0.458 atm
at 1273 K
Fe 3O4
O2 = 1/2 -2
-400
3/2 Fe + P °Ca = 0.018 atm
/5 V 2O 5 at 1273 K
-600 + O2 = 2
4/5 V -4 Mg
Al
= TiO2
-800 Ti + O 2 Ca
l O3
= 2/3 A 2
O
l+ 2 Fe
-1000
4/3 A -6

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

Table 1 Experimental conditions for the preparation of feed preforms.

Mass of sample, wi /g Cationic Calcined Calcined


Exp. Note
no. Feed Flux Binder molar ratio, temperature, time, (Corresponding figures)
V2 O5 MgO CaO Collodion1 RCat./V 2 Tcal. /K t00 cal. /h

A-1 2.68 1.19 — 4.02 1.0 1173 2 Fig. 6(a)


A-2 2.68 1.79 — 4.56 1.5 1173 2
A-3 2.68 — 1.67 4.66 1.0 1173 2
A-4 2.68 — 2.48 5.25 1.5 1173 2
A-5 2.68 1.19 — 4.09 1.0 873 ! 1173 2
A-6 2.68 1.79 — 4.60 1.5 873 ! 1173 2 Fig. 6(b), Fig. 7(a) (c), Fig. 8
A-7 2.68 — 1.67 4.76 1.0 873 ! 1173 2
A-8 2.68 — 2.48 5.29 1.5 873 ! 1173 2 Fig. 7(b) (d), Fig. 9
1
Collodion solution (5 mass% nitrocellulose in ethanol and ether) was used.
2
RCat./V ¼ xCat. =xV , xcat. : mole amounts of cations in flux, xV : mole amounts of vanadium.

(a) Flux V2O5 Binder


1100 1074°C
Mg3(VO4)2 + L Mixing / casting
Reduction temp. in this study (1273 K)
Preform fabrication
980°C
Temperature, T’ / °C

Feed preform
900
Mg3V2O8 + MgO
Mg2V2O7 + Mg3V2O8

Calcination
Mg2V2O7 + L

L 742°C
Reductant (Ca or Mg) Reduction

700 V2O5 + L Reduced preform


670°C MgV2O6 + L
MgV2O6 + 50% CH3COOH aq.,
640°C
Mg2V2O7
20% HCl aq., Leaching
Mg3V2O8

604°C Distilled water, Waste


Mg2V6O17

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

1200 and an adequate amount of mechanical strength was further


L granted to the preforms. Then, the calcined preforms were
installed in a reaction vessel and reduced by the Ca or Mg
Reduction temp. in this study (1273 K) 1015°C vapor in the reduction step. Figure 5(b) is a schematic
1000
illustration of the experimental apparatus used for producing
V metal by the PRP. Four pieces of the calcined preforms
(4–6 g each) containing vanadium oxides were placed in a
Ca3V2O8

800 778°C
thick-walled stainless steel vessel, and the reductant solid
Ca2V2O7
CaV2O6

was placed at the bottom of the vessel. Two times excess


618°C stoichiometric amount of reductant (Ca or Mg) was used in
600 the reduction experiment (see RR values in Table 2). The
0 20 40 60
V2O5 (CaO) reductant solid was physically isolated from the feed pre-
CaO content, x CaO (mol%) form, and the reductant vapor was supplied to the feed
preform. Sponge titanium was also placed at the bottom of
Fig. 3 Equilibrium phase diagram of (a) V2 O5 -MgO quasi-binary sys- the vessel for gettering the nitrogen gas in the system.
tem,26) (b) V2 O5 -CaO quasi-binary system.27) After being sealed by tungsten inert gas (TIG) welding, the
Production of Metallic Vanadium by Preform Reduction Process 1105

Table 2 Experimental conditions for the reduction experiments, and representative analytical results of vanadium powder obtained after
reduction.

Composition of vanadium powder


Cationic Excess Mass of samples, wi /g
obtained after reduction, Ci 3 /mass%
Exp. molar reductant Reduction Reduction
no. Flux Reductant ratio, ratio, temperature, time, Calcined
Tred. /K t00 red. /h Reductant,
RCat./V 1 RR 2 preform, CV CMg CCa CFe CCr
wR /g
wcal. /g
A-6-1 MgO Mg 1.5 2.0 1273 6 3.937 3.345 99.7 0.2 — 0.01 0.03
A-6-2 MgO Ca 1.5 2.0 1273 6 3.670 4.906 86.0 2.4 10.6 0.3 0.5
A-8-1 CaO Mg 1.5 2.0 1273 6 3.474 2.573 85.4 — 13.0 0.2 0.4
A-8-2 CaO Ca 1.5 2.0 1273 6 3.604 3.976 79.0 — 20.4 0.1 0.4
1
RCat./V ¼ xCat. =xV , xcat. : mole amounts of cations in flux, xV : mole amounts of vanadium
2
Excess reductant ratio: RR ¼ wR =wR,theo. , wR,theo. : stoichiometic mass of reductant necessary for reduction.
3
Determined by XRF; value excludes carbon and gaseous elements.

(a) ature. It was then successively rinsed with distilled water,


alcohol, and acetone, followed by drying in vacuum. The
phases in the sample were identified using X-ray diffraction
Alumina tube
analysis (XRD; Rigaku, Rint 2000, Cu–K line). The
Ceramics chamber composition of the sample was determined by X-ray
fluorescence spectrometry (XRF; JEOL Ltd., JSX-3210).
Heating element

Thermocouple
5. Results and Discussion

Alumina crucible 5.1 Calcination process


The plate-shaped preform was fabricated by casting feed
Feed preform
slurry prepared by mixing V2 O5 , flux, and the collodion
solution. The size of the preform was 50  20  4 mm, and
it was beige in color. Figure 6 shows representative photo-
(b)
graphs of the obtained samples after calcination experiment.
TIG weld As shown in Fig. 6(a), samples (Exp. A-1-Exp. A-4) did not
sustain their original shapes, after the calcination process at a
Stainless steel cover
constant temperature of 1173 K for 2 h because of melting
Stainless steel V2 O5 in the feed preforms immediately after starting
reaction vessel calcination procedure. Samples with a cationic molar ratio
Feed preform of RCat./V ¼ 1:5 (Exp. A-6 and Exp. A-8) maintained their
(V2O5 + flux) original shape (see Fig. 6(b)), after the calcination step at
temperatures ranging from 873 K to 1173 K in 2 h. In
Stainless steel plate contrast, other samples with RCat./V ¼ 1:0 (Exp. A-5 and
Reductant (Ca or Mg) Exp. A-7) did not retain their original shapes since they lost
their mechanical strengths due to the melting of V2 O5 .
Ti sponge getter
The preforms which retained their shapes were successfully
produced in the calcination process by adjusting both the
Fig. 5 Schematic illustration of the experimental setup for (a) the
calcination experiment, (b) the reduction experiment. amount of flux and the calcination temperature. Figure 7
presents the appearance and X-ray diffraction patterns of
the samples (Exp. A-6 and Exp. A-8) obtained after the
steel reaction vessel was then heated in an electric furnace calcination process. The shape and color of the preform were
maintained at a constant temperature of 1273 K for 6 h; the retained after performing calcination at temperatures rising
preforms reacted with the reductant vapor. from 873 K to 1173 K in 2 h. By the reaction between V2 O5
After 6 h of reaction, the reaction vessel was removed from and the flux, Mg2 V2 O7 or Ca2 V2 O7 were formed in the
the furnace and was quenched in water. Finally, the preforms obtained preforms. Although the melting point of Mg2 V2 O7
in the container were mechanically recovered at room is slightly lower than 1273 K (see Fig. 3), the preforms
temperature by opening the sealed vessel with a lathe. The demonstrated sufficient mechanical strength even at elevated
product in the preforms obtained after the reduction experi- temperatures. This is probably because MgO and Mg3 V2 O8
ment was recovered by leaching the preforms with an acid, in the preforms contribute to maintaining the shape of
i.e. by dissolving the reaction product (CaO/MgO), flux, preforms, and Mg2 V2 O7 is reduced to V metal or suboxides
and excess reductant in an acetic acid solution. The obtained before melting the parts of preforms. The detail reason is
product was rinsed with hydrochloric acid at room temper- under investigation.
1106 A. Miyauchi and T. H. Okabe

(a) Melted preform (a) Exp. A-6 (Flux: MgO, aR Cat. / V = 1.5)

(b) Exp. A-8 (Flux: CaO, aR Cat. / V = 1.5)

(b) Solid preform

(c) Exp. A-6 (Flux: MgO, aR Cat. / V = 1.5)


MgO JCPDS # 77-2364
Intensity, I (a.u.)

Mg2V2O7 JCPDS # 70-1163

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

5.2 Magnesiothermic reduction (Exp. A-6-1 and Exp. A-


8-1, reductant: Mg)
Figure 8 illustrates the appearance and the representative
XRD patterns of the samples with MgO flux obtained after 20 30 40 50 60 70 80
Angle, 2 θ (degree)
each step in Exp. A-6-1, and the experimental conditions for
reduction experiments are presented in Table 2. The color Fig. 7 The obtained sample after the calcination process. (a RCat./V ¼
of the preform changed to a jet-black color after the PRP xCat. =xV , xcat. : mole amounts of cations in flux, xV : mole amounts of
by Mg vapor at 1273 K for 6 h (Fig. 8(a)), and the shape of vanadium.) (a) Photograph of the preform (Exp. A-6, Flux: MgO,
RCat./V ¼ 1:5, Tcal. ¼ 873 ! 1173 K), (b) Photograph of the preform
the preform was slightly deformed. However, it was easy to
(Exp. A-8, Flux: CaO, RCat./V ¼ 1:5, Tcal. ¼ 873 ! 1173 K), (c) X-ray
recover the preform from the reaction vessel because it was diffraction pattern of the sample (Exp. A-6), (d) X-ray diffraction pattern
physically isolated from the vessel even after reduction. of the sample (Exp. A-8).
These results indicate that this PRP is suitable for avoiding
contamination from the reaction vessel. During the leaching
step in the acetic acid solution, the original shape of the after reduction as well as of other samples is listed in Table 2.
preform was lost and a powder with a grayish black color The XRF analysis revealed the purity of the obtained
was obtained without pulverizing the reduced preform vanadium powder to be 99.7 mass% V, 0.2 mass% Mg, and
(Fig. 8(b)). Figure 8(c) presents an XRD pattern of the 0.03 mass% Cr (Exp. A-6-1). In contrast, the preform with
preform after reduction at 1273 K for 6 h. All the complex CaO flux (Exp. A-8-1) was not completely reduced to V
oxides were reduced to V metal by the Mg vapor. The metal. The XRD analysis revealed that the black powder
morphology of the sample was sponge like metal powder. A obtained after leaching process consisted of V metal and
summary of the analytical results of the obtained V powder CaV2 O4 . This is probably because the calcium complex
Production of Metallic Vanadium by Preform Reduction Process 1107

(a) After reduction (a) After reduction

(b) After leaching (b) After leaching

(c) After reduction (c) After reduction

V : JCPDS # 22-1058 CaO JCPDS # 77-2010


Intensity, I (a.u.)

Intensity, I (a.u.)

MgO : JCPDS # 77-2364 CaV2O4 JCPDS # 74-1359

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

V : JCPDS # 22-1058 CaV2O4 JCPDS # 74-1359


Intensity, I (a.u.)
Intensity, I (a.u.)

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
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Yamaguchi, Y. Mitsuda, and K. Morita of The University 24) I. Barin: Thermochemical Data of Pure Substances, 3rd ed., (VCH
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Catalyst Cycle Co. Ltd. for providing valuable technical 26) R. C. Kerby and J. R. Wilson: Can. J. Chem. 51 (1973) 1032–1040.
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and Mr. K. Yanada for their useful discussions. Thanks are 21–28.

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