TRAVAUX 49, Proceedings of the 38th International ICSOBA Conference, 16 – 18 November 2020

CB04 - Impact of Quality Changes in Calcined Petroleum Coke (CPC)

on Anodes Used for Aluminium Production
Binuta Patra
DGM (R&D), National Aluminium Company Ltd, Bhubaneswar, India
Corresponding author: [email protected]
Abstract

Calcined Petroleum Coke (CPC) has been in use for more than 120 years to produce the carbon
anodes used in the Hall-Heroult Aluminium electrolysis process. Performance of the anodes in
the aluminium electrolysis process depends on many properties of CPC. It is seen that over the
last several years quality and availability of anode grade petroleum coke has been impacted by
changes in the petroleum refining industry. Refineries have started using sour crudes that have
high sulphur and metallic impurities due to shortage of sweet crudes coupled with high demand
for oil. As a result, RPC from refineries are having higher sulphur content and metal impurities.
Therefore, smelters worldwide are using CPC with higher sulphur content to meet their
requirements. The increasing trend of impurities in CPC used by Indian industry is a major
concern for the industry. In this paper, the quality variations observed in CPC used by NALCO
and their impact on anode quality is highlighted along with presentation of few R&D studies
carried out at NALCO, the findings of which may be helpful to deal with expected future quality
changes in CPC.

Keywords: Calcined Petroleum Coke, Anode, impurities.

1. Introduction

Calcined petroleum coke (CPC) is one of the major raw materials for the Aluminium Industry.
Like any other raw material, it plays a significant role in the aluminium production process. CPC
is used for fabrication of anodes used in the aluminium electrolysis process. Extensive research
is taking place since more than 30 years to find an alternative to this material. From the recent
reports [7][8], it is evident that though considerable progress has been made in finding right kind
of materials for making inert anodes, it may take many years to address the impending problems
associated with fabrication and use of inert anodes. Hence today more focus is required on the
carbon anodes made out of CPC & coal tar pitch (CTP) for continual improvement of performance
of the electrolytic pots producing aluminium metal.

In the present day, the global production of primary aluminium is around 64 Mt, China being the
single largest producer of aluminium contributing to 57 % of total world production. The global
demand of aluminum has grown at an average rate of 4.5 % in the past five years. If the same
trend continues in future, by 2025 the aluminum production will reach a level of about 87 Mt/a.
Primary aluminium installed capacity in India is today 4.1 Mt with expansion plans and other
development plans in place. Further, the Indian aluminum demand has grown at an average rate
of 12 % in the past four years. If the same trend continues in future, by 2025 the Indian aluminum
production will reach a level of about 8 Mt/a, which means increasing the production capacities.
In accordance to increase of aluminium capacity, requirement of CPC for Indian aluminium
industry is going to increase from the current 1.3 Mt to 2.6 Mt. Availability of suitable grade of
CPC for anode production is going to be a challenge for the Indian Aluminium industry. There is
a shortfall of 92 % CPC with <1.25 % S and 82 % CPC with 2.5 % S in India. It is seen that over
the last several years quality and availability of anode grade petroleum coke has been impacted
by changes in the petroleum refining industry. The refineries have started using sour crudes that
have high sulphur and metallic impurities due to shortage of sweet crudes coupled with high
demand for oil.

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National Aluminium Company (NALCO) established in 1981 in the state of Odisha has its smelter
complex situated at Angul. The plant has been set up in technical collaboration with aluminium
Pechiney and operates the AP18 pots in four potlines having total 960 pots augmented with its
own carbon plants equipped with most advanced technology producing prebaked anodes
NALCO, since its inception has been using CPC of different varieties. This paper focuses on the
impact of various properties of CPC on the anode quality. A few R&D studies carried out to find
possible solutions to improve anode quality in the face of deteriorating CPC quality are included
in this paper.

2. Calcined Petroleum Coke

2.1 Crude Oil to Coke

The choice of crude processed in a refinery is strongly affected by location of crude and refinery
design and is normally independent of coke quality considerations. Crude oil has an elementary
composition C: (84-87) %, H2: (11-14) %, S: 0.2 %, N2: 0.2 % and is a mixture of hydrocarbons
which range in boiling points from 0-80 °C. It is distilled under atmospheric pressure followed
by a distillation under vacuum. Typical products from a barrel of crude oil are light straight run
gasoline 11 %, reformer naphtha 25 %, kerosene 15 %, diesel fuel 10 %, gas oil 10 % and residue-
coker feedstock 8 %. The residue is heated to approx. 500 °C and is directed to the bottom of one
of the coke drums. Here sufficient retention time (32 h) and temp is provided in order to permit a
slow formation of coke (hence the term delay coking).

2.2 Coker Products

1. Shot coke; it is spherical in shape 2- few (25 cm) in size, have high CTE; have a slick shining
exterior coating of needle type carbon.

2. Fuel coke; fuel coke has a less optimal macrostructure, has a high coefficient of thermal
expansion (CTE). It is the least valuable material in the non-fuel market.

3. Sponge coke; sponge coke or honeycomb coke, the pore structure is more pronounced and CTE
is decreased. This is the anode grade coke.

4. Needle coke; it has a characteristic needle like surface. This coke has the lowest CTE and low
in metals and sulfur. Most of the graphite manufacturers use this coke.

2.3 Raw Petroleum Coke (RPC) to Calcined Petroleum Coke (CPC)

Raw petroleum coke is calcined to remove excess water and volatile matter in rotary kilns or shaft
kilns. Rotary kilns are most widely used for economic reasons. Calcination temps are between
(1250-1400) °C. The calcined coke leaving the kiln is discharged into a rotary cooler, where it is
quenched with direct water spray at the inlet and then cooled by a stream of ambient air. The
calcining operation can have an important influence on coke quality. Cokes with significantly
different volatile contents (quality and quantity) and impurity levels should be calcined
differently. Calciner process variables affecting CPC quality is given in Table 1.

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Table 1. Calciner process variables affecting CPC quality.

Calciner process variable Effects
Green coker volatile content As the VM increases, coke will experience higher heat up
& how fast the coke is heated. rates which reduces bulk density and porosity increases.

Calcining temperature Increase in calcinations temperature will increase the coke’s

real density and reduce the coke’s reactivity. (The preferred
real density should be where the binder coke reactivity
matches the filler coke reactivity). If the temperature is too
high, significant quantities of Sulphur in the coke will be
released increasing the cokes porosity.
Cooling water quality Contaminants like Ca & Na will increase the reactivity coke.

Storage transportation Sizing and storage activities can possibility add impurities.

2.4 CPC to Anodes

Green anodes are made by mixing around (55-60) % calcined petroleum coke, (30-35) % recycled
butts along with (14-15) % coal tar pitch and vibrocompacting to 1.25-1.27 T blocks. These green
anodes are baked in refractory brick lined baking furnaces to high temperatures (1090-1110) °C
anode baking temp) to attain the properties of stable and unreactive anodes for giving stable
performance in the electrolysis cells.
The anode manufacturing process involves the following major steps
- Preparation of dry aggregate consisting of various fractions of calcined petroleum coke
having different particle sizes & recycled anode butts by crushing, sieving, grinding &
proportioning
- Preheating the dry aggregate
- Mixing the dry aggregate with pitch in a mixer
- Vibrocompacting or pressing the green paste to form anode blocks
- Baking the green anodes in refractory lined bake ovens by indirect heating through heavy
furnace oil or flue gas following a regulated fire cycle.

Primary aluminium is produced by electrolytic reduction of alumina using the Hall-Héroult

processes. Alumina, an oxide of aluminium, is dissolved in a molten cryolite bath at
approximately (950-960) °C and electrolyzed in a reduction cell by direct current. Carbon
prebaked anodes are used as positive current carriers in production of aluminium and need to be
periodically replaced in the cell as they are consumed. These anodes have a lifetime of (24-30)
days and the remaining anode butt is cleaned and recycled back in the production of green anodes.

The overall chemical reaction in the aluminium production is summarized as in equation (1).

2Al2O3 (dissolved) + 3C (solid) → 4Al (liquid) + 3CO2 (gas) (1)

The theoretical consumption of carbon as per the reaction is 334 kg per one ton of aluminium
produced. However, the actual carbon consumption is (400-450) kg/t of aluminium produced. The
important anode performances include high resistance to oxidation to minimize excess carbon
consumption, high density and low permeability, good mechanical strength for structural integrity
and handling, low specific resistance values, high elemental purity to avoid contamination in
metal and high thermal shock resistance to avoid cell disruptions. Any variation in the properties
of CPC are reflected in the quality of anodes if process is not adapted to variations. Some inherent
properties of CPC are directly linked to the product anodes and may not get affected by the process
adaptions.

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3. Quality Aspects of CPC Affecting Anode Quality

Most of the CPC properties have a direct impact on anode quality and anode performance in the
electrolysis process. Their impact on anode quality/performance is shown in Table 2.

Table 2. Quality aspects of CPC and their impact on anode quality.

Sl. Parameters Range Anode quality/
No performance
1 Apparent Density (Hg), 1.7-1.8 Directly related to baked anode density.
g/cm3 Anode cycle is decided based on the baked
anode density.
2 Real Density, g/cm3 2.05-2.08 It indicates the calcination level of CPC
and baking level in anode making is
adjusted as per this value.
3 Hard grove grindability 33-42 It indicates the hardness of coke and ease
Index (HGI) with which fines are produced by ball mill.
4 Particle Size 30-40 It affects the level of dry aggregate fractions
(+4.75 mm-0.30 mm), in proportioning system. Density of anodes
% also gets affected.
6 % Sulphur (S) 0.5-3.00 It affects the CO2 reactivity of anodes and
baking level is adjusted if ‘S’ content is high
to minimise desulphurisation.
8 % Iron (Fe) 0.010-0.060 Fe content in aluminium metal is affected
9 % Silicon (Si) 0.010-0.040 Si content in aluminium metal is affected
10 % Vanadium (V) 0.002-0.025 It affects the air reactivity of anodes.
11 % Nickel (Ni) 0.002-0.025 It affects the air reactivity of anodes.
12 % Sodium (Na) 0.005-0.030 It affects the air & CO2 reactivity of anodes
13 % Calcium (Ca) 0.005-0.020 It affects the CO2 reactivity of anodes.
14 Air reactivity %/min 0.05-0.15 It affects the air reactivity of anodes
15 % CO2 reactivity 10-24 It affects the CO2 reactivity of anodes

4. Changes in CPC Quality and their Impact on Anode Quality

Coke apparent densities are decreasing over the years. Coke apparent density are dependent on
both crude type and coker operation. The preferred coke for anode making is sponge coke.
However, shot cokes having isotropic structure and high coefficient of thermal expansion are now
a days blended to lower the cost of coke. If present in large percentages anodes may experience
cracking problems and mechanical poperies will go down.

The trend of increasing vanadium, nickel and sulphur and other impurity levels is the most
problematic issue facing the industry today. Vanadium and Nickel occur as trace organometallic
impurities in crude oil and are soluble in crude oil which cannot be separated after processing.
These impurities are undesirable as these directly affect the metal purity. Usually, the high
Sulphur cokes are associated with presence of high values of Vanadium which is a catalyst for
reaction of carbon anodes with oxygen at elevated temperatures. Increased air burn means excess
anode consumption and cell performance disturbance. Increased Vanadium also affects the
conductivity of EC Wire rods produced in smelter cast houses. Calcium, silicon, sodium and iron
are also undesirable impurities in CPC. Increased calcium in CPC can have significant negative
affect on CO2 reactivity of coke and anodes.

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Average sulphur levels in CPC are rising. The rise has been from (1.2-2) % to above 3 % level.
Today cokes with sulphur levels of (4.5-5.5) % are routinely used for blending by the calcining
industry in place of 3.5 % sulphur cokes used previously. Higher sulphur content represent an
environmental problem for smelters and calcining industry. This also leads to higher coke
consumption. Quality changes observed in CPC and their impact on anode quality is given in
Table 3.

Table 3. Changes in CPC quality and their impact on anode quality and smelter
performance.
Quality changes in CPC Impact on anode quality and smelter performance
Decrease in coke density due to Anode density will decrease, and anode life will be
crude changes and higher volatile reduced
matters.
Cokes with more isotropic structure Increased anode consumption due to increased air
will be used (shot cokes) and CO2 reactivity.
Risk of anode cracking will increase.
Increased impurity levels particularly Higher air reactivity of anodes leading to increased
Vanadium net carbon consumption.
Metal purity will be affected, and conductivity of
wire rods will decrease.
Sulphur levels of high sulphur cokes Decrease in anode quality along with risk of
used in blends will increase. desulphurisation during calcinations and baking of
anodes.

5. Variation in Quality of CPC Received by NALCO

NALCO Smelter plant is having two carbon plants with installed capacities to produce around
230 000 t baked anodes per annum. Since the inception of the smelter plant, CPC is sourced from
4-6 suppliers. The CPC being received by NALCO can be broadly categorized into two types as
per the apparent density & impurities mainly sulphur and vanadium.

Type 1: Apparent density (1.74 -1.76) g/cm3, S (0.6-0.8) %, V (0.002-0.006) %

Type 2: Apparent density (1.71-1.73) g/cm3, S (1.5-3) %, V (0.015-0.025) %

The smelter plant receives around 70 % of its CPC supplies of the Type 2 variety. To understand
the impact of properties of CPC on anode quality, two typical CPCs were taken for R& D studies
as shown in Table 4.

Table 4. Properties of CPC used for R&D study.

Properties Unit CPC1 PC2
Apparent density (Hg) g/cm3 1.75 1.718
Real density g/cm3 2.07 2.06
Moisture % 0.02 0.01
Ash % 0.17 0.30
Fe % 0.007 0.019
Si % 0.032 0.022
S % 0.79 2.6
Ni % 0.006 0.019
V % 0.005 0.019
Na % 0.007 0.012
Ca % 0.005 0.012
HGI 37 34

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Properties Unit CPC1 PC2

Size + 4.75 mm % 37.5 32.5
Size -0.3 mm % 8.3 6.6
Grain stability % 74 72
Carboxy reactivity % 12 21.4
Air reactivity %/min 0.054 0.14

6. R&D Studies Towards Improvement of Apparent Density of Anodes

6.1 Increasing the Apparent Density of Anodes by Blending

Anode bench scale studies were carried out for both types of cokes shown in Table 4, using R&D
Carbon (Switzerland) equipment: anode bench scale plant RDC-161 and pilot anode baking
furnace RDC-166. The recipe used in the experiment was Very coarse: 20 %, Coarse: 22 %,
Medium: 20 %, Fines: 29 %, other baked: 9 %, Pitch: 14.5 %.

The results of bench scale anodes ACPC1 made from CPC1 & ACPC2 made from CPC2 and
anodes ACPC3 were prepared by blending 30 % of CPC1 coke in all fractions of CPC2 coke.
ACPC3 anodes have shown improved properties compared to ACPC2 is show in Table 5.

Table 5. Quality of anodes from two types of CPC.

Properties Unit ACPC1 ACPC2 ACPC3
Green anode density g/cm3 1.65 1.619 1.647
Baked anode density g/cm3 1.553 1.525 1.546
Real Density g/cm3 2.085 2.080 2.08
Air reactivity Residue % 90.81 65.65 69
Air reactivity loss % 8.71 23.05 19.9
Air reactivity dust % 0.48 11.29 11.1
Carboxy reactivity residue % 73.25 79.86 81
Carboxy reactivity loss % 13.98 12.92 11.9
Carboxy reactivity dust % 12.77 7.22 7.11

Anode density improvement

1,7
1,65
1,6
1,55
1,5
1,45
ACPC1 ACPC2 ACPC3

Green anode density gm/cc Baked anode density gm/cc

Figure 1. Anode density improvement by blending.

From the above results it is evident that anodes ACPC1 made from high apparent density and low
vanadium content show higher green and baked anode density and higher air reactivity residue
values whereas anodes made from low apparent density and high vanadium coke show lower
green and baked anode density and have lower air reactivity values. The carboxy reactivity values

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of ACPC2 anodes is better due to high sulphur in CPC2 coke. From the above results it is seen
that ACPC3 anodes have higher green and baked density (increase of 0.02 g/cm3). Air reactivity
residue figures for ACPC3 anodes have slightly increased and carboxy reactivity residue values
are almost same.

It can be seen that blending of good quality coke with lower quality coke is one of the options for
improving the quality of anodes. Proper procurement planning can be made by the industry and
good quality coke can be stored in a designated silo and blending may be carried out continuously
to achieve the results. Based on the above study improvements in the NALCO CPC specification
has been done over the years. NALCO is making efforts for procurement of at least 30 % (of the
total CPC requirement) higher density >1.74 g/cm3 CPC so that blending can be carried out
throughout the year. CPC calciners have also been asked to blend their RPC in such a manner so
as to achieve uniform better quality of CPC with respect to physical & chemical properties.

6.2 Increasing the Fineness of Fines (Surface Area) to Increase the Apparent Density of
Anodes

Anode bench scale experiments carried out with three green anode recipes by varying fineness of
fines (surface area as Blaine number) along with decreasing the quantity of fines is shown below
in the Table 6.

Table 6. Results of bench scale experiments on effect of fineness of fines on anode density.
Recipe 1 2 3
% Very course 18 18 20
% Course 18 19 22
% Medium 24 25 22
% Fines 29 27 25
% Other baked 11 11 11
% Pitch 14.9 14.9 14.9
% -200 mesh 68 72.5 78
Blaine number 3488 4034 4403
Green anode density g/cm3 1.61 1.625 1.645
Baked anode density g/cm 3 1.517 1.537 1.547

Blaine number vs Baked anode density g/cm3

1,55

1,54

1,53

1,52

1,51
2000 2500 3000 3500 4000 4500 5000

Figure 2. Anode density improvement with Blaine no of fines.

From the above experiment it is found that the green anode density and baked anode density
increase with increase in -200 mesh fines and Blaine number. % Fines and % Pitch in the recipe
is to be adjusted as per the fineness. With the increase in surface area of fines, the penetration of

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pitch is better, and the bulk density of fines also increase resulting in better quality anodes. The
% fines (-200 mesh) in NALCO green anode plants are being maintained at (80-85) % level
compared to the previous values of (70-75) %.

6.3 Increasing the Paste Mixing Temperature to Increase the Apparent Density of
Anodes.

Three batches of bench scale anodes were prepared with same pitch and at constant pitch
percentage & different mixing temperatures as shown in Table 7.

Table 7. Quality of anodes with increase of mixing temperature of paste.

Sample Identification Mixing temp Mixing temp Mixing temp
147 ºC 174 ºC 182 ºC
Green AD 1.611 1.634 1.644
Baked AD 1.526 1.546 1.559

1,66
1,64
1,62
1,6
1,58
1,56
1,54
1,52
1,5
1,48
1,46
147 174 182
g/cm3

Green AD g/cm3 Baked AD g/cm3 0 C

Figure 3. Anode density improvement with paste mixing temperature.

From the above experiment it is found that the green anode density and baked anode density
increase with increase in mixing temperature of anode paste. The experiments were carried out at
constant pitch percentage. Hence further optimisation of recipe in plant may be required for
getting the desired results. The temperature of mixing is normally kept 60 °C higher than the
softening point of pitch. Normally the softening point of pitch varies in between (110-115) °C.
Hence if the paste mixing temperature is kept above 170 °C, the mixing is better due to better
penetration of pitch inside the coke particles and not just on the surface. If the mixer is designed
for higher temperature mixing, CT Pitch with high softening point can also be used. Using pitch
with high softening point at higher mixing temperature can help in producing better density
anodes. At NALCO there are two green anode paste plants; GAP1 operating at mixing
temperatures 147 °C & GAP2 operating at 180 °C. As evident the green anodes from GAP1 plant
remain lower by 0.02 g/cm3 if the same coke is used in both the plants.

7. R&D Studies Towards Improvement of Reactivity Properties of Anodes

7.1 Interchanging the Fines Fraction of Two Types of CPC

Anode bench scale studies were carried out to find out the effect of replacing the fines fraction of
recipe by fines produced from good quality CPC.

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ACPC4 anodes using the fines produced from high grade coke in fines fraction of recipe have
better properties than ACPC2 anodes made from CPC2 coke. Air reactivity residue has increased
from 65.65 % to 85.44 %, carboxy reactivity residue has increased from 79.86 % to 83.94 %. As
shown in Table 8.

Table 8. Quality of anodes made by interchanging of fines fraction.

Properties Unit ACPC4

Green anode density g/cm3 1.625

Baked anode density g/cm3 1.535
Real density g/cm3 2.072
Air reactivity Residue % 85.44
Air reactivity loss % 12.89
Air reactivity dust % 1.67
Carboxy reactivity residue % 83.94
Carboxy reactivity loss % 9.56
Carboxy reactivity dust % 6.5

Air/CO2 reactivity improvement

100

50

0
ACPC1 ACPC2 ACPC4

%Air reactivity Residue %Carboxy reactivity residue

Figure 4. Air/CO2 reactivity improvement with use of fines of higher-grade coke.

The anodes made from using fines of better-quality coke show improvement in apparent density
as well as the reactivity figures of anodes of due to low impurity level of fines. Depending on the
availability of CPC the carbon plant unit operation flow sheet can be modified to accommodate a
separate bin in the circuit for storing only the ball mill fines fraction of good quality CPC for
blending.

7.2 Boric Acid Addition in Green Anode Recipe

A paper was published on R&D trial on improvement in oxidation behaviour of anodes in

ICSOBA 2017 [4] [9]. Based on the success of one-year actual trial in the plant, regular addition
of boric acid is carried out in two green anode plants of NALCO.

Improvement observed in NALCO anode quality due to regular addition of (0.1-0.20) % boric
acid in the green anode plant is presented in the Table 9.

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Table 9. Results of regular addition of boric acid in green anode plants to improve Air
Reactivity residue of anodes.
No addition of boric acid With addition of boric
(Dec. 2017-March 2018) acid (Dec 2018-March
2019)
Boric acid/T green anodes produced 1.175
Avg % Air Reactivity Residue (ARR) 68 83
Avg Metal purity (% Al) >99.7 >99.7

Due to the above improvement in Air reactivity residue of anodes, the net carbon reduction
observed was 3.7 kg/t of Al metal. This is equivalent to reduction in CO2 emission by around 13.6
kg/t Al metal. Cost wise the savings would be approx. 42.5 million/annum for NALCO plant
producing 0.46 Mt metal per annum. It was also observed that there was significant decrease in
number of fallen anodes, half fallen anodes and other anodic incidences in potline.

From the above data it is observed that by addition of 0.12 % boric acid in green anode recipe,
the air reactivity residue of carbon anodes shows significant improvement.

7.3 Boric Acid Addition in CPC at Coke Calcining Plant

Boric acid powder was added to the calcined CPC at the discharge end of the calcining process
(out of the cooler) when the temperature of the bulk material was between (140– 160) °C [10]. 2
kg boric acid was thoroughly mixed manually with one tonne hot CPC. CPC samples collected
was tested before and after doping with boric acid. Table 10 shows the test results of CPC3
(without doping) and CPC4 (with doping).

Table 10. Test results of CPC without and with doping of boric acid.
Properties Unit CPC3 CPC4
Apparent density (Hg) g/cm3 1.72 1.72
Real Density g/cm3 2.065 2.065
Fe % 0.020 0.020
Si % 0.019 0.019
S % 2.15 2.14
Ni % 0.018 0.018
V % 0.024 0.024
Na % 0.008 0.008
Ca % 0.009 0.010
CO2 reactivity % 13 0.8
Air reactivity %/min 0.41 0.04

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Carboxy reactivity % Air reactivity % /min

14 0,45
12 0,4
0,35
10
0,3
8 0,25
6 0,2
0,15
4
0,1
2 0,05
0 0
CPC3 CPC4 CPC3 CPC4

Figure 5. Decrease in CO2 reactivity Figure 6. Decrease in air reactivity

of CPC doped with boric acid. of CPC doped with boric acid.

Bench scale anodes ACPC5 & ACPC6 were also fabricated from CPC3 & CPC 4 which show
improvement in Air and CO2 reactivity residue values of anodes made from CPC doped with boric
acid, as shown in Table 11.

Table 11. Test results of anodes made from with and without doped CPC.
Properties Unit ACPC5 ACPC6
Green anode density g/cm3 1.621 1.629
3
Baked anode density g/cm 1.535 1.545
Real density g/cm3 2.078 2.084
Air reactivity Residue % 80.5 91.2
Air reactivity loss % 15.8 8.37
Air reactivity dust % 3.70 0.43
Carboxy reactivity residue % 73.5 86.0
Carboxy reactivity loss % 8.9 9.3
Carboxy reactivity dust % 17.6 4.7

Air reactivity & Carboxy reactivity of anodes made with

CPC doped with boric acid
100
80
60
40
20
0
ACPC5 ACPC6

%Air reactivity Residue Carboxy reactivity residue

Figure 7. Improvement in Air and CO2 reactivity of anodes using CPC doped with boric
acid.

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From the above experiment it could be observed that by using boric acid doped CPC for making
anodes, the CO2 and Air reactivity residue of anodes improve significantly. This solution can be
adapted by coke calciners in consultation with aluminium smelters. A measured quantity of boric
acid can be added at calciner by making special arrangements, to produce low reactive CPC.
Boron limit can be given in the specification of CPC by the smelters.

8. Dealing with High Sulphur Cokes

Sulphur levels may continue to rise due to practises of blending of fuel grade coke with anode
grade cokes at the coking/calciner’s operations for lowering the cost. In order to meet
environmental norms, SO2 scrubbing may be adopted more widely in the future by calciners and
smelters. Desulphurisation during anode baking needs to be checked by maintaining baking
homogeneity in anodes and avoiding excessive high anode baking temperatures.
At present sulphur level of CPC used by NALCO remains below 3 %. It is observed that when
% S in few CPC supplies is > 2.5 %, the CO2 reactivity of anodes made from such cokes is
significantly higher than the CO2 reactivity of anodes made from CPC with S < 1.5 %.

9. Summary and Conclusions

In this paper, the aluminium industry’s experience in dealing with the impact of utilising calcined
petroleum coke with lower density and higher impurities on anode quality in the recent years has
been described. It has been shown [5] that blending of cokes at calciners and smelters will remain
the dominant strategy to deal with the issue of quality changes. Impact of blending of CPC of
different qualities, impact of blending only the fines fraction of CPC having lower impurities,
impact of process parameters i.e. paste mixing temperature and Blaine number on anode quality
have been presented in the paper.

Increase in Sulphur, Vanadium & Nickel in CPC will remain the most obvious quality changes in
future. To deal with the issues of reactivity of anodes i.e. higher air reactivity losses due to high
vanadium CPC it is suggested to add boric acid in controlled manner without affecting the metal
purity. This methodology has been adapted by NALCO. The results of plant data are shown in
this paper. It has also been experimented that if CPC is pre-treated with boric acid at any suitable
point in the calcining process, the anodes made out of such cokes have superior Air & CO2
reactivity values.

The R&D studies presented in this paper may become useful for Aluminium Industries to address
the problem of density and reactivity properties of anodes which may arise due to non-availability
of suitable grade CPC at present and also in future. However, the role of calcining industry in
supplying good quality CPC also remain significant.

10. References:

1. Werner K Fischer, Anodes for Aluminium Industry (Compilation of papers), R&D Carbon
Ltd., Switzerland.
2. Kirstine Louise Hulse, Raw materials, formulation and processing parameters, R&D Carbon
Ltd., Switzerland.
3. Training manuals on Carbon Plant – AP18 Technology for National Aluminium Company
Ltd.
4. Binuta Patra, A. Palchowdhury, Improvement in oxidation Behaviour of Prebake anodes
used in NALCO smelter plant, Proceedings of 35th International ICSOBA Conference,
Hamburg, Germany, 2-5 Oc. 2017, TRAVAUX 46, 731-742.
5. Les Edwards, Evolution of Anode Grade Coke Quality, Light Metals 2012, 1208-1212.

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6. https://www.lightmetalage.com/resources/patents/primary-aluminum-inert-anode-and-
wettable-cathode-technology-in-aluminum-electrolysis/.
7. http://www.aluminum-production.com/inert_anode_technology.html.
8. Binuta Patra, Process for preparing prebaked carbon anodes having improved oxidation
resistance for aluminium production, NALCO Patent, Filed 29/KOL/2011, dated
10.01.2011, Granted No 289807, dated 22.11.2017.
9. Binuta Patra, Improvement in oxidation behaviour of calcined petroleum coke used for
production of anodes in aluminium industry, NALCO Patent, Filed 363/KOL/2014, Dated
21.03.2014.

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