“Experimental study on co-pyrolysis of petroleum coke and coals: Synergy effects and co-

gasification reactivity” – Jilin Li et al Fuel 279 (2020) 118368

S.No. Advantages Disadvantages Remarks

1. Higher carbon content Lower efficiency Greener and efficiently utilized by
2. High heating value Higher pollution gasification

S.No. Petroleum coke (PC) gasification restricted due to following reason

1. Lower reactivity
2. High graphitization degree
3. Undeveloped pore structure
4. Limited ash content

S.No. Studies improving petroleum coke gasification Reasons for not feasible
1. Increasing gasification temperature High cost and lower efficiency
2. Addition of alkaline and alkaline earth metals Expensive catalyst cost
as catalysts

S.No. Factors Results & Discussion

Gasification reactivity (GR) (PCGR < CHRGR < CLRGR); (PCGR < 1CxyGR:3PCGR < 1CxyGR:1PCGR <
and synergy behaviour: 3CxyGR:1PCGR)
a. TGA
1. b. Coal ash Higher R0.9 & AI – Higher gasification reactivity
Reaction rate vs conversion
c. Coal char type – smooth (PC + CHR)
– rapid & slower (PC + CLR)
2. Char structure variation In situ coal char – low ordered carbon (high reactivity)
Preprepared coal char - high ordered carbon (low reactivity)
3. Synergy effect in co OH & H free radical transfer from coal char to pet coke
pyrolysis makes carbon amorphous:
In situ coal char – more pronounced (high reactivity)
Pre prepared coal char – less pronounced (low reactivity)

PCGR – Pet coke gasification reactivity

CHRGR – Coal high rank gasification reactivity

CLRGR – Coal low rank gasification reactivity

x/y – High rank / low rank

R0.9 – Reactivity index (higher value indicates the presence of Alkaline and Alkaline earth metals)

AI – Alkali index
“Existence of Synergistic Effects During Co-pyrolysis of Petroleum Coke and Wood Pellet” – P.
Toshniwal et al., Int. J. Chem. React. Eng. 2016

Review Article

Co pyrolysis of petroleum coke and biomass: A comprehensive review on co pyrolysis reaction

parameters and synergetic effects.

Introduction

Petroleum coke is popularly known as “bottom of the barrel” in refineries. It is the final solid residue
produced by the delayed coking unit. Owing to its high carbonaceous and low ash content, calorific
value (HHV - High Heating Value) ranges from 7500 to 8500 kCal/kg. Heavier (high sulphur and
metals) the crude oil, poorer the quality of coke produced and vice versa. Petroleum coke are mainly
finding its end use as a fuel (alternative to coal), anode making, clinker production, steel making etc.,
Premium quality will be used as a feedstock and the poorer quality will be used a fuel grade.
Following are its major industrial drivers are cement, power plants, lime kiln, gasification, calcium
carbide, aluminium smelters, calciners, steel. Global petroleum coke market reached a value of 20.4
billion USD in 2020and it is expected to reach 30.6 billion USD by 2026 [1]. This is due to rising
demand of energy and aluminium sectors. Globally India is the largest importers of petroleum coke
from United States and Middle East countries [2]. Due to the emerging environmental concerns, On
December 2016, EPCA (Environment Pollution (Prevention and Control) Authority – nominated by
Supreme Court of India) imposed a ban on the use of imported petroleum coke due to presence of
high sulphur content which causes adverse effects on environment and public health [3].
Nevertheless, 72% of India’s calcined petroleum coke production is dependent on the imported
green petroleum coke raw material. Therefore, understanding country’s potential requirement is
essential. Gasification is one of the best available technology to utilize petroleum coke more
efficiently with less environmental emissions [4]. Presence of high carbon content makes the
gasification difficult. Also, it requires higher gasification temperature and needs more residence time
to complete the reaction. This is mainly because of presence of poly cyclic aromatic compounds and
higher graphitization degree at higher temperature [5,6]. Due to the above gasification limitations,
studies focused to improve the gasification reactivity. One of the ways is to add the alkali and
alkaline earth metals (AAEM) as a catalyst to increase the gasification reactivity [7]. Addition of such
catalysts is not economically viable. However, these catalysts are naturally present as ash content in
biomass and fossil fuels. Recent efforts found biomass to be a suitable co feedstock for petroleum
coke gasification. As biomass found to be a carbon dioxide neutral renewable resource [8]. Presence
of higher carbon and oxygen content in biomass will induce the synergetic effects in petroleum coke
reactivity.

Alkali metals on the carbonaceous surface sits as a active sites for chemisorption of oxygen thereby
weakens the C-C bonds. Followed by facilitation of gaseous product desorption after oxidation
process [9].

(Meaning: Alkali metals intercalates between highly ordered carbonate structure thereby weakening
the vanderwaals forces between the carbon layers. Whereas the bonds between carbon on the
same plane is stronger than between the planes. Due to this intercalation the vanderwaals forces
further weakens.)
Strong contact of alkali metal contact with the carbonaceous material found to increase the
reactivity when compared to lose contact which tends to evaporate at high temperature. Alkali
content tend to poison the reaction when its concentration increases beyond 10 wt.% [10].

Product distribution (LS PC + Sugar cane bagasse) - CO2, CO, CH 4, HCOOH, C6H5OH, CH3COOH [11].

Rice husk has high cellulose content (33.43%), low lignin content (18.25%), high volatile matter
(73.14%). Cellulose combust at low temperature and increases the peak temperature thereby
prolongs gasification [12].

Rice husk sequence of degradation – Hemicellulose (225 – 360 oC), Cellulose (360 – 450oC), Lignin (>
450oC). Degradation rate of blends is 36% during pyrolysis and 101.7% during char gasification
compared to individual gasification. Activation energy of petroleum coke is reduced from 126 to 86
kJ/mol when it is used in blending with rice husk [12].

To produce more H2, steam gasification agent is best compared to CO 2, O2 and air as a gasification
agent. Carbonaceous gasification provides,

(1) syngas to produce fertilizer, methanal, olefin, gasoline, diesel, natural gas and other
chemicals

(2) hydrogen for fuel cell production

(3) Fuel gas for integrated gasification combined cycle power

(4) reducing gas for iron industry

Biomass gasification produces CO, H2, CO2, H2O and other volatiles that are useful for the gasification
of petroleum coke. Gasification of individual samples takes place in single stage whereas blends in
two stages. Gasification Reactivity of blends increases with the increasing concentration of K 2O and
P2O5 in biomass ash which is not explained [13].

Ca, K, Na are conductive to gasification rate, Si & Al showed a negative effect [14].

Gasification reaction starts from the edge of carbonaceous materials [15]. Surface morphology of
carbon structure tend to change during gasification.

Cotton straw ash with petroleum coke char, increases the gasification reactivity compared to rice
straw ash addition. Specific reactivity index (R 0.5 ratio of petroleum coke char with addition of
biomass ash to R0.5 of petroleum coke char without addition of biomass ash) of the char with cotton
ash decreases significantly from 1000 to 1300 oC when compared to rice straw ash. This is due to the
devolatilization of catalyst elements or the melting of catalyst elements thereby modifying surface
microstructure. Thereby reducing/hinders the gasifying agent in reaching carbon surface. Increase in
biomass blending ratio with petroleum coke char increased the reactivity. Carbon structure becomes
more dis ordered after the addition of cotton straw ash. Shrinking core model is suitable for
petroleum coke gasification compared to random pore model 16].

Ash fusion temperature of petroleum coke even exceeds 1500 oC [17]

Calcium oxide is usually used as a flux to modify the AFTs of coal and petroleum coke during
gasification because the ion potential of Ca2+(20 nm−1) is lower than 25 nm−1[18]

Basic oxides like CaO, MgO, K2O and Na2O tend to terminate polymer formation and decrease the
AFTs [19, 20]
References

1. Expert Market Research Group, “Historical Market and Forecast (2016-2026)”,

www.expertmarketresearch.com
2. D. Gordon et.al., “Petroleum Coke Use in India and South Asia: Recent Trends and Emerging
Policy Options”, Connectivity and trading in power & energy: A regional and International
dimension, ASIN: B076ZHH2PR (2017)
3. Environment Pollution (Prevention and Control) Authority (EPCA) for NCR (National Capital
Region) report (2018)
4. J. L. Zhang et.al., “Kinetics of petroleum coke/biomass blends during co-gasification”, Int. J.
Miner. Metall. Mater., Vol. 23, No. 9 (2016)
5. X. Liu et.al., “Experimental Study on Co-gasification of Coal Liquefaction Residue and
Petroleum Coke”, Energy Fuels 25 (2011) pp. 3377–3381.
6. W. Huo et.al., “Study on CO 2 gasification reactivity and physical characteristics of biomass,
petroleum coke and coal chars”, Bioresource Technology 159 (2014) pp. 143–149.
7. M. Malekshahian et.al.,” Potassium catalyzed CO2 gasification of petroleum coke at elevated
pressures”, Fuel Processing Technology 113 (2013) pp.34–40.
8. C. Quan et.al., “Copyrolysis of Biomass and Coal: A review of Effects of Copyrolysis
Parameters, Product Properties and Synergistic Mechanisms”, Biomed Research
international (2016).
9. D. W. Mckee et.al., “The catalytic behaviour of alkali metal carbonates and oxides in graphite
oxidation reactions”, Carbon vol.13 (1975) pp. 381-390.
10. X. Zhann et.al., “Catalytic effect of black liquor on the gasification reactivity of petroleum
coke”, Applied Energy 87 (2010) pp. 1710–1715.
11. E.M.A. Edreis et.al., “CO2 Co-gasification of lower Sulphur Petroleum coke and Sugar Cane
Bagasse via TG-FTIR Analysis Technique”, Bioresour. Technol. Vol. 136 (2013), pp. 595–603.
12. Z.R.Gajera et.al., “Kinetics of co-gasification of rice husk biomass and high sulphur petroleum
coke with oxygen as gasifying medium via TGA”, Bioresource Technology 11 (2020) 100479.
13. E.M.A. Edreis et.al., “Kinetics, thermodynamics and synergistic effects analyses of petroleum
coke and biomass wastes during H2O co-gasification”, Int.J. Hydrogen ener. vol. 45 (2020)
pp. 24502 – 24517.
14. L. Ding et.al., “Interaction and its induced inhibiting or synergistic effects during co-
gasification of coal char and biomass char”, Bioresour. Technol. vol. 173 (2014) pp. 11 – 20.
15. L.S. Lobo et.al., “Kinetics and mechanism of catalytic carbon gasification”, Fuel vol. 183
(2016) pp. 457 – 469.
16. J. Yu et.al., “Promoting effect of biomass ash additives on high-temperature gasification of
petroleum coke: Reactivity and kinetic analysis”, J. of the Energy Institute vol. 93 (2020) pp.
1364 – 1372.
17. Q. Xiong et.al., “Ash fusion characteristics during co-gasification of biomass and petroleum
coke”, Bioresource Technology vol. 257 (2018) pp. 1 – 6.
18. Li et.al., “Investigating a high vanadium petroleum coke ash fusibility and its modification”,
Fuel vol. 211 (2018) pp. 767 – 774.
19. Vorres et.al., “Melting behavior of coal ash materials from coal ash composition. J. Eng.
Power Trans, ASME 101 (1997) pp. 118 – 142.
20. Kucukayrak et.al., “Investigation of the relation between chemical composition and ash
fusion temperatures for some Turkish lignites”, Fuel Sci. Technol. Interna. Vol. 11 (9) (1993)
pp. 1231 – 1249.