Metallurgist, Vol. 44, Nos.

7-8, 2000

CHEMICAL PRINCIPLES OF A TECHNOLOGY

FOR M A K I N G PURE VANADIUM PENTOXIDE

V. A. Kozlov and A. E. Demidov

The chemistry of vanadium and the technology for making it have not progressed to their present state without errors
and missteps, which have alternated with surprising discoveries of lasting importance. One of the main achievements has been
the development of the classical method of producing pure vanadium oxide, which is based on the reaction of oxides of vana-
dium with alkali metals to form vanadates of sodium or calcium, crystallization of a complex salt from solution via conversion
or an exchange reaction involving the exchange of an alkali metal for an ammonium group in low-solubility (at room tempera-
ture) ammonium vanadates, and thermal decomposition of the vanadates to pure vanadium oxide. The equations describing the
chemical reactions in the classical crystallization-based technology for producing vanadium oxide are shown below:
Dissolution:

VO 3 + Na + ~ NaVO3aq;

Oxidation:

2NaVO3a q + (NH4)2SO4 ---->,,[,2NH4VO3 + Na2SO4;

Decomposition:

2NH4VO 3 + V205 + 2NH 3 + H20.

The technology was developed for the small-scale production of vanadium oxide from rich concentrates containing more
than 30% V205 (such as camotites, commercial vanadium oxide, and the converter slags produced at factories in South Africa).
As the scale of production grew, certain unforeseen problems arose with the original technology in connection with the
composition of the raw material and use of the waste water from the process. A new technology was developed to process prod-
ucts with a lower concentration of vanadium. For example, acidic vanadium-bearing converter slags are now processed by
so-called sylvinite, soda, sulfate, and nitrate variants of a technology based on hydrolysis. The basic chemical equations of the
reactions which occur in the processing of such slags with a nitriding roasting are as follows:
Roasting:

KCI~
NaC1 C12
FeO. V203 + 02 + Na2CO 3 ~ 2NaVO 3 + CO 2 + cr - Fe203 ;

NO x

Leaching:

NaVO 3 + aq = NaVO3aq;

Institute of Metallurgy and Concentration of the Republic of Kazakhstan (Almaty, Kazakhstan) and the Chusovoi
Metallurgical Plant. Translated from Metallurg, No. 8, pp. 52-53, August, 2000

428 0026-0894/00/0708-0428525.00 9 Kluwer Academic/Plenum Publishers

 TABLE 1. Composition of Titanomagnetite Ores Used by the World's Leading Producers of
Vanadium, % (by mass)

Components S. Africa China Finland Canada New Zealand Russia

Fe 50.0-57.0 30.0-35.0 35.0 40.0 58.0 59.0

'rio 2 11.0-20.0 10.0-12.0 15.0 35.0 8.0 2.3
v205 1.5-2.0 0.3-0.6 0.35 0.3 0.6 0.6
sio 2 2.0-3.0 20.0-30.0 19.0 4.3 4.5 3.6
A1203 10.0-20.0 10.0 3.5 5.5 2.0
MnO 0.1 1.2 0.6 0.2
Cr203 0.1 0.1 0,01 0.1

TABLE 2. Composition of Vanadium-Bearing Converter Slag Used by the World's Leading Producers of
Vanadium, % (by mass)

Working components Neutral components Molar ratio

Recommended
Country
processing methods
V205 MnO CaO FeO SiO2 TiO2 Cr203 MgO P205 Mn/V MnCa]V
Russia:
Nizlmiy Tagil combine 18.65 8 . 9 0 3.60 38.00 17.60 7 . 7 0 2 . 4 0 2.60 0.02 0.63 1.08 Manganese
Chusovoi plant 14.35 8 . 5 0 2.20 37.00 18.30 8 . 0 0 6 . 9 0 0.70 0.02 0.77 1.15 Manganese
South Africa 23.56, 3 . 5 0 1.50 33.80 17.10 3 . 7 5 5 . 7 5 2.38 0.05 0.20 0.35 Sodium
Manganese
New Zealand 15.48 14.70 1.13 30.30 20.30 15.00 0 . 8 4 0.75 0.02 1.25 1.30 Manganese

Crystallization:

NH4C1 ~ NaC1
NaVO3aq + (NH 4)SO 4 ~ ,l. NH4VO 3 + NaSO 4 ;
NH4NO3/./at AMV NaNO 3

Recrystallization: dissolution of sediment composed of ammonium metavanadate (AMV) in H20 with allowance for
the temperature coefficient of solubility, filtration and cooling of the hot AMV solutions.
Thermal decomposition of AMV in air at 550~

2NH4VO 3 ~ V203 + H20.

The classical hydrolysis-based technology is based on the reaction of oxides of vanadium with salts of sodium and man-
ganese during roasting, two-stage leaching in water and sulfuric acid, mixing of the solutions, hydrolytic separation of vanadi-
um oxide as a precipitate (AMV), and melting of the vanadium oxide to obtain the commercial product.
In the final analysis, the production of a unit of vanadium oxide entails an increase in the volume of waste water that
is formed and the complexity of its chemical composition, along with a sharp deterioration in the quality of the finished prod-
uct. That product is suitable only for use in the production of low-grade ferrovandium and serves as the raw material for the
classical crystallization-based variant of the given technology.
All of the technical improvements that have been made to the classical hydrolysis-based technology in recent years
have been minor. Neither Western nor Russian science has devised a cost-effective solution to the problem of utilizing the waste
water obtained in the classical crystallization- and hydrolysis-based technologies for producing vanadium oxide.

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 Most of the research scientists and production-process engineers working on the problem have not yet been able to
divorce themselves from the narrow conceptual framework of the classical crystallization-based technology for making pure
vanadium oxide. This mindset has become the main roadblock to the development of an economical and environmentally clean
production process. The existing technology is being closely re-examined in light of this and the fact that there is currently no
proven chemical method of processing complex vanadium-bearing converter slags formed in the pyrometallurgical processing
of concentrates obtained from low-vanadium titanomagnetite ores (the reserves of which are enormous).
Tables 1 and 2 show the chemical composition of crude titanomagnetite ores and the vanadium-bearing converter slags
formed at factories in the leading vanadium-producing nations.
Shown below are the chemical principles behind the classical hydrolysis-based technology for producing commercial
vanadium oxide from converter slags, which involves a nitriding roasting and is carried out in the sylvinite variant (developed
by M. N. Sobolev) and the soda variant (developed by S. A. Amirova):
Roasting with 10% (mass) NaCI or 8-10% (mass) Na2CO 3 at 750~

FeO.V203+11~O2+ 2NaC1 - + 2 N a V O 2 + C12 +l/22ct-Fe203,

(Na2CO 3) (CO 2)

FeO. V203 + 1~ 02 + Mn203 ---) Mn2VO 7 + ~ o~- Fe203 ;

Leaching:

NaVO 3 + H20 = NaVO3aq,

Mn2V207 + 2H2SO4 pH 2.5 ) H4V207 + 2MnSO4 '

Mn2V207 +3H2SO 4 pH < 1.0 )(VO2)2SO4 + 2 M n S O 4 + 3 H 2 0 ;

Precipitation:

NaVO 3 + H4V207 H2SO4 > .~ VO(OH)3 + Na2SO 4 ,

NaVO 3 + (VO2)2SO 4 --) ,[,VO(OH)3 + Na2SO4;

Refining:

VO(OH) 3 1200~ ) V205m 1 + H 2 0 .

All of the above-examined variants of the classical hydrolysis-based technology for making commercial vanadium
oxide are inefficient when used in processing slags of variable chemical and phase composition. Meanwhile, waste-water recy-
cling has become even more of a problem and is augmented by the equally complex problem of cleaning the waste gases - chlo-
rine, sulfur anhydride, and oxides of nitrogen.
The next important advance in the processing of vanadium-bearing converter slags was the replacement of the use of
reactive additives by oxidation roasting (proposed by N. P. Slotvinskii-Sidak). The replacement of sodium by calcium and the
introduction of two-stage leaching with sulfuric acid (proposed by S. D. Grekov) has not only improved the quality and yield of
the finished product in the hydrolysis-based technology, but it has also partially solved the problem of having a closed water-cir-
culation system. This lime-hydrolysis-based technology includes roasting with limestone at 850~ leaching with acid (anion-
ic at pH 2.5 and cationic at pH < 0.5), mixing, hydrolysis at 95~ and refining. The chemical principles behind the technolo-
gy are presented below:
Roasting:

FeO. V203 + 02 + CaCO 3 --) Ca2V203 + CO 2 + ~ o~- Fe203 ;

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 Leaching:

Ca2V207+H2SO 4 pH2.5 >H4V207+,~CaSO4_ anionic,

Ca2V207+H2SO 4 pH<0.5 ,~(VO2)2SO4+CaSO4_ cationic;

Mixing and hydrolysis:

H4V207 + (VO2SO 4) Ca(OH)2 ~ ~, VO2(OH)+ ,~ CaSO 4 ;

pH 1.5

Refining:
1200~
VO(OH) 3 ~V205comm + H 2 0 .

This technology has made the waste-water problem less acute. However, manganese is an undesirable impurity in the
solutions obtained from leaching the residue formed in the hydrolytic deposition of vanadium. The manganese content of the
finished product is limited by the specifications, The manganese concentration of the solution is reduced when the charge used
for roasting contains an excess of calcium oxide - at high temperatures, calcium displaces manganese from vanadates. Nearly
all of the calcium is bound and forms gypsum during leaching with sulfuric acid.
Unfortunately, the leading Russian specialists have not given enough importance to the role played by manganese in
the technologies used to recover vanadium. A sorption-crystallization technology that employs manganese and can be used to
obtain vanadium oxide from converter slags under the conditions which exist at Russian factories was developed in 1976 (by
V. A. Kozlov). Its chemical principles are as follows:
Sintering:

FeO.V203 + ~ - F e 2 0 3 . 450~ >Fe304 +V203,

V203 + 2MnO 2 850~ >Mn2V207 ,

2Fe304 +~2202 85~176 >3(ot_Fe203);

Leaching:

Mn2V207 +H2SO4 pH 2.0-2.5 )H2V207a q + MnSO4aq +MnSO4 -anionic,

Mn2V207 + H2SO 4 . pH 0.370.5 >(VO2)2SO4aq + MnSO4a q _ cationic;

Sorption:

(R3NH)2SO4org + 2H4V207a q --> 2(R3NH)H3V207org + H2SO4;

2R3NH4V207org +H2SO 4 1%H2SO4 >MnSO4aq, Fe2(SO4)3a q - washing of impurities from the anion exchanger;
Desorption (regeneration of the anion exchanger):

R3NH 4 . V207org + NH4NO3aq pH 7.5 >NH4H3V207a q + RNHNO3aq ;

Filtration of hydrates of Si, Fe, and Mn from a solution of NH4H3V207 at pH 8.0;

Crystallization of AMV:

NH4H3V207 + NH40 H pH 7.5-8.0 > .]. 2NH4VO 3 + 2H20;

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 Recharging of AMV:

2RNHNO 3 + H2SO 4 NH4NO3 >(RNH) 2 SO 4 + 2NH4NO 3 + H20 ;

NH4OH

Thermal decomposition of AMV:

2NH4VO 3 55~176>V205 + NH 3 + H 2 0 ;

Electrolysis of manganese sulfate:

MnSO4 + H20 = MnO 2 + H2SO4.

Manganese dioxide is deposited on the anode at a current density of 100 A/m 2 and a temperature of 92~
Decomposition of the spinellide FeO.V203 in an acid converter slag begins with the oxidation of wustite to magnetite
and the precipitation of active V203, which reacts with the oxides of manganese, calcium, and sodium. The probability of the
formation of vanadates increases in this series of oxides (with allowance for the Gibbs free energy). In practice, V203 reacts
mainly with MnO 2 to form manganese vanadate, and only after this does calcium or sodium replace manganese. It has been
proposed that the decomposition of the slag during roasting be made easier by using a method which employs a binary reaction
involving spinel-hematite (Fe203) and manganese oxide (Mn203).
Sorption leaching of vanadium from the residue by the following scheme:

Mn2V207 +2(R3NH)2SO4org +H2SO4 pH 2.0 >(R3NH)4V207org +MnSO4 '

5Mn2V207 + (R3NH)2SO4 + 9H2SO4 pI-I2.0 >(R3NH)2H4VIoO28 + 10MnSO4 + 7H20

makes it possible to use three countercurrent stages to extract up to 95% of the vanadium and saturate the anion exchanger with
V205 up to the level 350 kg/ton. The saturated anion exchanger is separated from the pulp, washed, and subjected to desorp-
tion. The pulp is separated into a solution and a filter cake; the solution is used in the production of manganese, while the fil-
ter cake is subjected to additional leaching with 5-7% H2SO 4.
C o n c l u s i o n s . Use of the manganese-sorption technology makes it possible to:
- facilitate the decomposition of vanadium and improve the indices of the sintering (roasting) operation as a result of
the dual action of hematite and manganese oxide on spinel;
- combine the processes of leaching and the sorption of polymeric complexes of vanadium on anion exchanger alu-
minum (porous); this eliminates the supercooling the vanadium from solutions;
- efficiently separate vanadium from manganese during sorption, washing, and desorption;
- crystallize AMV from highly concentrated systems;
- precipitate manganese in the form of a commercial product;
- attain a value of 80-90% for the index characterizing the amount of vanadium obtained as a finished product from slag;
- obtain both commercial vanadium oxide and vanadium oxide of grades VNO-1 and VNO-2;
- obtain high-quality manganese dioxide - grade EDM (electrolytic grade).
The sludge formed in the process can be used in sintering and blast-furnace smelting.

REFERENCES

l. M. N. Sobolev, Production of Vanadium from Kerch Iron Ores [in Russian] (1935).
2. M. N. Sobolev, Recovery of Vanadium and Titanium from Ural Titanomagnetites [in Russian] (1936).
3. M. N. Sobolev, N. S. Krasil'nikov, and K. A. Bol'shakov, Redk. Met., No. 6 (1933).
4. M. N. Sobolev, A. I. Polyakov, and A. I. Sukharkov, "Production of ferrovanadium in Germany," Byull. IIINChM, 59,
No. 15, 13 (1946).

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5. D. S. Belyankin and V. V. Lapin, "Vanadium in the converter slags at the Chusovoi Metallurgical Plant," Izv. Akad. Nauk
SSSR, No. 11, 1649 (1946).
6. A. Yu. Polyakov and A. V. Rudneva, "Study of vanadium-bearing converter slags," Izv. Akad. Nauk SSSR, No. 4, 45
(1957).
7. V. V. Averin, R. A. Karasev, A. Yu. Polyakov, and A. M. Samarin, "Effect of manganese on the activity and solubility
of oxygen in liquid iron," Izv. Akad. Nauk SSSR, No. 11, 52 (1956).

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