INDIAN INSTITUTE OF SPACE SCIENCE AND

TECHNOLOGY, THIRUVANANTHAPURAM

A STUDY REPORT ON COKING OF KEROSENE

Submitted by

Rahul Anand

Rahul_anand_gunjan@yahoo.com

In

4th Semester, BTECH-AEROSPACE ENGINEERING

In

Liquid Propulsion System Center (LPSC)

Trivandrum

December-January, 2009
 ABSTRACT

Kerosene is used as a fuel in semi cryogenic engines which also serves the purpose of coolant in
regenerative passage. At high temperatures, kerosene gives carbonaceous deposits commonly known as
coke. Coking reduces the heat transfer across the chamber wall of the engine as it sticks to the inner
walls of the passage, creating an insulating layer between the coolant and the chamber wall. Studies on
coking of hydrocarbon rocket fuel have been carried out worldwide but the mechanism of its formation
is still uncertain. In this report, we discuss the various ways in which coking can occur and the measures
which can be taken to suppress coking.

proportionally higher heat fluxes to the chamber

NOMENCLATURE
walls. As the coolant travels along the

SEM- Scanning Electron Microscopy regenerative passage, its temperature increases.

GC- Gas Chromatography
MS- Mass Spectroscopy
PAH- polyaromatic hydrocarbons
Isp- Specific Impulse
INTRODUCTION
Semi cryogenic liquid rocket engines use
kerosene as the fuel along with liquid oxygen as
oxidizer. They have the advantage of being
relatively low cost, creating low pollution,
reusable and having high performance. Safety
and cost factors associated with the storage and
handling of kerosene also gives it an edge over
liquid hydrogen.
Kerosene is used as regenerative coolant in the
semi cryogenic engine to keep the chamber wall
material at safe operating temperatures. Prior to
combustion, fuel is circulated through channels
in the chamber wall to carry the heat away.
Engine performance increases by operating at
high chamber pressures, which results in
At elevated temperatures, hydrocarbon fuels
can decompose and leave behind solid deposits
on the wetted surfaces in a process called
‘coking’. These deposits decrease the
effectiveness of cooling by forming an
insulating layer over the inner wall of the pipe.
They act as a thermal barrier, which increases
the wall temperature of the combustion
chamber and can eventually cause material
failure. Coking is a major challenge associated
with the use of kerosene as fuel in aerospace
applications, and we will discuss its formation
and ways to reduce it in this paper.
Coke is a carbonaceous substance formed from
kerosene in the flow passage when the
temperature goes beyond a certain limit, known
as the ‘coking limit’. This temperature rise has
to be controlled so as to eliminate the coke
formation in the regenerative passage. The
thermal stability of kerosene depends upon
many parameters like its chemical composition,
amount of non hydrocarbon compounds like
sulphur, nitrogen and oxygen present in
kerosene, material of the piping, flow
conditions and residence time of the kerosene in
the passage. The deposition starts at around
100°C and continues to increase as the degrade with the deposition. This is
temperature increases as a result of pyrolytic because of the reaction with the sulphur
reactions. present in the kerosene, which leads to
the formation of brittle copper sulphide.
The sulphur and the oxygen molecules present
3. Kerosene is a mixture of more than 100
in the fuel can facilitate coking. Therefore,
hydrocarbons, with n-dodecane and its
studying the mechanism of formation of coke
derivatives being the prominent
becomes essential to deduce techniques for
components. Sulphur is present in trace
suppressing it. There are many models for the
amounts (<30ppm) along with
coking mechanism but it varies with the
aromatic(5%), olefins, dienes and
composition of the kerosene and system
naphthenes. Coke can be formed in
parameters.
different ways from all these
components at different temperatures.
4. At low temperatures (~200°C), coking
OBSERVATIONS ON COKE occurs mainly due to rearrangement
FORMATION and condensation. At high temperatures
(>350°C), Coke formation involves
1. Depositions from fuels at high
dehydrogenation, cyclisation,
temperatures is the agglutination of
isomerization and hydrogen transfer in
carbonaceous solid pellets cohered by
addition to condensation.
colloid material [1]. It occurs mainly due
5. The mechanism for coke formation is a
to the agglomeration of oxidative non
free radical consecutive reaction:
hydrocarbon chemicals in the kerosene.
aliphatic-polycyclic-resins-asphaltenes-
This is inferred by studying the
coke. Isolation of the intermediate has
deposits, which show that sulphur,
shown a continuous increase in the
nitrogen and oxygen content of the
molecular weight, degree of aromaticity
deposits is always higher than the
and C:H ratio.
original fuel. These impurities can react
6. Asphaltenes are complex molecules,
with thermally generated free radicals
believed to consist of associated system
during the course of the reaction to
of polyaromatic sheets, bearing alkyl
form stable solids. Studies conducted in
side chains. They are highly polar and
this field have shown that removing
surface active. Preheating of fuel prior
these impurities improve the thermal
to their burning encourages
stability of kerosene.
precipitation of asphaltenes, which
2. It has been found that the rate of
ultimately break down to give coke.
deposition increases if copper is used as
Asphaltene deposition is the
the wall material. The walls start to
consequence of the thermal instability
 of kerosene. Kerosene is thought to be a
colloidal system and asphaltenes are the
dispersed phase. They are stabilized by
resins, formed as intermediates during
the course of reaction.

Fig: butadiene undergoing Diels-Alder reaction

with ethane.

RECOMMENDED ACTIONS
TO CONTROL COKING

There are a few measures which can be

Fig: Coke obtained from asphaltene on heating
adopted to suppress coking. They are as
kerosene.
follows-:
7. The SEM results of the copper sample
after coking showed heterogeneous (i) By plating the inner surface of the

deposition. The maximum deposits regenerative coolant passage with some

inert material would affect the rate of
were found at the middle portion,
coking, as copper acts as a catalyst for
which is the hottest part. This can be
pyrolysis of the hydrocarbons, which
explained by the adsorption properties
ultimately lead to the formation of coke.
of the copper which acts as a catalyst.
Some eligible materials are Nickel, Gold,
The coke formed in this region is a
mixture of pyrolytic and asphaltic coke. Silver, Zirconium or some other noble

8. Formation of such huge rings from metals.

condensation of long chain paraffins (ii) By increasing the flow rate, the
and aromatics can be explained by the residence time of the fuel in the
Diels- Alder reaction, shown by the regenerative passage would decrease and
[9]
dienes present in the kerosene. These hence, the deposition may decrease.
dienes on cycloadditions can increase
the size of the rings considerably. It (iii) By distillation of the kerosene fuel by

may be noted that the rate of reaction special methods like Deer Distillation[1] to

increases with temperature. remove suspended impurities. The oxidative

coke, formed during the initial stages of
heating is mainly due to the presence of
oxygen, sulphur and nitrogen atoms in the
fuel.
(iv) Precooling the fuel before it is sent to
the regenerative passage, will increase the
margin of the coking limit.
(v) By hydrogenating the fuel before it is
kept in the storage tank, we can suppress
coking to a large extent as the ring
propagation is believed to be caused due to
[9]
the presence of dienes. Hydrogenation
prior to heating would reduce the amount of
unsaturation compounds, thus preventing
coking and would also result in an increase
in the calorific value of the fuel.
(vi) By adding metal particles like
Aluminum to the fuel would increase the
Isp of the fuel. If we add a composite of
boron (or boron hydride) and a suitable
transition metal, it could reduce coking by
forming organometallic complexes with the
active compounds like asphaltene, formed
during the course of the reaction. Boron
hydride addition would inhibit coke
formation to some extent. This has to be
further studied to understand completely. A
similar method has been employed in the
aviation industry and NASA has also used
aluminium gelled RP-1 for spaceflight.
Laboratory experiments and some more
research in this field may help us find a
suitable element which would wash away
the coke without affecting the combustion.
(vii) The use of gelled propellants is another
area of research which can lead to a
solution to the coking problem. Here, an
external gellant is used which creates a
cross linked structure in the liquid fuel, like
a long chain polymer. This would increase
the thermal stability of the hydrocarbons
present in kerosene, thereby reducing
coking. The other advantages of using
gelled propellants are safer handling,
reduced slosh, reduced the O/F ratio leading
to lighter exhaust gases, less leakage and
greater Isp than normal liquid propellants.
(viii) The use of nanometal additives or
nanocomposites is another alternative. Once
the precursors to the coking reactions are
known completely, we can design a
nanocomposite can be designed which
would increase the Isp as smaller particles
undergo more efficient combustion. It
would also trap the coking process by
reacting with the precursor element. As of
now, availability and the cost of
nanoparticles is an issue so it can be
pursued later.
(ix) According to literature, semi cryogenic
technology was used by both the US and
USSR. Though the US engines have
reported coking, the Russians didn’t face
this problem. It is not surprising since the
kerosene used by Russia (RG-1) was
superior in quality compared to RP-1, used
by US. RG-1 was low in sulphur content
(<1ppm), aromatic content (approx 5%) and
low dienes content, as these are thought to
be the major facilitations for coking. RG-1
was 3% denser than the RP-1.
(x) Boriding the inner surface of wall of the
cooling passage can help in reducing coking
as Boron being a trivalent element has
capability to form complexes readily. It can liquid kerosene, oxidative coke is formed.
form complexes with the depositing At high temperatures, coke is mainly
asphaltene and dissolve away. Boriding the pyrolytic because of cracking. It is due to
surface will also increase the hardness and the formation of acetylene, benzene and
smoothness of the surface. other PAHs. A catalytic coke is formed
because the wall material acts as a catalyst.
CONCLUSION, DISCUSSIONS &
When the pyrolysed kerosene is cooled
RECOMMENDATIONS
down, asphaltic coke can appear. It is

To understand the coking phenomenon, we because of condensation of PAHs. These

must have the knowledge of the major different types of coke may have

components of the kerosene before heating amorphous, tubular or filamentous structure

as well as during the course of heating at depending upon the temperature at which

different temperatures. The study of the they are formed.

intermediates can help us to understand the

REFERENCES
precursors and mechanisms of coke
formation. For this GC/MS can be [1] Liang, Yang, Zhang, ‘Investigation of
employed to analyze the samples of heat transfer and coking characteristics of
kerosene as it has been successfully used to hydrocarbon fuels’, Journal of Propulsion
study volatile mixtures with more than and Power, Vol.14 No.5, pp. 789-796,
hundred components. X-ray spectroscopy or September-October 1998.
13
C NMR spectroscopy of the coke samples
[2] Giovanetti, Anthony J., ‘Deposit
can help us elucidate on the actual structure
formation and heat transfer in hydrocarbon
of the coke formed at that particular
rocket fuels’, NASA Report 168277,
temperature (given in appendix). The
October 1983.
structure of the coke may help for
conducting a retro-organic analysis of the [3] Wickam D.T., Alptekin G.O., Engel
coking mechanism. Study of this J.R., Karpuk M.E., ‘Additives to reduce
mechanism is essential for the development coking in endothermic heat exchangers’,
of a semi cryogenic engine indigenously, 35th AIAA/ASME/ASEE Joint Propulsion
and the design of a synthetic kerosene to Conference and Exhibit, 20-24 June 1999
suit the needs of ISRO.
[4] Goodger E.M., Hydrocarbon Fuels,
APPENDIX 1 Mcmillan publication, 1960, pp. 483-486.

Coke formed at different temperatures has [5] Zhiming Fan, Watkinson Paula,
different structure. At low temperatures ‘Formation and characteristics of
(<473K), if some oxygen is present in the carbonaceous deposits from heavy
hydrocarbon coking vapours’, Industrial &
Engineering Chemistry Research,
Vol.45,No.19, September 13, 2006, pp-
6428 to 6435.

[6] Evaluation of coking limits of kerosene-

preliminary results, Report no-
LPSC/SCED/TR/051/08

[8] Brown Sarah, Frederick Robert A.,

‘Laboratory scale thermal stability
experiments on RP-1 and RP-2’, Journal of
Propulsion and Power, Vol.5 No.2,
October-November 2007.

[9] Wickham D.T., Alptekin G.O.,. Engel

J.R and Karpuk M.E., TDA Research Inc,
‘Additives to reduce coking in endothermic
heat exchangers’, AIAA 99-2215