STUDY ON PHYSICAL-CHEMICAL PROPERTIES

OF PETROLEUM COKES*

S. BIRGHILA1, I. CARAZEANU POPOVICI1, A. DUMITRU2

1
Ovidius University, Chemistry Department, Constanţa, 900527, Romania
E-mail: [email protected]; [email protected]
2
Ovidius University, Chemical Technology and Engineering Department, Constanţa, 900527, Romania,
E-mail: [email protected]
Received September 10, 2010

The calcined petroleum cokes are used in production of aluminum anode-grade,

graphite electrode, needle-grade, titanium dioxide pigments. Petroleum coke (green and
calcined) is produced by the high pressure thermal decomposition of heavy petroleum
process streams and residues. Green coke undergoes additional thermal processing to
produce calcined coke. Various properties of calcined cokes from several refineries
were analyzed. Coke properties evaluated are: moisture, volatile carbon matter, ash and
metals (Mo, Ni, Cu, Zn). The results of investigation showed that all coke contains the
highest content of nickel (625 to 5353 ppm) which is the most represented metal
component in the coking feedstock. The physical-chemical properties showed that
analyzed coke has a low volatile matter content, low ash and metallic content in
samples A and C. Therefore, coke A and C can be used in production of anodes for the
aluminum or as carburizer in the foundries. Due to the high content of the ash and
metallic content, coke B, can be recommended as burning agent.
Key words: aluminum anode-grade, petroleum coke, moisture, volatile carbon
matter, metals.

1. INTRODUCTION

The petroleum coke belongs to a group of materials with high carbon content.
It is produced by coking of feedstocks obtained from residue of primary and
secondary oil refining processes [1]. At present, these are three different types of
coking processes: delayed, fluid and flexicoking, the he delayed coke is mostly
used. Coke products from a delayed coker are classified as shot, sponge or needle
coke depending on their chemical and physical characteristics. Shot coke, almost
always solid as fuel is hard, having spherical form and physically produced through
precipitating asphaltenes; sponge coke, mostly used for anode-grade is dull and

*
Paper presented at the 11th International Balkan Workshop on Applied Physics, July 7–9,
2010, Constanta, Romania.

Rom. Journ. Phys., Vol. 56, Nos. 7–8, P. 976–982, Bucharest, 2011
2 Study on physical-chemical properties of petroleum cokes 977

black, having porous, amorphous structure; and needle coke, not used in anode
production is silver-gray, having crystalline broken needle structure, and
chemically produced through cross linking of condensed aromatic hydrocarbons
during coking reactions.
Green petroleum cokes are mostly used as utility fuels and as feedstocks for
further upgrading calcinations. The calcined petroleum cokes are used in
production of aluminum anode-grade, graphite electrode, needle-grade, titanium
dioxide pigments. The carbon anodes used in the production of aluminum are
manufactured by carbonization of a blend of petroleum coke with a small
proportion of coal tar binder pitch. Impregnation with more pitch is commonly
used to produce the dense anodes needed to meet the required performance
standards. Consumption rates of the anodes in the molten fluoride salt electrolysis
cell are high, approaching 0.5 t of carbon for each tonne of aluminum produced [2].
Hence, large quantities of coke are required for carbon anode manufacture to
satisfy the demands of the indigenous aluminum industry. There are a number of
factors which determine the quality of petroleum coke: such density, metal and
sulphur content, electrical resistivity. Knowledge of structure parameters also
contributes to characterization and utilization of petroleum coke [3-4].
Impurity levels in petroleum cokes have been progressively increasing in
recent years as the refineries have been obliged to accept a higher proportion of
heavy sour crudes. This trend, and changes in refinery practice dictated by the
economics of the petroleum market aimed at maximizing the yield of lighter high-
value products, have resulted in an increase in the S content of the petroleum coke
[5]. Impurities in the crude oil become concentrated in the coke and can have
undesirable effects on aluminum production. Metal impurities, such as V and Ni,
catalyze carbon oxidation reactions and lead to higher carbon consumption in the
electrolysis cell. Other impurities collect in the refined aluminum and can lower its
value. An alternative supply of anode coke is required to supplement, or eventually
replace, calcined petroleum coke supplies [6-9].
Casada, Rolle, et al. [10] investigated the influence of nickel on reduction
cell anodes. Nickel alone does not significantly effect anode, but including anode
butt material increased CO2, reactivity. Leach et al. [11] evaluated calcined coke
and anode core properties to predict carbon consumption and anode performance in
aluminum reduction cells. Calcined cokes having a range of properties can produce
quality prebake anodes that yield low, stable carbon consumption. Concern over
release of certain trace elements to the environment as a result of coke utilization
has made the determination of these elements an increasingly important aspect of
coke analysis.
This paper presents the results of investigation of physical-chemical
properties of calcined petroleum coke, used in aluminum anode-grade carbon or as
carburized in the foundries. Coke properties evaluated are: moisture, volatile
carbon matter, ash and metals (Mo, Ni, Cu, Zn)
978 S. Birghila, I. Carazeanu Popovici, A. Dumitru 3

2. EXPERIMENTAL

Sample
Representative samples of petroleum cokes for this study have been obtained
from various refineries (A, B and C). The cokes were produced by delayed coking
process from feedstock consisting pyrolytic residue of oils. Calcination was
performed by thermal treatment of green coke at 11000 C during 3 hours.
Determination of moisture and volatile matter content
Moisture content was determined by heating the coke samples at 1100 C to
constant mass and volatile matter content was determined applying the standard
ASTM D 3175 method [12].
Determination of ash content
The ash content was determined by first drying 5g of coke at 1100 C to
constant mass and then ashing it at 7500 C for 2 hours, until constant ash mass was
obtained.
Determination of metal content
Metal content was determined applying the standard ASTM D 3686
method using an atomic absorption spectrometry whit flame atomizer [13-14].
Atomic absorption spectrometry is still one of the most versatile analytical
tools. This technique has been applied to the determination of many elements in
several kinds of samples, particularly using flame atomizers (FAAS). The
sensitivity in FAAS could be improved when the atomization step occurs in a
heated tube; a conventional air-acetylene flame has been used for this purpose. The
main advantage of this system is the enhancement on sensitivity due to the increase
on the concentration of atoms in the optical path [15].
A ZEENIT 700 atomic absorption apparatus equipped with air-acetylene
flame was used to determine individual elements. Calibration standards are
prepared from stock solutions; the corresponding absorbance response for each
standard is plotted versus concentration for calibration. Samples responses are
compared directly with the calibration curve.
Metal calibration curves have linear shape in 0–30 mg/L range for Ni and
0–10 mg/L for Mo and 0–6 mg/L for Cu and Zn. Analyses were made in triplicate
and the mean values are reported. Table 1 summarized the instrumental parameters
to be used.

Table 1
Instrument parameters
Element Wavelength, nm Oxidant-Fuel
Mo 313.3 Air-C2H2
Cu 324.8 Air-C2H2
Ni 232.0 Air-C2H2
Zn 213.9 Air-C2H2
4 Study on physical-chemical properties of petroleum cokes 979

3. RESULTS AND DISCUSSION

Typical ranges of calcined coke properties for aluminum anode-grade

specifications are listed in the Table 2 [16].

Table 2
Coke properties for aluminum anode-grade
Property Calcined
S wt % 1.7 – 3.0
Ash wt % 0.1 – 0.3
V [ppm] 165 – 350
Ni [ppm] 120 – 350
Volatile matter wt % < 0.25

Table 3 summarizes the results of analyses of coke physical-chemical

properties.

Table 3
Cokes physical-chemical properties
Property A B C
Ash wt % 0.23 0.39 0.28
Volatile matter wt % 0.13 0.20 0.15
Moisture wt% 0.28 0.37 0.33

The relatively low values of moisture and volatile matter content indicate that
the calcination process was successful. It is advisable to have the carburizer,s
volatile matter content below 1% due to risk of possible explosion in contact with
the melt.
Volatile matter content of petroleum cokes analyzed varies in the range
0.13–0.20%, the limit of 0.25% maximum is frequently imposed in order to be
used as anode material. The volatility differences are not significant between the
three types of petroleum cokes. The volatility measures lead to significant
considerations regarding petroleum coke structure and reactivity.
All samples analyzed are low in moisture, the content ranges between
0.28–0.37 %.
The ash content indicates the presence of inorganic admixtures in coke. The
analyzed sample contains 0.23–0.39 % of ash, in which the content of metals Mo,
Ni, Zn and Cu as micro – components of coke was determined (Figure 1).
980 S. Birghila, I. Carazeanu Popovici, A. Dumitru 5

200
160 Cu Mo
Concen tration [ppm]

Concentration [pp m]
150
120
100
80
40 50

0 0
A B C A B C
Pe troleum c oke Petrole um coke

-a- -b-
300 Zn 6000 Ni

Concentration [ppm]
Conce ntration [ppm]

200 4000

100 2000

0 0
A B C A B C
P etroleum coke P et role um coke

-c- -d-
Fig. 1 – Metals content in petroleum cokes: a) Cu; b) Mo; c) Zn; d) Ni.

There are differences between calcined cokes analyzed as a function of crude

oil source. However the ash chemistry of petroleum coke remains significant due to
issues of slagging and fouling, and traces metal emissions.
The low content of ash and microcomponents in samples A and C is
advisable in carburizers. In production of anodes for the aluminum the ash content
should be kept below 0.3%.
A consequence of high ash content is formation of higher quality of slag,
which can cause difficulties in operation and lower utilization. So, utilization
depends on carburizer’s chemical composition, its reactivity and its physical
properties.
On the other hand, possibility of carburizer’s dissolution is determined by
physical properties, microstructure and by the distribution and type of structural
elements.
The results of investigation showed that all coke contains the highest content
of nickel (625 to 5353 ppm) which is the most represented metal component in the
coking feedstock.
Metals, mainly vanadium and nickel, occur as metal chelates or porphyrins in
the asphaltene fraction. Some metals are intercalated in the coke structure and are
not chemically bonded, so they become part of the ash and particulates. Metal
6 Study on physical-chemical properties of petroleum cokes 981

concentrations in coke normally increase upon calcining due to the weight loss
from evolution of the volatile matter [17]. Mo content of calcined cokes studied
varies less in the large of 53.7 to 156 ppm compared to Ni, Zn and Cu content.
The data from Figure 1 show high concentration of all metals in sample B.
Based on the obtained values, coke B, produced from high asphaltenes feedstocks,
can be recommended as burning agent.
Therefore, the metals content is determined by the composition of the
feedstockes used in the coking process, which in turn are dependent upon the
composition of the crude oil and refinery processing from which the feedstock is
derived.
High-quality petroleum coke is produced from feedstocks with a high content
of polycyclic aromatic hydrocarbons, with low content of asphaltene and metallic
and non-metallic admixtures.
All these concentrations are in range of previously determined concentrations
for different petroleum coke samples reported by other authors as well [18-19].

4. CONCLUSIONS

The physical and chemical properties of some petroleum cokes produced in

several different refineries have been examined.
Coke properties evaluated are: moisture, volatile carbon matter, ash and
metals (Mo, Ni, Cu, Zn).
The results showed that analyzed coke has a low volatile matter content, low
ash and metallic content in samples A and C. Therefore, coke A and C can be used
as carburizer in the foundries or in production of anodes for the aluminum.
Due to the high content of the ash and metallic content, coke B, can be
recommended as burning agent.
The results have shown that coke properties vary and are depending upon the
source of the crude oil and the quality specifications dictated by producing
refinery.
High-quality petroleum coke is produced from feedstocks with a high content
of polycyclic aromatic hydrocarbons, with low content of asphaltene, metallic and
non-metallic compounds.

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