Waste Management xxx (2015) xxxxxx

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Recovery of vanadium from spent catalysts of sulfuric acid plant by

using inorganic and organic acids: Laboratory and semi-pilot tests
Ceren Erust a, Ata Akcil a,, Zyuldyz Bedelova a,b,c, Kuanysh Anarbekov a,b,c, Aliya Baikonurova c,
Aysenur Tuncuk a
a
Mineral-Metal Recovery and Recycling (MMR&R) Research Group, Mineral Processing Division, Department of Mining Engineering, Suleyman Demirel University, TR32260
Isparta, Turkey
b
National Center on Complex Processing of Mineral Raw Material of the Republic of Kazakhstan, Almaty, Kazakhstan
c
Kazakh National Technical University named after K.I. Satpaev, 22 Satpaev Str., 050013 Almaty, Kazakhstan

a r t i c l e i n f o a b s t r a c t

Article history: Catalysts are used extensively in industry to purify and upgrade various feeds and to improve process
Received 11 August 2015 efficiency. These catalysts lose their activity with time. Spent catalysts from a sulfuric acid plant (main
Revised 2 November 2015 elemental composition: 5.71% V2O5, 1.89% Al2O3, 1.17% Fe2O3 and 61.04% SiO2; and the rest constituting
Accepted 4 December 2015
several other oxides in traces/minute quantities) were used as a secondary source for vanadium recovery.
Available online xxxx
Experimental studies were conducted by using three different leaching systems (citric acid with hydro-
gen peroxide, oxalic acid with hydrogen peroxide and sulfuric acid with hydrogen peroxide). The effects
Keywords:
of leaching time, temperature, concentration of reagents and solid/liquid (S/L) ratio were investigated.
Leaching
Metal recovery
Under optimum conditions (1:25 S/L ratio, 0.1 M citric acid, 0.1 M hydrogen peroxide, 50 C and
Spent catalyst 120 min), 95% V was recovered in the presence of hydrogen peroxide in citric acid leaching.
Vanadium 2015 Elsevier Ltd. All rights reserved.
Waste management

1. Introduction residues economical in terms of natural resources saved.

Catalysis has been defined as the process by which chemical
reaction rates are altered by the addition of the catalyst. Catalysts
have very wide range and the number of uses is increasing every-
day. However, the catalysts deactivate by and by. When the activ-
ity of the catalyst declines below the acceptable level, that catalyst
is usually regenerated and reused, but regeneration is not possible
every time (Furimsky, 1996; Marafi and Stanislaus, 2008a). After a
few cycles of regeneration and reuse, the catalyst activity may
decrease, and further regeneration may not be economically feasi-
ble (Wahoud et al., 2011). The U.S. Environmental Protection
Agency classifies spent catalysts as hazardous wastes (USEPA,
2003).
Spent catalysts considered as secondary resources would
decrease the consumption of primary resources and would provide
great economic benefits. Valuable metals (V, Ni, Mo, Co, etc.) in the
form of oxides or sulfides are usually extracted from primary ores
at very low concentrations (a few ppm). Excavation of huge
amounts of rock with the water and energy consumption required
for processing such ores makes the recovery from oil-refining
Corresponding author.
E-mail address: ataakcil@sdu.edu.tr (A. Akcil).
Furthermore, the concentration of those metals in the spent
catalysts is much greater than the concentration of those metals
in primary ores. Due to strict environmental regulations for
disposal, different processes have been examined to treat waste
catalysts in a meaningful way. One effort is to recover valuable
metals through economically and environmentally sustainable
techniques (Marafi and Stanislaus, 2008a; Akcil et al., 2015).
Vanadium (V) especially has strategic and industrial importance
due to its applications in many technological fields (Moskalyk and
Alfantazi, 2003). V has many and continually increasing industrial
applications. Today, vanadium consumption in steel industry
amounts to 85% of its total consumption; other applications are
in vanadium bearing titanium alloy, chemical industries and an
alloying agent to produce ferro-vanadium. V is employed for the
manufacture of a variety of V compounds, many of which in turn
are employed to prepare catalysts such as hydrocarbon oxidation
catalysts and catalysts for the manufacture of sulfuric acid
(H2SO4) (Khorfan et al., 2001). The common grade of V in processed
ores is usually less than 2%. As a result, many industrial sub-
products have been investigated and used for V recovery, including
converter and smelter slag, or spent catalysts (Gupta and
Krishnamurthy, 1992). Vanadium is never found in its pure state
and present primary resources are not sufficient to satisfy V

http://dx.doi.org/10.1016/j.wasman.2015.12.002
0956-053X/ 2015 Elsevier Ltd. All rights reserved.

Please cite this article in press as: Erust, C., et al. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids:
Laboratory and semi-pilot tests. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.12.002
2 C. Erust et al. / Waste Management xxx (2015) xxxxxx

demand (Liu et al., 2003) and to ease an insufficient supply of
domestic resources; many countries comprehensively utilize sec-
ondary resources containing V (Shao et al., 2009).
Average service life of vanadium catalysts is 12 years. For this
reason, 7770 tons of spent catalyst is revealed from sulfuric acid
plant per year in Turkey (Eti Mine Company, 2013). The H2SO4 pro-
duction process can be divided into three main reactions, namely
(Tveit, 2003);
Combustion of sulfur : S O2 ! SO2
Catalytic oxidation : SO2 1=2O2 ! SO3
Sulfur trioxide absorption : SO3 H2 O ! H2 SO4
When producing H2SO4 through the contact process, an impor-
tant step is to produce sulfur trioxide by passing a gas mixture of
sulfur dioxide and oxygen over a catalyst (Eq. (2)). The oxidation
of SO2 to SO3 is slow and needs a very high temperature to have
a realistic rate without the use of a catalyst (Ognyanova et al.,
2009).
Most industrial waste is now treated as a substance for reuse
and as a source of valuable raw materials. Such type of waste is
spent V catalyst the amount of spent V catalyst accumulated in
Poland is estimated to be approximately 3000 Mg (Grzesiak,
2006). The problem of deactivated and decommissioned industrial
catalysts is very serious and has not been solved yet in a compre-
hensive manner (Mazurek et al., 2010; Mazurek, 2012, 2013).
Extraction of the V present in spent catalysts by leaching
method has been studied by many researchers, as indicated by
the summary of the studies shown in Table 1. Aqueous solutions
of ammonia and ammonium salts, various concentrations of inor-
ganic acids (e.g., HCl, H2SO4, HNO3), oxidants and alkalis have been
used as leaching solutions.
Among organic reagents (e.g., citric acid, oxalic acid), water-
soluble organic acids have been attracted more attention (Marafi
and Stanislaus, 2008b). Lee et al. (1992) and Zeng and Cheng
(2009) reported that oxalic acid can be used as a complexing agent
to selectively extract V from the spent HDS catalysts. Beuther and
Flinn (1963) compared the efficiencies of many organic acids such
as oxalic acid, lactic acid, citric acid, glycolic acid, phthalic acid,
malonic acid, succinic acid, salicyclic acid and tartaric acid for
leaching metals (V, Mo, Ni and Co) from a spent hydrotreating cat-
alyst. Aqueous solutions of the acids (1%) were used at ambient
temperature and pressure in this study. Oxalic acid was found to
show the highest efficiency for leaching all four metals. The metals
V (47%), Mo (59%), Co (60%) and Ni (56%) were leached by 1 wt%
oxalic acid solution. The effect of reagent concentration and other
conditions of leaching were not investigated and optimized.
A study published by Mulak et al. (2006) was studied on opti-
mizing the parameters for the extraction of Mo, Ni, V and Al from
a spent HDS catalyst using aqueous oxalic acid solution mixed with
hydrogen peroxide (H2O2). The results showed that addition of
1
H2O2 to oxalic acid up to 3.0 M H2O2 enhanced the leaching of met-
als remarkably, and thereafter the leaching remained relatively
2
stable. The highest extraction of metals from the spent catalyst
(at 50 C with a solution of 0.5 M oxalic acid with 3.0 M H2O2)
3
was found to be 90% Mo, 94% V, 65% Ni and 33% Al in 4 h of
leaching.
In another study, ammonium metavanadate was precipitated
from the purified solutions at pH 7.27.6, a ratio of (NH4)2SO4/
V2O5 and at room temperature. Increasing the sulfate concentra-
tion was shown to adversely affect the precipitation of ammonium
metavanadate. Conversion of metavanadate into polyvanadate was
achieved by repulping in hot distilled water (9095 C) and in pH 2.
Vanadium pentoxide (98.8% V2O5) was produced by firing poly-
vanadate precipitate at 560 C (Gladyshev et al., 2015).
At the same time, bioleaching has been applied for the recovery
of spent catalyst, and several studies have recently been focused on
spent catalyst (Beolchini et al., 2012). Bioleaching is today consid-
ered a novel approach for metal mobilization from various solid
matrices: mineral ores, fly ash, sewage sludge, spent batteries
and electronic scrap materials. Spent catalysts are only some of
the solid wastes that can potentially be treated by means of
bioleaching (Santhiya and Ting, 2005; Marafi and Stanislaus,
2008b). In a study conducted by Beolchini et al. (2012),
Fe/S-oxidizing bacteria were applied to spent refinery catalysts to
assess the performance of bioleaching in metal mobilization.
For spent refinery catalysts, the improvement in metal extraction
observed in the presence of microbial activity confirms the key
role of Fe/S-oxidizing bacteria and ferrous iron with 1% solid
content (w/v). They were showed that recovered Ni, V, Mo of
83%, 90% and 40%, respectively.
The main purpose of the present work was to investigate the
recovery of V from the spent catalyst with H2SO4, oxalic acid and
citric acid leaching. Metals are able to form soluble metal com-
plexes, with the addition of H2O2 as effective reagent. The studied

Table 1
Summary of some studies carried out on recovery of V from spent catalyst.

Source of waste Leaching conditions V recovery (%) References

Spent catalyst In a solution of 0.05 N sodium nitrate (NaNO3), pH 8.00, at 25 C and 1:15 S/L ratio 39 Lai and Liu
(1997)
Spent H2SO4 catalyst H2SO4 leaching (15% H2SO4; 1 h; 100 C; 1/5 S/L ratio) + Oxidative precipitation (73% efficiency) 96.6 Khorfan et al.
(2001)
Spent Hydro-desulfurization The leaching step with acid mixture (50 mL 70% HNO3 + 25 mL of 96% H2SO4 + 25 mL of 37% HCl) 99 Lai et al. (2008)
(HDS) catalysts in 2 h at 70 C
Spent H2SO4 catalyst The roasting step (400 C) 78 Ognyanova
The acidic leaching step (0.3 M H2SO4) in 6 h at 80 C and 1:10 S/L ratio et al. (2009)
The alkaline leaching step (4 M NaOH) in 2 h, followed by acidic leaching (0.5 M H2SO4)
Spent catalyst (NiMo/Al2O3) In a solution of 0.50 M oxalic acid (H2C2O4) and 0.66 M H2O2, at 70 C 80 Madeja (2011)
Spent V catalyst A 180250 lm catalyst in 4 h at 323 K in the presence of 2% oxalic acid solution at 1:25 S/L ratio 91 Mazurek
(2013)
V cake 2 M H2SO4 and 40 g/L Na2SO3 at 40% pulp density, 70 C for 1 h 93.1 Okudan et al.
(2015)
Selective catalytic reduction 5 M NaOH solution, 1:5 S/L ratio at 393 K for 3 h (continuous air stirring, 10 mL/min, 0.05 MPa 96.5 Huo et al.
(SCR) catalysts (2015)
Spent selective catalytic 2 M NaOH, 0.2 M Na2CO3, 300 C, and 1:20 S/L ratio 86.6 Kim et al.
reduction (SCR) catalyst (2015)
Spent diesel exhaust catalyst The ammonia concentration of 4.5 M, leaching temperature of 413.15 K, reaction time of 2 h, the 46.25 Zhao et al.
H2O2 solution concentration of 1.0 M and 1:20 S/L ratio (2015)

Please cite this article in press as: Erust, C., et al. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids:
Laboratory and semi-pilot tests. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.12.002
 C. Erust et al. / Waste Management xxx (2015) xxxxxx 3

process conditions included parameters of concentration of of HNO3 and HCl. Metal contents (27,076 ppm V, 4.9 ppm Co,
reagents, temperature and S/L ratio. 41.3 ppm Cu, 51.2 Ni, 100 ppm Al, 102.5 ppm Fe) were determined
by the ACME Analytical Laboratories Ltd. (Canada) with AAS (Agi-
lent AA 240FS).
2. Materials and methods

2.1. Materials 2.2. Methods

The spent catalysts were obtained from the converter unit of
the Eti Mine Company Sulfuric Acid Plant in Bandirma (Balikesir,
Turkey). The catalyst samples (cylindrical, with an average diame-
ter of 4 mm and 8 mm in length) were ground to 150l by a jaw
crusher to improve leaching efficiencies. Then, they were dried in
drying oven at 100 C for 2 h. All acids, sodium carbonate and
hydrogen peroxide employed were analytical grade (Merck). For
estimating the main chemical composition, 0.15 g of the sample
was dissolved in aqua regia (10 mL) containing a 1:3 volume ratio
Leaching tests were performed in shaken flasks (600 mL) at 25,
50, 80 C. When the required temperature was reached, the spent
catalyst was added and the stirring was started. The samples were
mixed using a magnetic mixer with heater (Velp, Arec) and a dig-
ital overhead mixer (Teflon-coated impeller tip) (Heidolph, RZR
2021) at a stirring rate of 150 rpm (Fig. 1A). According to the opti-
mum analysis results obtained, semi-pilot scale reactor leaching
tests were performed in glass reactors with the capacities of 2 L
and 20 L in working volumes of 1.5 L and 15 L, respectively, with

A
Stirrer

Thermomet

Reactor

Heated
magnetic
stirrer

B C

Digital
overhead stirrer

Reactor

Heating unit
& circulator

Fig. 1. Experimental apparatus for laboratory (A 500 mL) and semi-pilot (B 2 L, C 20 L) scale reactor leaching.

Please cite this article in press as: Erust, C., et al. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids:
Laboratory and semi-pilot tests. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.12.002
4 C. Erust et al. / Waste Management xxx (2015) xxxxxx

Table 2 3. Results and discussion

Experimental conditions for recovery of V from spent catalyst.a

Oxalic acid concentration (M) 0.25, 0.5, 1 3.1. Leaching tests

H2O2 concentration (M) for oxalic acid tests
Citric acid concentration (M)
H2O2 concentration (M) for citric acid tests
H2SO4 concentration (M)
H2O2 concentration (M) for H2SO4 tests
S/L ratio
Temperature (C)
Time (min)
a
1:25 S/L ratio, 50 C leaching temperature and 120 min leaching time are con-
stant values when the other parameters change.
controlled temperature and stirring rate (Fig. 1B and C). The work-
ing temperatures in the reactors were maintained by circulating
water through the jackets of the reactors using heating/cooling cir-
culators (Labo D-300 and D-350). The S/L ratio, leaching time, tem-
perature and concentration of the leaching reagents were studied
under the experimental conditions (reagents and their concentra-
tion ranges have been stated according to the results of pre-
leaching tests) shown in Table 2.
H2O2 is widely known to be able to play a role as an oxidizing
and reducing agent (Vegli et al., 2006), and the purpose of its
use in the experiment was to see the behavior of V during acidic
leaching. At the end of the leaching procedure, the solution was fil-
tered, leach liquor was separated from the solid and the concentra-
tion of V in the leach liquors was determined by titration with
0.2 M KMnO4 solution (Okudan et al., 2015). V recovery percent-
ages were calculated according to Eqs. (4) and (5) by taking the
average of the three analysis.
B X  0:02  5=3  0:08294
%V X  0:02  5=3  0:05094  100=B
X: Amount of spent KMnO4.
B: Amount of V in stock solution.
0.5, 1, 2
0.1, 0.15, 0.2 The effects of the oxalic acid, citric acid, H2SO4 and H2O2 con-
0.1, 0.5, 1 centration variables on V leaching efficiency in leaching tests with
0.5, 1, 2 H2O2 are presented in Fig. 2. An increase in citric acid and H2SO4
0.25, 0.5, 1 did not lead to an increase in V efficiency. Therefore, it is more con-
1:50, 1:25, 1:10 venient economically to use a low concentration of these acids. In
25, 50, 80
Fig. 3, the efficiency graphics are given the increased concentration
60, 120, 240
of H2O2 according to the acid used. The 0.5 M of H2O2 was deter-
mined to be appropriate in H2SO4 leaching with H2O2. The maxi-
mum value of the H2O2 concentration in oxalic acid leaching and
the minimum value of the concentration of H2O2 in citric acid
leaching were selected.
The concentration, temperature and leaching time had a posi-
tive effect for oxalic acid leaching with H2O2, the optimal S/L ratio
in the oxalic acid with H2O2 leaching tests was set as 1:25, and the
leaching efficiency was observed to be reduced at a 1:10 S/L ratio
because of the dissolution rate. The low H2O2 concentrations seem
to be insufficient. Under optimum conditions (1:25 S/L ratio, 0.5 M
oxalic acid, 2 M H2O2, 70 C and 120 min), V leaching efficiency
was observed to be approximately 67.4%.
Secondly, citric acid leaching tests with H2O2 was studied for
the recovery of V from waste spent catalyst. The influence of citric
acid and H2O2 concentration, S/L ratio, leaching temperature and
leaching time on the reaction were investigated (Fig. 24). The
results indicated that the concentration is low for the recovery rate
of V when the leaching temperature is 25 C or leaching time is
60 min. Under the conditions of 1:25 S/L ratio, 0.1 M citric acid
and 0.1 M H2O2, almost all of V was recovered at 95%. Generally,
the leaching yields increase with time, although the V efficiency
values at 120 and 240 min are almost same, 95% and 95.4%
4 respectively.
The analysis showed that the leaching temperature is found to
be important for leaching yields of V with a positive effect. V dis-
5 solution increased with temperature, thus 50.7%, 90.8% and 92.5%
V efficiencies were obtained at 25, 50 and 80 C, respectively in
H2SO4 leaching with the addition of H2O2. An increase in H2SO4

95.7 96.4
100 A 100 B 95.1
Efficiency of V (%)

Efficiency of V (%)

80 80
67.4 67.7

60 51.9 60

40 40

20 20
0.25 0.5 1 0.1 0.15 0.2
Oxalic acid concentration (M) Citric acid concentration (M)

100 C 90.8 91.5 92.4

Efficiency of V (%)

80

60

40

20
0.5 1 2
H2SO4 concentration (M)

Fig. 2. The effect of acid concentrations on V efficiency in oxalic acid with 2 M H2O2 (A), citric acid with 0.1 M H2O2 (B), H2SO4 with 0.5 M H2O2 (C) leaching tests.

Please cite this article in press as: Erust, C., et al. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids:
Laboratory and semi-pilot tests. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.12.002
 C. Erust et al. / Waste Management xxx (2015) xxxxxx 5

100 A 100 B

Efficiency of V (%)

Efficiency of V (%)
95.1 95.3 95.5
80
67.4 95
60 55.9
90
40 33.5

85
20

0 80
0.5 1 2 0.1 0.5 1
H2O2 concentration (M) H2O2 concentration (M)

100 C 90.8 91.6

Efficiency of V (%)
80 73.4

60

40
0.25 0.5 1
H2O2 concentration (M)

Fig. 3. The effect of H2O2 concentration on V efficiency in 0.5 M oxalic acid with H2O2 (A), 0.1 M citric acid with H2O2 (B), 0.5 M H2SO4 with H2O2 (C) leaching tests.

100 A 100 B
80 80
Eciency of V (%)

Eciency of V (%)

60 60
Oxalic acid with H2O2 Oxalic acid with H2O2
40 Citric acid with H2O2 40 Citric acid with H2O2
H2SO4 with H2O2 H2SO4 with H2O2
20 20

0 0
1:50 1:25 1:10 25 50 80
S/L rao Leaching temperature (C)

100 C
Eciency of V (%)

80

60
Oxalic acid with H2O2
40 Citric acid with H2O2

20 H2SO4 with H2O2

0
60 120 240
Leaching me (min)

Fig. 4. The effects of S/L ratio (A), leaching temperature (B) and leaching time (C) on V efficiency.

concentration seems not to be significant because V efficiencies are in citric acid leaching with H2O2, under optimum conditions
over 90% (Fig. 2C). In Fig. 4A, the leaching efficiency of V increases (1:25 S/L ratio, 0.1 M citric acid, 0.1 M H2O2, 50 C and 120 min)
gradually as the S/L ratio increases. Increasing the S/L ratio and in H2SO4 leaching with H2O2 under optimum conditions
enhances the diffusion of the reaction medium and makes the reac- (1:25 S/L ratio, 0.5 M H2SO4, 0.5 M H2O2, 80 C and 120 min) 68%,
tion more complete, which is advantageous for leaching. V effi- 95% and 92.5% V was recovered respectively.
ciency values in 1:50 and 1:25 S/L ratio were very close to each
other for all cases, so decreases in the ratio from 1:50 to 1:25 did 3.2. Semi-pilot leaching tests
not change the leaching yields.
In oxalic acid leaching with H2O2, under optimum conditions Because of the V recovery efficiencies in oxalic acid with H2O2
(1:50 S/L ratio, 0.5 M oxalic acid, 2 M H2O2, 50 C and 120 min), leaching tests are lower than V recovery efficiencies in H2SO4

Please cite this article in press as: Erust, C., et al. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids:
Laboratory and semi-pilot tests. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.12.002
6 C. Erust et al. / Waste Management xxx (2015) xxxxxx

Table 3
The parameters of the semi-pilot (SP) reactor tests.

Code Citric acid (CA) concentration (M) H2O2 concentration (M) S/L ratio Temperature (C) Time (min)
CASP1 (2 L) 0.1 0.1 1:25 50 120
CASP2 (2 L) 0.2 0.1 1:25 50 120
CASP3 (2 L) 0.1 0.1 1:50 50 120
CASP4 (2 L) 0.1 0.1 1:25 50 60
CASP5 (20 L) 0.2 0.1 1:25 50 120
H2SO4 (SA) concentration (M) H2O2 concentration (M) S/L ratio Temperature (C) Time (min)
SASP1 (2 L) 0.5 1 1:25 50 120
SASP2 (2 L) 0.5 0.5 1:50 50 120
SASP3 (2 L) 0.5 0.5 1:25 80 120
SASP4 (2 L) 0.5 0.5 1:25 50 240
SASP5 (20 L) 0.5 0.5 1:25 80 120

99.2 Spent Catalyst

99.2 98.9 98.9
100 98.0 98.1 (27076 ppm V)
96.9 CASP1
CASP2
96
CASP3
Efficiency of V (%)

92.4
CASP4 Grinding
92 CASP5
SASP1
87.1
88 86.5 SASP2
SASP3
SASP4 Sieving +100 m
84
SASP5

80 -100 m

Fig. 5. The efficiencies of V in semi-pilot tests.

Citric acid Leaching

(1:25 S/L ratio
and citric acid leaching tests with the addition of H2O2, these tests Hydrogen peroxide
120 min, 50C, 150
(oxalic acid with H2O2 leaching tests) were not included in semi-
pilot leaching tests. Citric acid and H2SO4 semi-pilot leaching tests
were carried out with the addition of H2O2 that were represented
as CASP and SASP respectively (Table 3). The efficiencies of V are Filtration Solid
shown in Fig. 5. V leaching is observed to increase with an increase
at 80 C. The V leaching efficiencies were the same for CASP2 and Liquid
SASP3.
The cost of leaching was only half of organic (citric and oxalic) Analysis with
acid leaching. For this reason, the effects of H2SO4 and organic acid titration
(alternative for H2SO4) were investigated. The leaching efficiency (0.2 M KMnO4)
of V increased with an increase in citric acid concentration from
0.1 to 0.2 M. V recovery decreased with the increased S/L ratio
and decreased leaching time. By using citric acid instead of
H2SO4 with lower acid concentrations, high V recoveries (99.2%)
were obtained as in H2SO4 leaching tests. 95.% V2O5 recovery
The objectives of this study were to examine the V solubility
Fig. 6. Flow sheet for recovery of V from spent catalyst.
during the acid leaching of spent catalyst at 50 C when using a
weak acid and low concentration in comparison with strong acid
and high concentration. The conventional acid leaching is carried 4. Conclusions
out in strong acid at high concentration and temperature. How-
ever, the conventional leaching may not be very economical. Thus, Leaching tests were conducted to recovery of V from spent cat-
this study proposed to use a weak organic acid at low concentra- alyst using different leaching agents. Leaching parameters such as
tion and a temperature of 50 C. Further increasing the tempera- S/L ratio, initial acid concentration, temperature and time were
ture to 80 C was not so advantageous because of accelerated varied to optimize the leaching process. To obtain the most effi-
decomposition of the reagents and because more copper dissolves. cient dissolution of V, the best conditions seem to be 0.1 M citric
Therefore, the optimum temperature appears to be 50 C, so all acid, 0.1 M H2O2, 50 C, 1:25 S/L ratio and 120 min. Under these
other variable experiments were carried out at this temperature. conditions, the yields are approximately 95% for V. The dissolution
The experimental results obtained by leaching tests suggest a pos- rate was observed to be independent of 150 rpm stirring rate, and
sible flow sheet to recover V from spent catalyst by taking into those results suggest that the rate is not influenced by transport
account the operating costs (cost per unit of a product) (Fig. 6). processes. All subsequent experiments were carried out at a

Please cite this article in press as: Erust, C., et al. Recovery of vanadium from spent catalysts of sulfuric acid plant by using inorganic and organic acids:
Laboratory and semi-pilot tests. Waste Management (2015), http://dx.doi.org/10.1016/j.wasman.2015.12.002
 C. Erust et al. / Waste Management xxx (2015) xxxxxx
stirring rate of 150 rpm to ensure the invariance of this parameter.
The V recovery yield has been found to increase with temperature
but decrease with an increase in S/L ratio. The strongest influence
of temperature on leaching efficiency is observed. However, V
extraction at a temperature above 50 C increases only slightly.
Such methods could be adapted from the recovery of V from
other resources such as V-bearing minerals, black shale, stone-
coal and petroleum coke. The principle is that the V is embedded
in the crystal structure of the ore, which can be dissolved by acids
at high temperatures to generate water-soluble vanadates that are
easy to leach out with water.
Acknowledgements
This collaborative research study was based on the results of
bilateral contacts of the Mineral-Metal Recovery and Recycling
Research Group, Mineral Processing Division, Department of Min-
ing Engineering, the Suleyman Demirel University, Isparta, Turkey
and the Kazakh National Technical University named after K.I. Sat-
paev, Mining and Smelting Institute after O.A. Baikonurov, Almaty,
Kazakhstan. The authors express their sincere gratitude to the Sci-
entific and Technological Research Council of Turkey (Project no:
TUBITAK 111M220) for using of laboratory equipments. The
authors would like to thank the Eti Mine Company Sulfuric Acid
Plant in Bandirma (Balikesir, Turkey) for kindly providing samples.
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