DOI 10.

1007/s11015-019-00836-5

Metallurgist, Vol. 63, Nos. 3-4, July, 2019 (Russian Original Nos. 3-4, March–April, 2019)

DEVELOPMENT OF A PRODUCTION SCHEME FOR UTILIZING VANADIUM

PENTOXIDE HYDROMETALLURGICAL PRODUCTION WASTE

U. A. Kologrieva,1 A. I. Volkov,2 A. S. Kirichenko,3

V. M. Ermolov,4 and M. G. Mirakova UDC 661.888.1

A hydrometallurgical method is considered for treating the lime sediment of drainage water from hy-
drometallurgical production of vanadium pentoxide in order to obtain vanadium-manganese concentrate.
Vanadium master alloys are smelted from the obtained concentrate.

Keywords: vanadium, waste, vanadium pentoxide, hydrometallurgy, sludge, lime precipitate, leaching.

Currently the problem of utilizing production waste (slag, slurry, scale, ash, etc.) accumulated during treat-
ment of natural and technogenic raw materials is one of the main problems for metallurgical production. These
materials in the form of dumps occupy a considerable area and are an ecological hazard due to the content of
harmful impurities within them. At the same time, it is possible to consider them as secondary resources con-
taining valuable components. The task of processing complex raw material and production waste also becomes
more important in view of the exhaustion of rich ore reserves.
One form of this raw material is vanadium production waste. Technogenic technology for producing pure
vanadium includes four stages: preparation of vanadium cast iron; conversion of cast iron into steel semi-
product and vanadium converter slag; preparation of technical grade vanadium pentoxide from slag; production
of ferrovanadium. Sometimes vanadium slag is used directly for steel alloying and melting vanadium master
alloys [1]. The main proportion of ferrovanadium is used for melting alloy steels (rail, corrosion-resistant, etc.).
The production scheme for preparing vanadium pentoxide includes preparation of vanadium-containing raw
material, oxidation firing, leaching, and precipitation of vanadium compounds [2]. Within Russia vanadium
pentoxide is produced by two enterprises, AO EVRAZ Vanadii Tula, an AO Chusov Metallurgical Plant
(AO ChMZ). The hydrometallurgical production waste of vanadium pentoxide are dump slurries and residues
of neutralizing drainage (lime treatment residue) [3]. Dump slurries form after leaching vanadium from cinder
(fired charge based on vanadium slag) and have the following chemical composition, wt.%: 1.5–4.5 V2O 5 ,
40–55 Fe 2O 3 , 5–12 MnO, 6–12 TiO 2 , 2.5–5.5 Cr2O 3 , 13–18 SiO 2 ; ≤ 15 CaO. Detailed studies of vanadium
slag and slurry have been provided in [4–6]. After deposition of vanadium compounds there is formation of
drainage that contains sulfuric acid residue, calcium, magnesium, manganese, vanadium, and iron ions, etc.
In order to neutralize them treatment with lime milk or ozone is used. In the first case a lime treatment residue is
obtained that contains, wt.%: 0.5–5.0 V2O 5 , 9–12 MnO, and 28–32 CaO. The residue from ozone treatment,
only obtained on AO ChMZ, contains 15–20% V2O 5 and 58–63% MnO.

GNTs FGUP I. P. Bardin TsNIIchermet, Moscow, Russia.

1
E-mail: ufowka@mail.ru.
2
E-mail: rhenium@list.ru.
3
E-mail: prof-andrey@mail.ru.
4
E-mail: ferrosplav@chermet.net.

Translated from Metallurg, Vol. 63, No. 4, pp. 78–82, April, 2019. Original article submitted February 4, 2019.

0026-0894/19/0304-0403 © 2019 Springer Science+Business Media, LLC 403

404 U. A. KOLOGRIEVA, A. I. VOLKOV, A. S. KIRICHENKO, V. M. ERMOLOV, AND M. G. MIRAKOVA

In AO EVRAZ Vanadii Tula there is formation of about 80 thousand tons per year of slurry materials [7],
and in AO ChMZ about more than 20 thousand tons [8], which are mainly untreated and stored in slurry pits.
The slurry is used as an iron-containing additive during production of clinker for cement, and a charge additive
in metallurgy, in particular for preventing formation of sinter during firing of vanadium-containing materials.
The lime treatment residue is used in the cement industry [7]. A disadvantage of these utilization methods is the
fact that the expensive component (vanadium) is not extracted.
The aim of the work is to study the possibility of processing lime treatment residue with preparation of
technical grade vanadium-containing product.
Research was carried out a sample of lime treatment residue from AO EVRAZ Vanadii Tula metallurgical
production with particles of a size of – 0.16 mm. sample leaching and filtration was performed in a glass
Nutsch-filter (DIEHM, Germany) with a volume of 5 liters fitted a stirrer and heated jacket, with S:L = 1:5 and
leaching duration of 1 h. after the end of filtration the cake was washed on the filter with hot water (S:L = 1:10),
dried, and subjected to chemical analysis. From the solution obtained by increasing pH vanadium concentrate
was precipitated that was also washed with hot water with S:L = 1:10, then calcined at 500–550°C.
Chemical analysis of the original sample and solid leaching residues was carried out in an Axios mAX Ad-
vanced (PANalytical, Netherlands) X-ray fluorescence spectrometer. The chemical composition of the original
lime treatment residue, wt.%: 1.26 V2O 5 , 42.1 CaO, 1.35 FeO, 1.01 SiO 2 , 0.05 TiO 2 , 6.44 MnO, 1.09 MgO,
0.19 Al 2O 3 , 20.2 SO 3 , 26.0 calcination loss.
X-ray phase analysis was performed by means of a X’Pert PRO MPD (PANalytical, Netherlands) X-ray dif-
fractometer. The main mineral components of the lime treatment residue are, wt.%: 33 gypsum
( CaSO 4 ⋅ 2H 2O ); 23 calcite ( CaCO 3 ); 10 bentorite ( Ca 6 (Cr, Fe)2 (SO 4 ) 3 (OH)12 ⋅ 26H 2O ); 8 portlandite
( Ca(OH)2 ). Vanadium containing phases were not detected.
In order to treat this material a study was made of hydrometallurgical methods based on selective leaching
of vanadium with sulfuric and hydrochloric acids.
In the first stage of the work the effect of solution concentration was studied H 2SO 4 (5–25%) and HCl
(5–20%) on V2O 5 (Fig. 1a, b) and MnO extraction (Fig. 2a, b) into a solution from lime treatment residue with
different process temperatures. With leaching of residue with H 2SO 4 solution the degree of vanadium and
manganese extraction increased with an increase in H 2SO 4 concentration to 20%, and then its starts to decrease.
The maximum degree of extraction of V2O 5 into solution is 65% and for MnO it is 47.5% that is achieved with
an H 2SO 4 concentration of 20% and temperature of 90°C. At the same time the degree of vanadium extraction
into solution by sulfuric acid is not markedly affected by temperature, with the exception of an experiment with
a concentration of 5% H 2SO 4 . During leaching of residue with HCl solution the degree of extraction into solu-
tion for vanadium and manganese increases with an increase in acid concentration. Almost complete extraction
into solution of vanadium and manganese (99–100%) is achieved without heating the solution with an HCl con-
centration of 20%. The same results have been achieved with a reduction in acid concentration (15%), but with
heating the solution to 90°C.
It is well known that oxidation firing of vanadium pentoxide hydrometallurgical production slags has a fa-
vorable effect on V2O 5 extraction into solution [9]. Firing of lime treatment residue was performed at 1000–
1050°C in a muffle furnace. Results of conducting leaching studies into to H 2SO 4 solution for fired lime treat-
ment residue showed a reduction in the extraction of V2O 5 (Fig. 1c) and MnO (Fig. 2c) into solution compared
with the original sample. During leaching with HCl solution for vanadium from a fired specimen temperature
has almost no effect on the degree of extraction. Almost complete extraction of vanadium is achieved only with
an HCl concentration of 29%, and with 5–10% the degree of vanadium extraction is significantly lower com-
pared with an original specimen.
DEVELOPMENT OF A PRODUCTION SCHEME FOR UTILIZING VANADIUM PENTOXIDE HYDROMETALLURGICAL PRODUCTION WASTE 405

(a) (b)

(c)

Fig. 1. Dependence of V2O 5 extraction into solution from original (a, b) and fired lime residue (c) on acid concentration and temper-
ature.

The degree of manganese extraction in a fired specimens is significantly lower than in an unfired specimen,
but with use of HCl solution heated to 90°C and a concentration of 20% almost complete extraction is achieved.
Therefore, by changing the conditions for material preparation and leaching it is possible to control the
chemical composition of the solution obtained, including the ratio of manganese and vanadium content, and fi-
nally affecting the composition of the master obtained. During the lime treatment residue utilization scheme
preference was given to hydrochloric acid leaching treatment (HCl concentration 20%), since this method makes
it possible to extract vanadium and manganese more completely.
In the second stage of research with neutralization of hydrochloric acid solution by NH 4 OH (35%) to
pH 10 and orange colored residue was obtained. After separating it from solution a concentrate of the following
chemical composition is yielded, wt.%: 29.0 V2O 5 , 45.35 MnO, 3.01 CaO, 2.09 Al 2O 3 , 7.63 SiO 2 , 5.65 FeO,
2.68 Cr2O 3 . Complete extraction V2O 5 from the original lime treatment residue into concentrate is 85–90%,
and MnO is 90–92%. The lime treatment residua process scheme is provided in Fig. 3.
406 U. A. KOLOGRIEVA, A. I. VOLKOV, A. S. KIRICHENKO, V. M. ERMOLOV, AND M. G. MIRAKOVA

(a) (b)

(c)

Fig. 2. Dependence of MnO extraction into solution from original (a, b) and fired lime residue (c) on acid concentration and temper-
ature.

In the third stage of research a study was made of melting alloys of the concentrate obtained. Five melts
were made in a Tamman resistance furnace. For this a charge was loaded into an alundum crucible, which con-
sisted of vanadium concentrate (100 g) ferrosilicon FS75 (15–25 g) and lime (45 g). The alundum crucible was
placed in a graphite crucible in order to exclude melt spillage. The gap between the crucibles was filled with
corundum powder. The crucible was placed in a furnace. In all tests the temperature was increased during
30 min to the prescribed temperature (1600°C) after reaching the prescribed temperature short-term crucible
heating was conducted for 15 min. the optimum consumption of reducing agent was determined, i.e., 20 g for
100 g of original concentrate. The chemical composition of the master alloy obtained, wt.%: 52 Mn, 24 V,
20 Fe, 3 Сr, and 0.8 Si. The field for application of the vanadium-manganese master alloy for mass production
steels is for steels containing 0.04–0.10 wt.% V.
DEVELOPMENT OF A PRODUCTION SCHEME FOR UTILIZING VANADIUM PENTOXIDE HYDROMETALLURGICAL PRODUCTION WASTE 407

Fig. 3. Production scheme for treating lime drainage water residue.

From one ton of lime treatment residue by the technology proposed it is possible to obtain 0.2 tons of con-
centrate (dry weight) and 0.09 tons of master alloy. The weight of solid residue is 0.2 tons, and it is possible to
use it in the production of building materials.

CONCLUSIONS

1. A study has been made of extraction of vanadium pentoxide into solution by sulfuric and hydrochlo-
ric acids from residue of drainage water lime treatment of the AO EVRAZ Vanadii Tula hydrometallurgical
408 U. A. KOLOGRIEVA, A. I. VOLKOV, A. S. KIRICHENKO, V. M. ERMOLOV, AND M. G. MIRAKOVA

production. Optimum leaching conditions have been selected: HCl concentration 20%; S:L = 1:5; time 1 h.
In this case the degree of V2O 5 extraction into solution is 90%, and for MnO it is 99%.

2. A hydrometallurgical scheme has been developed for drainage water lime treatment residue including the
following stages: residue leaching; residue filtration and washing; residue calcining with preparation of vanadi-
um-manganese concentrate. Concentrate chemical composition, wt.%: 29.0 V2O 5 , 45.35 MnO, 3.01 CaO,
2.09 Al 2O 3 , 7.63 SiO 2 , 5.65 FeO, and 2.68 Cr2O 3 .

3. As a result of these test melts for master alloy from vanadium-manganese concentrate of a silicothermal
process in a Tamman resistance furnace master alloy of the following composition has been obtained 52 Mn,
24 V, 20 Fe, 3 Сr, and 0,8 Si.

Work was performed with RFFI financial support, project 18-29-24074 mk.

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