EXTRACTIVE REMOVAL OF

VANADIUM AND MOLYBDENUM

FROM SPENT
HYDRODESULFURIZATION
CATALYST
A. D. ROJAS-RODRGUEZ*, N. N. LPEZ-CASTILLO AND M. J. CRUZ GMEZ**
* Facultad de Ingeniera, Universidad Anhuac Mxico Norte, Edo. de Mxico,
Mxico, 52786.
** Departamento de Ingeniera Qumica, Facultad de Qumica, Universidad
Nacional Autnoma De Mxico (UNAM), Mxico D.F., 04510.

SUMMARY: Molybdenum-containing catalysts are used in petroleum-refining industries for

hydrodesulfuration processes. These catalytic processes generate huge quantity of spent
catalyst. With the increasing demand of metal values and environmental awareness, spent
catalysts can serve as a secondary source for metal recovery. Extractive removal of
molybdenum and vanadium were carried out from spent hydrodesulfurization (HDS) catalyst,
in presence of an alkaline solution, to change vanadium and molybdenum into water-soluble
compounds. Various parameters such as temperature, time, and NaOH addition have been
studied extensively. Additionally, conditions for the maximum recovery of molybdenum and
vanadium have been established; at 100 C, with a retention time of 12 h, and using 5 wt.%
NaOH solution, it was possible to extract 95% of molybdenum and vanadium from the spent
catalyst.
1. INTRODUCTION
Vanadium is an important by-product used, almost exclusively, in ferrous and non-ferrous
alloys due to its physical properties such as high tensile strength, hardness, and fatigue
resistance. The global supply of vanadium originates from primary sources such as ore
feedstock, concentrates, metallurgical slags, and petroleum residues. Other vanadium reserves
include potential recovery from oil-bearing sands, shale gas, phosphate rocks, and crude oils
(Moskalyk & al, 2003).
In the past, spent catalysts were discarded for landfill; however, air, soil, and ocean
pollution caused by these waste catalysts became a rising problem. Increasing environmental
concerns and legislation regarding the disposal of hazardous residues is forcing companies
and countries to start processing their own waste products and residues.

Spent hydroprocessing catalysts have been classified as hazardous wastes by the

Environmental Protection Agency in the USA (Rapaport, 2000). Additionally, it presents a
new business opportunity for rejuvenating, recycling, and transforming the spent catalyst into
an environmentally acceptable and safe material. In refineries, the spent catalyst problem can
be treated by several alternative methods such as disposal in landfills,
regeneration/rejuvenation and reuse, metals reclamation, and employment as raw materials to
produce other useful products. In the study published by Marn S. Villarreal & al (1999),
NaOH aqueous solutions, concentrated and diluted, at 23.8 atm were used as a leaching agent
to extract V from catalysts.
Inoue K. & al (1996) studied a spent Co-Mo/Al2 O3 catalyst mainly deposited with V and
Ni from its operation. The catalyst was roasted at 973 K, suspended in 63% H 2SO4, and
evaporated to dryness. Subsequently, it was dissolved in water and filtered to remove small
silica amounts. The filtrate was then diluted until a pH of 1.2 was reached; this solution was
extracted by a series of commercial extracting agents. The separation of Co and Ni from Al
can be achieved but the procedure may be too expensive.
Krzysztof M. & al (2010) treated a spent vanadium catalyst, which was leached with an
urea solution to recover vanadium, potassium, and iron. Results showed that 180250 m
catalyst leached for 1 h at 20 C in presence of 40% urea solution at a liquid: solid ratio of
10:1, the extent of leaching for V, K, and Fe was about 78%, 90%, and 29%, respectively.
In the study published by Chen Y. & al (2006), extraction of molybdenum and vanadium
from ammonia leaching residue of spent catalyst was investigated, by roasting the residue
with soda carbonate, followed by a hydrometallurgical treatment of the roasted products. One
load was roasted at 750 C for 45 min and the roasted mass was then leached with water, with
this roasting process, over 91.3% of molybdenum and 90.1% of vanadium was extracted.
Once the leach liquor was purified, an extraction solvent, consisting of trialkylamine and
secondary octyl alcohol dissolved in sulfonated kerosene, was used to extract molybdenum
and vanadium from the leach liquor. In the whole process, a total of 88.2% of molybdenum
and 87.1% of vanadium extracted were achieved.
In the present study, spent catalyst obtained from the H-Oil (gasoleum
hydrodesulfurization) Unit of PEMEX (Ptroleos Mexicanos) Refineries was used. The
purpose of this research was to determine the process conditions (calcination time and
temperature, NaOH concentration, reaction time and temperature) to recover the maximum
amount of V and Mo as V2O5 and MoO3, respectively.

2. MATERIALS AND METHODS

2.1 Samples
All samples had a particle size within the range of 1.5 to 7.3 mm, and they contained nickel
and molybdenum as active constituents. Reagents used such as H2O, V2O5, KOH, NH4OH,
Na2CO3, HCl, and NaOH were of AR grade. Reactions were performed in a 250 mL round
bottom flasks.

2.2. Analytical tests

Chemical composition of the products was determined by Infrared spectroscopy, X-ray
fluorescence, scanning electron microscopy, and X - ray diffraction.

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2.3 Calcination of the sample

Since the sample contains about 30% hydrocarbons and elemental sulfur (Rojas & al, in
press). The spent catalyst was calcined to remove those compounds and to oxidize vanadium
sulfide.
2.4 Selection of the alkaline solution
Vanadium compounds present in the spent catalyst form vanadates, which are water soluble
compounds in alkaline medium. Hence, the more suitable alkaline medium to obtain these
vanadium soluble compounds was selected. Once the reaction was performed, the obtained
suspension was centrifuged to separate the two phases (solid and liquid). Since the solid phase
has the unreacted V2O5, it was placed in a desiccator and weighed.
2.5 Vanadium and molybdenum extraction
A 14 g sample from the spent calcined catalyst was taken and dissolved in the previously
selected alkaline solution. Sample concentrations are provided in Table 1. The vanadates and
molybdates solution was then decanted, keeping the aluminum and nickel undissolved
compounds in the solid phase. Afterwards, the solution was acidified with 35% HCl to a pH
of 1.5 2.0, in order to precipitate vanadium, as V2O5 and molybdenum as MoO3.

3. RESULTS AND DISCUSSION

3.1. Calcination temperature
20 g of the spent catalyst were calcined during 6 hours with a temperature ranging between
300 and 600 C. The concentration of the remaining Vanadium was determined. In the plot
shown in Figure 1, it can be observed that in a temperature range of 300 - 450 C vanadium
concentration remains constant. In this range, V2S5 loses sulfur through the chemical reaction
below (equation 1) (Buchanevich & al 1965), where vanadium sulfide transforms into vanadyl
sulfate.

V2 S 5

10O2

(VO 2 ) 2 SO4

4SO3

(1)

Vanadium concentration decreases at 500 C. This reduction may be explained by the

development of a decomposition reaction of sulfate (equation 2) that causes vanadium losses
(Buchanevich & al, 1965).

(VO2 ) 2 SO4

V2O5

SO3

Table 1 - Chemical analysis data for the calcined spent catalyst

Compound Al4C3
V2O5
MoO3
NiAlO4
(VO2)2SO4 -Al2O3
wt.%
38.11
0.21
11.33
11.18
6.22
11.07

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(2)

Other
1.33

From 600 C, the reduction on vanadium concentration is attributed to the volatilization of

the pentoxide, taking into account that its melting point is 660C.
The calcination temperature selected was 450 C, providing it is the maximum temperature
where vanadium concentration remains constant.
3.2 Calcination time
A sample of 20 g from the spent catalyst was calcined at 450 C, during a period of time of 1
to 6 hours (Figure 2). The amount of hydrocarbons eliminated increases as the calcination
time goes on. After 2 and 3 hours, the weight losses of the initial amount of the spent catalyst
were of 23% and 24%, respectively; however, after 4 hours the catalyst showed a constant
weight loss of 25%. Therefore, it can be concluded that 4 h is the best calcination time.

mgV/g Spent catalyst calcined

40.0
35.0

33.7

33.7

33.7

30.0

27.5

25.0

27.0

24.4

20.0
15.0
10.0
200

300

400
500
Temperature [C]

600

700

Figure 1. Effect of the calcination temperature on vanadium concentration.

22.0
21.0
20.0

Sample calcined [g]

20.0
19.0

18.0
17.0
15.6

16.0

15.2

15.1

15.0

15.0

15.0

15.0
14.0
0

4
Time [h]

Figure 2. Effect of the calcination time on the remaining mass.

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%Transmitance

Spent Catalyst

Wabenumber cm -1

%Transmitance

Spent Catalyst calcined

Wabenumber cm -1

Figure 3. IR Spectra for the raw and calcined sample, respectively.

Figure 3 shows the IR spectra for the raw spent catalyst and the calcined sample. The signal
found at 2924.05 cm-1 corresponds to methylene groups (-CH2 -), and at 2854.04 cm-1 to
methyl groups (-CH3). The 1494.98 cm-1 band, and its confirmation at 745.82 cm-1, stands for
the presence of aliphatic compounds. The signal at 1463.97 cm-1, and its confirmation at
722.66 cm-1, indicates the presence of long-chain hydrocarbons (HC). While the 1647.07 cm-1
and 844.82 cm-1 bands are due to the presence of unsaturated HC.
The IR spectrum for the calcined sample no longer shows signals at 2924 and 2854 cm-1,
which originally corresponded to the presence of methyl and methylene groups. Neither do
the signals for long-chain aliphatic compounds (745 1494 cm-1 and 722 1463 cm-1)
appear.
3.3 Alkaline solution
In this step, 1 g of pure V2O5 was used mixed with the corresponding stoichiometric amounts
of different compounds in aqueous solution. (Equations 3, 4, 5, 6).

V2 O5

Na2 CO3

2 NaVO3

V2O5

2 KOH

2 KVO3

2 NaOH

2 NaVO3

V2 O5
V2 O5

2 NH 4 OH

CO2

(3)

H 2O

(4)

2 NH 4VO3

H 2O
H 2O

(5)
(6)

At the same time reaction 6 develops, reactions 7 and 8 take place.

NH 4 OH

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NH 3

H 2O

(7)

3V2O5 4 NH 3

3V2O3 6 H 2O 2 N 2

(8)

According to the data provided in Table 2, the best alkaline solution was NaOH, considering
93% of the treated vanadium pentoxide was dissolved in this solution.
3.4 Effect of reaction time on vanadium and molybdenum extraction
A calcined spent catalyst sample was treated with 2% sodium hydroxide solution, during a
period of time of 8 to 14 hour, at a constant temperature of 25 C; results are shown in Figure
3. After performing the reaction during 14 hours, a reduction on the % Mo extracted occurred
possibly due to a decrease in the surface area. Within a 12 hour period, 70.4% of V and 71.0%
of Mo were extracted; therefore, a reaction time of 12 h was determined as optimum.
3.5 Effect of NaOH concentration on vanadium and molybdenum extraction
In this test, 2-6 wt.% NaOH solutions were used for a 12 hour period of time, at a constant
temperature of 25 C (Figure 5). V and Mo extraction is enhanced as NaOH concentration
increases; however, once a 5 wt.% concentration is reached, the amount of V (82.5%) and Mo
(86.5%) extracted remains constant and unaffected by the addition of NaOH. This may caused
because as NaOH concentration increases more aluminum compounds are dissolved, hence
aluminum hydroxide is produced.
3.6 Effect of reaction temperature on vanadium and molybdenum extraction
In order to determine the most suitable reaction temperature, four temperatures were tested:
25, 100, 150, and 200 C. As shown in Figure 6, the optimum temperature is 100 C. For Mo,
the % amount extracted is diminished providing that once 150 C are reached, the reaction to
produce Ni(OH)2 soluble is favored.
4. CONCLUSION
Spent gasoil hydrodesulfurization catalyst may be used as a secondary source for V and Mo.
The most suitable conditions for hydrocarbons and elemental sulfur removal are calcination
during 4 hours at 450 C. It is possible to recover up to 95% of V and Mo, if the product
reacts with 5 wt.% NaOH solution at 100 C, with a reaction time of 12 hours. The remaining
product from the dissolution reaction contains nickel and aluminum.
Table 2 - Mass of V2O5 dissolved in each alkaline solution tested
Alkaline solution
NH4OH
Na2CO3
KOH
wt.% V2O5 dissolved 13.40
91.41
90.00

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NaOH
93.01

75.0
70.4

70.0

71.0
71.0

%Recovery

68.2

65.0

65.0

61.2

60.9

60.0

55.0

55.1

"V"
"Mo"
50.0
6

10

12

14

16

Time [h]

Figure 4. Effect of Reaction Time on V and Mo extraction.

95.0
86.5

90.0
85.0

86.5

82.0

80.0

82.5

82.5

%Recovery

75.0
70.0

74.1

65.0

69.3

60.0
55.0
50.0
45.0

47.1

40.0

"V"

35.0

"Mo"

30.0
1

NaOH [%w]

Figure 5. Effect of NaOH Concentration on V and Mo Extraction.

100.0
95.1

95.0
90.0

95.3

95.2

95.3

88.2

85.0

88.0

%Recovery

80.0
75.0
70.0
65.0

64.5

60.0
55.0
50.0

47.9

45.0

"V"

40.0

"Mo"

35.0
30.0
0

75

150

225

Temperature [ C]

Figure 6. Effect of the Reaction Temperature on V and Mo Extraction.

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ACKNOWLEDGMENTS
The authors wish to acknowledge the help of Ph. D. Victor Hugo Del Valle -Muoz and the
Prof. Pedro Guillermo Hijar-Fernandez. This work was supported by CONACYT.

REFERENCES
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Inoue K., Tsuyama H., & al, (1996) Extraction and selective stripping of molybdenum (VI)
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