Light Metals 2009 Edited by: Geoff Bearne

TMS (The Minerals, Metals & Materials Society), 2009

Quality of Russian Petroleum Cokes for Aluminum Production

V.Yu. Buzunov, A.S. Tayanchin, I.V. Cherskikh, V.M. Polovnikov
Technology Directorate in RUS-Engineering Krasnoyarsk Office
Key words: coke, anode formulation, electrolysis, aluminum
Abstract

Russian coke market: Review

Green petroleum coke is produced at six oil refineries in the

Russian Federation. In 2007, the total output of green petroleum
cokes was about 1200 thousand tonnes. The Russian cokes can
conditionally be divided into three groups: the first (S<1.8%,
V<0.025%) includes the cokes made by the oil refineries of
Volgograd, Omsk and Angarsk, the second (S2.7%,
V0.035%) includes the coke made by Perm oil refinery, the
third (S4%, V0.07%) cokes made by Novokuibyshevsk and
Novoufimsk oil refineries. Cokes with S<1.8% amount to 50%
of all cokes produced. The CO2 reactivity of Russian cokes is
relatively low (up to 15%) after calcination in rotary kilns.

Green petroleum coke in the Russian Federation is produced at

six oil refineries. In Russian and CIS countries, the delayed
cokers were built only to produce special coke types consumed
by the aluminum and steel industry, i.e. to produce anode and
electrode cokes with high density and low content of metals and
sulfur. Therefore, in the former USSR the delayed cokers were
built only by the oil refineries having access to local sweet oil
(Baku, Krasnovodsk, Guriev, Kherson, Volgograd) or had
supply of Western Siberian sweet oils (Angarsk, Omsk,
Pavlodar). According to Petrocoke in Russia-Promising
Technologies [1], Russian oil refineries operate eight types of
delayed cokers. Concept description of Russian delayed cokers
is given in Tables 1, 2.

To produce anode paste the aluminum smelters generally blend

cokes produced from several sources. Because of instability of
the coke market, the composition of blends is not constant,
therefore, each smelter blends cokes based on current supplies.
The paper presents experience of applying different coke
mixtures in different smelters of the Company.

Out of eight delayed cokers operations, only three (Perm,

Novokuibyshevsk and Ufa) process high sulfur-bearing oil to
produce coke of fairly good quality, however they are high
sulfur and vanadium content.

Table 1: Russian Delayed cokers: General Characteristics

Manufacturer
1. Bashneftechim (Ufa)
2. Lukoil Volgogradneftepererabotka (Volgograd)
3. Lukoil Volgogradneftepererabotka (Volgograd)
4. Lukoil Volgogradneftepererabotka (Volgograd)
5. Lukoil Permnefteorgsintez (Perm)
6. Sibneft, Omsky refinery (Omsk)
7. Angarsk petrochemical company (Angarsk)
8. Novokuibyshevsk NPZ ( Novokuibyshevsk )

Design
capacity on
feed, t/y x 103
300
300
300
600
600
600
600
1500

Year of
commissioning
1955
1963
1966
1982
1970
1971
1971
1986

Coking operating parameters

Feed temperature at the
Pressure in
exit of the furnace,
reactor P
485-490
0.18
480-485
0.18
480-485
0.18
482-487
0.22
477-483
0.32
480-486
0.35
473-477
0.37
480-485
0.28

Table 2: Green Petroleum Coke output in Russian Oil Refineries

Manufacturer
Ufa
Volgograd
Perm
Omsk
Angarsk
Novokuibyshevsk
Total Russia

Volume
Processed,
t/y x 103
220
980
1080
607
505
642
4 034

2000
Green Coke,
t/y x 103

Coke yield,
% mass

49.5
243.9
244.4
155.4
112.0
155.6
960.8

22.5
24.9
22.6
25.6
24.1
24.2
23.8

927

Volume
Processed,
t/y x 103
435.0
943.8
842.4
575.3
530.8
519.6
3846.9

2005
Green Coke,
t/y x 103

Coke yield, %
mass

194.4
252.3
221.6
168.6
145.8
166.1
1108.8

35.5
26.7
26.3
28.8
27.5
32.0
28.8

Today, petroleum coke with less than one-percent sulphur is not

available in Russia and the deficit of low sulphur anode coke for
the aluminum industry is covered by supplied primarily from
China.

A Consultants study [2] demonstrated that the Russian cokes

(Figure 3 and Table 4) exhibit typical microstructures with
acceptable mercury porosity and vibrated bulk density values.

The cokes of the Russian Federation can conditionally be divided

into three groups: The first group, (S<1.8%, V<0.025%) includes
the cokes made at the Volgograd, Omsk, and Angarsk oil
refineries. The second group, (S2.7%, V0.035%) is the coke
made at the Perm oil refinery. And the third group, (S4%,
V0.07%) are made at the Novokuibyshevsk and Ufa oil
refineries (Figure 1).The average quality rating of all Russian
cokes is given in Table 3.

25
Reactivity in CO2, %

20
15
10
Omsk

Volgograd

Ja
nF e 07
b0
M 7
ar
-0
Ap 7
rM 07
ay
-0
Ju 7
n0
Ju 7
lA u 07
gS e 07
p0
O 7
ct
N 07
ov
D 07
ec
-0
Ja 7
n0
Fe 8
b0
M 8
ar
-0
Ap 8
rM 08
ay
-0
Ju 8
n0
Ju 8
lA u 08
g08

Figure 2: 2 Reactivity of Russian CPC

0,12
Novo-Kuibyshevsk,
Ufa

Vanadium , %

0,10

Table 4: Technical quality of Russian cokes

Volgograd,
Omsk,
Angarsk

0,08
0,06

Manufacturer

Perm

0,00
1

3
Sulphur, %

Mercury
porosity, cm3/g

Bulk density
g/cm3

2.031

0.102

0.865

2.031
2.029
2.030

0.113
0.115
/

0.858
0.859
0.860

NovoKuibyshevsk
Omsk,
Volgograd
Perm

0,04
0,02

Real density,
g/cm3

Figure 1: Sulfur and Vanadium content in Russian cokes

VBD, g/cm3

The Volgograd and Omsk oil refineries have rotary kiln

calcination facilities where they calcine 45-60% of their product.
RUSALs two largest smelters, Bratsk and Krasnoyarsk each have
four rotary kiln calciners. The rotary kilns, forty-five meters in
length and three meters in diameter are used for the production of
calcined coke used in their for Sderberg cell technology.
The CO2 reactivity of the Russian cokes is relatively low. Figure
2, shows the reactivity of calcined cokes from Omsk and
Volgograd used in production of prebaked anode at the
Sayanogorsk Aluminium Smelter.

0,95
0,93
0,91
0,89
0,87
0,85
0,83
0,81
0,79
0,77
0,75

Novo-Kuibyshevsk

Omsk/Volgograd

Pavlodar
More Isotropic

More Anisotropic
7

10

11

12

GPC Volatiles, %

Figure 3: GPC Percent Volatile versus CPC Vibrated Bulk

Density

In line with the world trend of feedstock degradation, the Russian

cokes exhibit increasing percentages of sulfur and vanadium.
Because of this, RUSAL smelters like the smelters in other
countries are adopting new methods of employing these cokes in
production without deterioration of smelter performance.

Figure 4 shows the changes in supplies over the last five years to
RUSALs smelters of green petroleum coke according to
classification into the three relative groups.

Table 3: Volatile Content and Green Cokes Impurities

Manufacturer
Omsk
Volgograd
Angarsk
Perm
Novo-Kuibyshevsk
Ufa

Volatiles, %
8
8
8
8.5
8
9.8

S, %
1.4
1.6
1.5
3.0
4.4
4.0

Ash, %
0.15
0.20
0.10
0.15
0.28
0.38

928

Fe, %
0.015
0.020
0.010
0.020
0.022
0.045

Si, %
0.020
0.015
0.010
0.010
0.026
0.034

V, %
0.015
0.020
0.015
0.040
0.087
0.070

Na, %
0.006
0.010
0.010
0.010
0.012
0.013

is then supplied with coke from only one group. Moreover, the
calcination process parameters (throughput and calcination
temperature) are established for different combinations of green
coke based on green coke properties.

100%
90%
80%
70%
60%

57,3%

53,6%

45,4%

43,5%

51,4%

70,3%

Table 5: Sources of Bratsk Supplied Green Petroleum Coke

2003-2008, Percent

50%
40%

29,8%
24,7%

30%
20%
10%

26,2%

40,0%

34,5%

Source
Angarsk
China
Volgograd
Pavlodar
Perm
Ufa
Brazil
Omsk
Turkmenistan

13,1%
16,6%

18,0%

20,2%

24,7%

2003

2004

2005

2006

16,5%

14,0%

2007

2008

0%
(S4%, V0,07%)

(S2,7%, V0,035%)

(S<1,8%, V<0,025%)

Figure 4: Green Coke Supplies to Smelters

From Figure 4, it can be seen that the percentage of coke with low
sulfur content in the last five years has decreased by about a third,
from 70.3% in 2003 to about 43.5-51.4% in 2007-2008. The main
cause of the redistribution is mostly due to increasing supplies of
coke with S2.7% and V0.035%. Currently, supplies of green
cokes (including imported) with sulfur content exceeding 1.8
percent with vanadium over 0.025 percent meet half of the
demand of RUSALs smelters.

2003
32,5
45,6
0,0
0,7
12,1
6,5
0,0
0,0
2,5

2004
32,5
37,4
1,3
14,5
3,8
4,1
0,0
4,5
1,8

2005
30,8
35,9
0,0
8,2
0,0
19,6
0,0
0,0
5,5

2006
37,1
18,7
6,4
3,9
9,8
24,0
0,0
0,0
0,0

2007
35,9
12,2
9,4
27,3
15,3
0,0
0,0
0,0
0,0

2008
40,9
15,1
8,2
20,2
13,0
0,0
2,5
0,0
0,0

The conditionally constant mixture is made by blending the cokes

in several stages from unloading, calcining, and use in the
transportation, crushing and in-process storage. Calcined coke
real density (2.030.02 g/cm3) is used to monitor the quality and
stability of calcination.

Use of Russian Petroleum Cokes in the Company Smelters

The cokes with elevated volatile content (among them are the
cokes supplied from China and Brazil) are calcined at higher
temperature up to 123050 0. The sulfur content is constantly
evaluated in the total blend after calcination to monitor the
effectiveness of the blending process. If the sulfur content differs
considerably from the weighted average calculated from the sulfur
level and proportion in the blend of each green coke this is
indicative blending process problems and adjustments to the
process are made.

The essentials of anode paste production are determined by the

productive capacity of the smelter the higher the anode paste
demand the larger is the volume of coke to be processed. For
example, the Krasnoyarsk Aluminium Smelter annually consumes
about 400 thousand tonnes of green coke in the production of
Sderberg anode paste. Since none of the potential suppliers are
capable of supplying this volume of green coke, the smelter can
be processing green cokes from 4 to 8 suppliers at any given time.
The basic principles for storing and blending have been
determined for processing the assortment of cokes:
Similar Grades (for example, volatile content): The
blend is formed from all cokes supplied to the smelter
with account of their quality and percentage of supply.
This provides for maximum possible consistency of
properties of the coke aggregate used to produce the
anode paste.
Physical and Chemical Properties: The first priority
classification principle is the sulfur content.

Krasnoyarsk Aluminium Smelter (KrAZ)

In 2007, KrAZ produced about 870 thousand tonnes of primary
aluminium using Sderberg technology and about 480 thousand
tonnes of anode paste.
The smelter uses the green cokes from six domestic suppliers and
imported cokes primarily from China and the Ukraine (Table 6).
Table 6: Sources of Krasnoyarsk Supplied Green Petroleum
Coke 2003-2008, Percent

To illustrate consider the operational experience of Krasnoyarsk

and Bratsk smelters.

Manufacturer
Omsk
Novokuibyshevsk
Volgograd
Pavlodar
Perm
China
Brazil
Turkmenistan
Ufa
Ukraine
Azerbaijan

Bratsk Aluminium Smelter

In 2007, Bratsk produced about 995 thousand tonnes of primary
aluminum, and about 500 thousand tonnes of anode paste using
cokes of the domestic manufacturers Angarsk, Volgograd, and
Perm oil refineries and imported cokes mostly made in China.
Table 5 presents dynamics of green petroleum cokes supplies
from different manufacturers from 2003 to 2008. From Table 5 it
can be seen that the assortment of cokes is inconsistent and
subject to changes.
By the above principles, the cokes are conditionally divided into
two groups based on sulfur content. Each group of cokes is
unloaded and stored at the coke storage separately. Each calciner

2003
16,1
27,7
15,6
11,4
1,9
7,4
0,0
19,9
0,0
0,0
0,0

2004
12,1
33,0
18,9
0,0
32,0
0,0
0,0
3,1
0,9
0,0
0,0

2005
15,3
20,9
11,1
7,7
37,7
0,0
0,0
7,3
0,0
0,0
0,0

2006 2007 2008

18,1 19,0 18,4
25,6 32,1 27,1
2,4
0,0
0,0
12,5 0,4
7,2
36,1 37,2 28,5
5,3
9,4
8,8
0,0
0,0
3,2
0,0
0,0
0,0
0,0
0,0
0,0
0,0
1,8
2,1
0,0
0,0
4,6

The cokes supplied to the smelter are conditionally divided into

three groups: Group I high sulfur content: Novokuibyshevsk oil

929

refinery; Group II medium sulfur: Perm, Pavlodar oil refineries

and Group III low sulfur content: Omsk, Volgograd, China,
Ukraine and Azerbaijan. Within each group, the green cokes are
blended by loading and storing in separate coke storage zones.
The conditionally constant mixture is made by alternate loading of
green coke into the crushers and receiving hoppers of each
calciner. This ensures consistency of coke mixture to be calcined.
The quality and stability of calcination on each calciner is
monitored by real density of calcined coke (2.030.02 g/cm3).
Blending process effectiveness is monitored in analogy by
evaluating actual sulfur and vanadium content in the anode paste
and weighted average calculated value determined by the
proportion of each group coke used.

3,00

0,050
0,045

2,50

0,96

0,50

0,94

2,29

2,23

2,25

2,00

2,15

1,00

1,50

0,030
0,025
0,020

vanadium %

0,035

1,50

0,96

sulfur, %

0,040
2,00

0,015

0,00

0,010
2000 2001 2002 2003 2004 2005 2006 2007 2008
content S

content V

Figure 5: Percent Sulfur and Vanadium Krasnoyarsk Sderberg

Anode Paste

This practice of using cokes from different suppliers provides for

steady and satisfactory quality as witnessed by the laboratory
baked Sderberg anode paste sample with: resistivity 65-70
*m; compressive strength 35-40 MPa; porosity 25-30%;
2 reactivity 20-25 mg/cm2*h and air reactivity 120-130
mg/cm2*h. In actual cell operation, the anode paste consumption
is about 515 kg/t Al and carbon dust is somewhat high at about 30
kg/t Al.

The weighted average sulfur content in the anode paste produced

for the experimental cells was 0.8% higher than in the
conventional paste. The paste with elevated sulfur content
increased stud corrosion rate by 20% (Figure 6); increased anode
voltage drop by 0.012 V; and it increased iron content in
aluminum metal by 0.02% on the average even with shot-blasted
studs.

Domestic petroleum cokes are also used by Sayanogorsk

Aluminium Smelter to produce prebaked anode blocks since
Sayanogorsk does not have calciners. The calcined coke is
supplied from both the Omsk and Volgograd oil refineries with
real density 2.06-2.09 g/cm3. The cokes from each producer are
unloaded separately and used in production of single coke source
green anodes.

88,0
86,0
84,0

mm

82,0
80,0
78,0

Use of Anode Paste with Elevated Sulfur and Vanadium

Content

76,0
74,0
72,0

In line with the world trend, the chemical characteristics of

Russian cokes are deteriorating, and this is primarily attributed to
the increase in sulfur and vanadium levels. Figure 5 illustrates
dynamics of deteriorating coke as the average increase in sulfur
and vanadium levels in the Krasnoyarsk Aluminium Smelter
anode paste production, 2000 to 2008.

30.11.07 31.12.07 31.01.08 31.03.08 30.04.08 31.05.08

pilot group

control group

Figure 6: Dynamics of Stud Erosion (Reduction in Diameter)

It should be noted, that tests of anode paste made from coke with
high sulfur and vanadium content did not demonstrate negative
impact on anode performance in either anode paste consumption
or carbon dust generation. The tests are continuing and the final
results shall be presented at the Conference.

Green petroleum coke with high sulfur content from the

Novokuibyshevsk oil refinery (S4.0%, V0.075%) was calcined
and used to produce anode paste for testing on the experimental
group of cells at Krasnoyarsk to evaluate the effect of anode paste
with elevated sulfur and vanadium content on the anode quality
and cell performance. The studies showed that the quality
characteristics of the anode paste made on the basis of this coke
meet the smelter requirements as tested in the laboratory except
for an increase of resistivity and air reactivity (an increase on the
average by 10-15 mg/cm2*h). In certain batches, sulfur content in
the anode paste was up to 3.3%, and vanadium content up to
0.081%.

Conclusion
The world tendency of deterioration in coke quality manifesting
as elevated percentages of sulfur and vanadium introduces
additional considerations in blending and their use in larger
smelters. In some cases, the main difficulties are due to lack of
production area or facilities for the blending of the coke with good
quality with the cokes of lesser quality for the production of good
anode quality. The main challenge under existing production
conditions is to produce carbon products (anode paste, anode
blocks) with optimum characteristics to provide for required
electrolysis parameters.
RUSAL is continuing to carry out work and experimental
programs aimed at evaluating the feasibility of using high-sulfur
cokes (S>4%) for the anode paste and prebake anodes. During the
process, additional experience will be gained on the performance
of very high sulphur and high vanadium cokes.

930

The goal of this work is to establish the parameters for forecasting

or predicting the possible changes in electrolysis process caused
by increasing sulfur and vanadium content in the anode.
However, it is recognized that one of the main challenges to using
high sulphur and vanadium cokes will be dealing with sulphur
dioxide emissions and contamination of the aluminium with iron
and vanadium.

Acknowledgments
The authors express their gratitude to Barry Sadler for the
possibility to use results of his studies and John A. Johnson for
critical remarks.
References
1.

2.

Elshad Telyashev, Petrocoke in Russia-Promising

Technologies (Conference Oil and Gas Processing
and Petrochemistry 2006 Ufa, 2006).
Barry Sadler (Calcination of petroleum coke in rotary
calciners, Krasnoyarsk, 2004)

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