ISSN 1070-4272, Russian Journal of Applied Chemistry, 2006, Vol. 79, No. 4, pp. 539!543. + Pleiades Publishing, Inc.

, 2006.
Original Russian Text + V. S. Kolosnitsyn, S. P. Kosternova, O. A. Yapryntseva, A. A. Ivashchenko, S. V. Alekseev, 2006, published in Zhurnal Prikladnoi
Khimii, 2006, Vol. 79, No. 4, pp. 551!555.

INORGANIC SYNTHESIS
ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
AND INDUSTRIAL INORGANIC CHEMISTRY

Recovery of Nickel with Sulfuric Acid Solutions

from Spent Catalysts for Steam Conversion of Methane
V. S. Kolosnitsyn, S. P. Kosternova, O. A. Yapryntseva,
A. A. Ivashchenko, and S. V. Alekseev

Ishimbai Branch of Ufa State Technical University of Aviation, Ishimbai, Bashkortostan, Russia
Institute of Organic Chemistry, Ufa Scientific Center, Russian Academy of Sciences, Ufa, Bashkortostan, Russia
PALLAD NPF, Salavat, Bashkortostan, Russia

Received May 6, 2005; in final form, December 2005

-
Abstract Certain fundamental aspects of leaching-out of nickel with sulfuric acid solutions from spent
catalysts for steam conversion of methane under static and dynamic conditions were studied.
DOI: 10.1134/S1070427206040069

At present, a considerable attention is given to of nickel from raw materials with various acids and
the problem of utilization and processing of solid solutions of ammonia and ammonium salts.
wastes containing nonferrous metals. Wastes of this
kind are toxic substances hazardous to the environ- The use of ammonia for leaching-out of nickel
ment, on the one hand, and a valuable chemical raw relies on the fact that nickel hydroxides readily react
material, on the other. with ammonia to give stable complexes of various
compositions. This circumstance serves as a basis
A widely occurring type of solid wastes from pet- for recovery of nickel from oxidized ores [3], spent
rochemical and oil refining industries are spent cat- catalysts [4], and worked-out electrodes of nickel3iron
alysts, including nickel3alumina catalysts for steam batteries [5, 6]:
conversion of methane. In the course of operation,
the catalysts lose activity as a result of changes in Ni(OH)2 + 6NH3 6 [Ni(NH ) ](OH) .
3 6 2
their composition and structure. At high temperatures
(600 3700oC), the catalyst undergoes sintering and its It was found that addition of ammonium salts to
active surface area decreases.1 In the course of time, aqueous solutions improves the efficiency of dissolu-
a considerable fraction of nickel cations diffuses from tion via the buffer action precluding accumulation of
the catalyst surface deep inside alumina, active nickel OH! ions:
oxide is converted on alumina into inactive nickel
aluminate, and spinel-like compounds, inactive in Ni(OH)2 + 4NH3 + 2NH4Cl 6 [Ni(NH ) ]Cl
3 6 2 + 2H2O.
catalysis, are formed [1, 2].
In some cases, deactivated catalysts are regenerated, It has been suggested to leach-out nickel from ox-
but this cannot be done for a large number of cat- ide raw materials with solutions of (NH4)2SO4 and
alysts. They are removed from the process and re- (NH4)2CO3 and with mixtures of these at pH 6 3 8 [7]:
processed.
Commonly, two methods are suggested for recov-
NiO + (NH4)2SO4 + 4NH4OH 6 [Ni(NH ) ]SO
3 6 4 + 5H2O.

ery of nickel from ores and raw materials of tech-
nological origin: pyrometallurgical technique, whose
main product is ferronickel obtained at high tempera-
tures, and hydrometallurgical, based on leaching-out
ÄÄÄÄÄÄÄÄÄÄ
1 The temperature of steam conversion of methane is 800oC.
539
Leaching-out of nickel from ores and raw materials
of technological origin with solutions of mineral acids
was suggested in [8312].
However, the leaching methods described in the lit-
erature have certain disadvantages. For example, the
540 KOLOSNITSYN et al.
leaching solutions used are not always harmless: am-
monia, which is the most frequently used to leach-out
nickel, is a toxic gas. The leaching techniques sug-
gested by certain authors [8, 13] meet technological
difficulties. Autoclave leaching requires expensive
special apparatus. Use of acid solutions with pH < 1
for leaching-out of nickel complicates the process of
selective recovery of nickel from a solid matrix.
Nevertheless, the hydrometallurgical method for
nickel recovery, compared with the pyrometallurgical
technique, is the most promising because it conforms
to the principle of combination of environmental and
economical interests (markedly diminishes the number
of technological procedures, does not require fuel
expenditure for high-temperature processes, minimizes
the amount of solid wastes and toxic discharges into
the atmosphere). One more advantage of the given
technique is that it can recover from leaching solu-
tions, at an appropriate choice of methods used, both
metallic nickel (electrolytically) and its salts.
An analysis of published data demonstrated that,
despite the wide variety of methods for leaching-out
of nickel from raw materials of technological origin,
including spent catalysts, the fundamental aspects of
nickel recovery by the hydrometallurgical technique
are far from being fully understood.
The difficulty encountered in leaching-out of nickel
consists in that part of nickel is in the form of com-
pounds that are formed in the course of operation of
a catalyst and the composition of these compounds is
frequently unknown. Also, a certain part of nickel
may be situated deep inside (in pores) catalyst par-
ticles, at places inaccessible to the leaching solution.
One more difficulty is that, to obtain a product solu-
tion enriched with the target component, the leaching
solution should be selective with respect to the metal
being recovered and should not dissolve the catalyst
matrix.
The aim of this study was to examine the funda-
mental aspects of the process of nickel leaching-out
with sulfuric acid from spent nickel3alumina catalysts
for methane conversion.
EXPERIMENTAL
In the course of exploitation, a deactivated catalyst
is removed from reactors as it loses its activity and is
delivered to storage in batches. This gives a mixture
of spent catalysts that differ in the content of nickel,
degree of coking, porosity, particle shape, and other
properties.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY
As objects of study served spent nickel3alumina
catalysts of K-905 and K-87 brands for steam con-
version of methane. These catalysts are fabricated by
joint precipitation of nickel and aluminum hydroxides,
with the subsequent forming and calcination. There-
fore, nickel oxide is distributed throughout the cat-
alyst volume.
Grains of K-87 catalyst are gray cylinders about
15 mm in diameter and a height of 14 mm, and those
of K-905 catalyst are rings with outer and inner
diameters of 15 and 10 mm, respectively, and a height
of 14 mm.
An average sample was originally taken from
a batch of mixed catalysts. Then the sample was re-
duced to 100 3200 g by the ring-and-cone method [10].
It was noticed that the catalysts differ in outward
appearance. It was assumed that the degree of nickel
leaching-out from these catalysts will also vary. To
elucidate this question, part of catalyst samples were
classified into portions: portion 1, dark gray particles
of K-905 catalyst; portion 2, gray particles of K-905
catalyst; portion 3, black particles of K-87 particles;
and portion 4, gray particles of K-87 catalyst.
The content of nickel in a catalyst was deter-
mined by X-ray fluorescence analysis and by com-
plexometric titration.
The X-ray fluorescence analysis was made as fol-
lows. A 50-g catalyst sample was calcined in a muf-
fle furnace at 600oC for 2 h and then ground in
a ball mill to a dustlike state. The resulting powder
was compacted into pellets 10 mm in diameter and
5 mm high.
The catalyst samples were analyzed on a Spectro-
scan-4 automated X-ray spectrometer (Spektron-
OPTEL, St. Petersburg, Russia). The error in nickel
determination did not exceed 2.5%.
To determine the content of nickel by complex-
ometric titration, a 150-g catalyst sample was crushed
in an agate mortar to a particle size of 2310 mm,
placed in a 500-ml flask, poured over with 300 ml of
a 20% sulfuric acid solution, and the mixture was
boiled for 20 324 h. Preliminary studies demonstrated
that nickel is completely recovered from the catalyst
under these conditions.
The thus obtained leaching solution was titrated
with Na2EDTA at pH 9, maintained with an ammonia
buffer mixture. Murexide served as indicator.
The content of nickel in the catalyst sample was
7.05% according to the results of complexometric ti-
Vol. 79 No. 4 2006
 RECOVERY OF NICKEL WITH SULFURIC ACID SOLUTIONS FROM SPENT CATALYSTS 541

tration, and 7.04% as indicated by X-ray fluorescence Table 1. Ni recovery from catalysts with sulfuric acid
analysis. solutions of various concentrations under static conditions
(weight of catalyst sample 50 g)
Nickel was leached-out from the catalyst under
ÄÄÄÄÄÄÂÄÄÄÄÂÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄ
static and dynamic conditions.
Acid ³ Acid ³Leach- ³ Ni concentration in ³ Degree
Nickel was leached-out under static conditions as concen- ³ vol- ³ ing ³the leaching solution ³ of re-
follows. The reactor having the form of a cylindrical tration, ³ ume, ³ time, ÃÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄ´
³ ³ covery,
glass vessel (height 15325 cm, diameter 338 cm, vol- M ³ ml ³ h ³ g l!1 ³ M ³ %
ume 200 31000 ml) with a discharge cock was charged ÄÄÄÄÄÄÁÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄ
with a weighed portion of a mixture of spent catalysts. First stage
Then a prescribed volume of a sulfuric acid solution
0.5 ³ 75 ³ 59 ³ 21.2 ³ 0.36 ³ 55
was poured into the reactor. Every hour, the acid so-
1.0 ³ 75 ³ 59 ³ 23.1 ³ 0.39 ³ 61
lution was discharged from the reactor, a sample for
2.4 ³ 60 ³ 59 ³ 29.5 ³ 0.50 ³ 58
analysis was taken, and the solution was again poured
3.7 ³ 67 ³ 59 ³ 23.6 ³ 0.40 ³ 56
into the reactor. The experiment was performed until
a constant nickel concentration was reached in the Second stage
leaching solution.
0.5 ³ 75 ³ 43 ³ 7.1 ³ 0.12 ³ 70*
In the case of leaching under dynamic conditions, 1.0 ³ 75 ³ 43 ³ 7.7 ³ 0.13 ³ 77*
a weighed portion of a catalyst was placed in a conical 2.4 ³ 60 ³ 43 ³ 8.3 ³ 0.14 ³ 72*
vessel, poured over with a prescribed volume of a sul- 3.7 ³ 67 ³ 43 ³ 7.4 ³ 0.13 ³ 69*
furic acid solution, and agitated with a mechanical
Third stage
stirrer at a rate of 40 350 rpm. Samples for analysis
were taken from the leaching solution at regular in- 0.5³ 75 ³ 6.5 ³ 3.0 ³ 0.05 ³ 76**
tervals of time. As a pH value of 2 was reached in 1.0³ 75 ³ 6.5 ³ 3.0 ³ 0.05 ³ 83**
the leaching solution, concentrated sulfuric acid was 2.4³ 60 ³ 6.5 ³ 5.3 ³ 0.09 ³ 81**
added to pH 0.7. The experiment was terminated as 3.7³ 67 ³ 6.5 ³ 5.3 ³ 0.09 ³ 79**
a constant nickel concentration was reached in the ÄÄÄÄÄÄÁÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄ
leaching solution at pH 2. * Total degree of recovery in the first and second stages.
** Total degree of recovery in the first, second, and third stages.
The sulfuric acid solutions were prepared by dilu-
tion of concentrated (91392%) sulfuric acid. The con-
centration of sulfuric acid in the solutions prepared tainment of equilibrium by the leaching process is not
was determined by acid3base titration. related to formation of nickel-saturated leaching so-
The influence exerted by the concentration of sul- lutions in the reactor volume. The solubility of nickel
furic acid on the rate and extent of nickel leaching-out sulfate in sulfuric acid solutions was evaluated. It was
from the catalyst under static conditions was studied. found that the solubility of nickel sulfate at 25oC is
Irrespective of the acid concentration, complete recov- 59 g l!1 in a 30% sulfuric acid solution and 103 g l!1
ery of nickel from the catalyst could not be achieved. in a 5% solution.
Therefore, leaching was performed in several stages
in order to obtain the maximum possible degree of It was assumed that the equilibrium position is
nickel recovery. For this purpose, the leaching solu- determined in this process mode by saturation with
tion was discharged after a steady state was attained. nickel of leaching solutions that fill pores in catalyst
After that the catalyst was poured over with the same particles and by blocking of these pores by nickel
volume of a fresh sulfuric acid and leaching was con- sulfate precipitated from saturated solutions.
tinued until a new steady state was attained. The re- To confirm the blocking of pores in catalyst par-
sults obtained are listed in Table 1. ticles by nickel sulfate, an attempt was made to per-
The studies demonstrated that equilibrium is at- form a microscopic study of the cross-section of cat-
tained in the second and third stages of leaching at alyst samples before and after leaching. However, no
a lower nickel concentration in solution: about 0.13 M reliable and unambiguous results confirming that crys-
in the second stage, and 0.07 M in the third. In all talline nickel sulfate is present in the pores of catalyst
cases, the concentration of sulfuric acid has no effect particles could be obtained. Therefore, to verify
on the degree of nickel recovery (nickel concentration the assumption made above and to examine the pos-
in leaching solutions). These facts indicate that the at- sibility of preventing the blocking of the pores in the
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 79 No. 4 2006
542 KOLOSNITSYN et al.

Table 2. Ni recovery from catalysts with a 1% sulfuric acid solution under static conditions, with the leaching solution
strengthened at regular intervals of time (initial H2SO4 concentration in the leaching solution 0.1 M)
ÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÂÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄ
Weighed ³ Acid ³ ³ Leaching ³ Final Ni concentration in the leaching solution ³ pH of the ³ Degree
o
portion of ³ volume, ³ T, C ³ time, ÃÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ´
³ ³ leaching ³of recovery,
a catalyst, g ³ ml ³ ³ h ³ g l!1 ³ M ³ solution ³ %
ÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÅÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄ
250 ³ 500 ³ 25 ³ 384 ³ 23.16 ³ 0.40 ³ 0.75 ³ 82.3
5000 ³ 10 000 ³ 15 ³ 233 ³ 28.47 ³ 0.49 ³ 1.65 ³ 81.3
100 ³ 150 ³ 20 ³ 233 ³ 20.65 ³ 0.36 ³ 1.13 ³ 88.4
ÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÁÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄ

o
Table 3. Ni recovery from catalysts with 1% sulfuric acid solutions under dynamic conditions (total leaching time 240 h,
s : l = 1 : 2, temperature 23 C, pH of the leaching solution 1)
ÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÒÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄ
Cat- ³Ni concentration in the leaching solution ³ Degree º Cat- ³Ni concentration in the leaching solution ³ Degree
alyst ³
ÃÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄ´³ of recov- º alyst ÃÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄ´
³ ³of recov-
sample³ g l !1 ³ M ³ ery, % º sample³ g l!1 ³ M ³ ery, %
ÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄ×ÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄ
1 ³ 8.1 ³ 0.14 ³ 23 º 3 ³ 12.7 ³ 0.22 ³ 36
2 ³ 10.0 ³ 0.17 ³ 28 º 4 ³ 19.5 ³ 0.34 ³ 55
ÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÐÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄ

catalyst by particles of nickel sulfate, leaching under
static conditions with a dilute (1%) sulfuric acid so-
lution, strengthened at regular intervals of time, was
studied.
The leaching solution was strengthened with a 20%
sulfuric acid solution after the solution pH reached
values of 233. The volume of the 20% sulfuric acid
solution added to the leaching solution was chosen so
as to restore the initial concentration of sulfuric acid
in the leaching solution. The leaching-out of nickel in
this mode was also performed until the leaching so-
lution was saturated with nickel ions. The results ob-
tained in these experiments are listed in Table 2. In
all cases, leaching solutions with a high concentration
of nickel sulfate and greater degree of nickel leaching-
out from the catalyst were obtained. The results of
these experiments confirmed the validity of the as-
sumption that the catalyst pores are blocked by nickel
sulfate when concentrated sulfuric acid solutions are
used as a leaching agent.
A study of the leaching process under static con-
ditions demonstrated that its rate is low. The possible
reason may be the appearance of an outer-diffusion
control over the leaching process. Therefore, leaching
was studied under dynamic conditions, because the
outer-diffusion limitations are lifted in this mode.
Nickel was leached from four catalyst samples
differing in the outward appearance with a 1% sul-
furic acid solution at 20 325oC, with permanent
RUSSIAN JOURNAL OF APPLIED CHEMISTRY
strengthening of the leaching solution. The results
of these experiments are listed in Table 3. It can be
seen that the degree of nickel recovery does rather
strongly depend on the type of a sample, but does
not exceed 55% at the very best.
As demonstrated by the results of the experiments,
the concentration of the sulfuric acid solution has
no effect on the extent of nickel leaching-out from
catalyst particles. In leaching-out of nickel with
both concentrated and dilute sulfuric acid solutions,
the degree of nickel recovery is virtually the same
(553 60%). The experimental study also revealed that,
in leaching-out of nickel with a dilute (1%) sulfuric
acid solution under dynamic conditions, the degree
of nickel recovery from the catalysts is lower than
that in leaching with the same solution under static
conditions, with the leaching solution periodically
discharged from the reactor and the same solution
poured in.
It follows from the experimental results that
the leaching-out of nickel from the catalyst is limited
by its diffusion from catalyst pores into the bulk of
the leaching solution. In those cases when the rate
of nickel diffusion from the catalyst pores is lower
than the nickel dissolution rate, nickel sulfate is de-
posited in the catalyst pores, pore mouths are com-
pletely blocked by solid products, and leaching ter-
minates. Agitation of the leaching solution (dynamic
mode) does not lift the inner-diffusion limitations.
Vol. 79 No. 4 2006
 RECOVERY OF NICKEL WITH SULFURIC ACID SOLUTIONS FROM SPENT CATALYSTS
The leaching rate can be markedly raised if the cat-
alyst pores are periodically freed of the leaching so-
lution.
CONCLUSIONS
(1) Nickel recovery from spent alumina3nickel
catalysts for methane conversion mainly occurs in
the inner-diffusion region and is controlled by the rate
of nickel diffusion from catalyst pores into the bulk
of the leaching solution.
(2) The maximum possible degree of nickel re-
covery from catalyst particles (85390%) and the min-
imum expenditure of the reagents are achieved in
leaching with a dilute (1%) sulfuric acid solution,
with permanent strengthening of this solution in
the course of leaching and catalyst pores periodically
freed of the leaching solution.
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