An introduction to fouling in fired

heaters: part 1
Erin Platvoet
XRG

F
ouling is the accumulation and formation of
unwanted materials on the surfaces of pro-
cessing equipment. It is an extremely com-
plex phenomenon and considered the major
unresolved problem in heat transfer (Bott, 1995).
Fouling in refineries and petrochemical plants
has an impact on safety, reliability, operation, the
environment and profitability. The cost of fouling
is believed to be more than $2 billion per year in
U.S. refineries alone (source: www.energy.gov)
due to increased production costs, production
losses, unit shutdowns and high maintenance
costs. Fouling is further exacerbated by contin-
ued increase in use of heavy, unconventional oil
sources, deeper residue conversion to light ends,
tightening environmental demands and fuel
standards and increased production complexity.
The goal of this article is to provide an over-
view of the most common types of fouling in fired
heaters and preventive strategies. It addresses
areas inside the tubes, on the outside of radiant
tubes, convection section, burners, air preheaters
and selective catalytic reduction (SCR).
Fouling is generally classified by six categories.
The first three are commonly found in fired heat-
ers and related equipment.
Fouling inside fired heater tubes
Particulate, reaction, and corrosion fouling
occur inside fired heater tubes. The most com-
mon one is reaction fouling in the form of cok-
ing, which is driven by temperature, residence
time, velocity, and feed composition. The heat-
ers that are the most prone to this type of fouling
are the ones that process crude feeds, due to the
wide range of components they require. This is
especially true for refineries that turned to alter-
native heavy feedstocks that are more cost-effec-
tive to process. For example, bitumen (asphalt)
is a highly viscous semi-solid form of petroleum.

Type Definition

Particulate fouling Accumulation of suspended particles in the liquid or gaseous process streams onto the
heat transfer surfaces. Main drivers are concentration of particles and fluid flow velocity.
Example: fouling of convection banks due to dust and soot.

Reaction fouling Chemical reactions on the heat transfer surfaces. The surface material itself is not a
reactant but can be a catalyst. Main driver is temperature. Example: thermal cracking of
hydrocarbons in the fluid film.

Corrosion fouling Accumulation of corrosion product on the heat transfer surface. The heat transfer surface
material itself reacts to produce the corrosion products. The products of corrosion can
cause particulate fouling downstream.

Precipitation fouling Crystallization of dissolved salts from saturated solutions due to solubility changes with
temperature. Example: scaling in boiler tubes.

Biological fouling The attachment of living materials to the heat transfer surface.

Solidification fouling Freezing of high-melting components from a multi-component solution on subcooled

surfaces. Example: wax formation on subcooled surfaces.

Table 1

www.digitalrefining.com May 2022 1

 Canada has the largest reserve of natural asphalt
(“tar”) in the tar sands, which is a combination
of clay, sand, water, and bitumen. Tar sands can
be mined and processed to extract the bitumen,
which is then refined into oil.
The first problem that occurs when heating
Tar Sands Bitumen is the potential for particu-
late fouling by clay particles. Alumina Silicate
clay particles that are normally dispersed in a
colloidal system lose solubility and deposit upon
heating. The silicate deposits have low thermal
conductivities and form a significant resistance
against heat transfer. This type of fouling usually
occurs in the convection section or the top of the
radiant section. Clay deposits can only be removed
by pigging, not by spalling or steam air decoking.
This type of fouling is particulate fouling and
therefore driven by concentration and velocity.
To minimise particle deposits, it is recommended
to keep cold oil velocity above 6 ft/s at a mini-
mum and ideally above 10 ft/s. Consider adding
velocity steam to the convection inlet to increase
the tube side velocity.
Figure 1 Two types of flame interactions creating two distinctly different flux profiles
2 May 2022
A second problem is that bitumen typically
contains 16 – 25% asphaltenes. Asphaltenes are
heavy, polyaromatic molecules that contain sul-
phur, nitrogen, and heavy metals. Asphaltene
molecular weight is in the range of 500 – 3,000
but the apparent molecular weight can be up to
300,000 due to association by polar constitu-
ents. Their weight and molecular structure make
asphaltenes strong fouling precursors and must
be kept in solution as much as possible to prevent
excessive deposition.
On the other end of the spectrum, we have
shale oil. The production of shale oil, also known
as Light Tight Oil (LTO), has grown exponen-
tially in the last 10 years. Shale oil has many fea-
tures that are attractive to refiners; it is a light
oil with a low viscosity, a low asphaltene con-
centration (typically less than 0.1 wt%), a low
sulphur content, and due to its recent abun-
dance, has become a very economic feedstock.
Unfortunately, there are downsides to using LTO
as well. It is highly paraffinic, with long chain
alkanes of 20 to 50 carbon atoms). This has sig-
www.digitalrefining.com
nificantly increased the risk of wax deposition on
cold walls of tanks and processing units.
Another downside for vaporisation of LTO
inside a fired heater is that its physical proper-
ties are very inconsistent. Day to day variations
in density and solids content can be very wide,
even for shale oil coming from the same basin. A
high variability in vaporisation potential can lead
to excessive vaporisation inside the tubes, which
can lead to dry points. Dry points should always
be avoided since they leave behind residue and
cause excessive fouling.
Refineries in the US are not designed to pro-
cess either heavy bitumen or shale oil. They are
historically designed for medium crudes and
cannot readily process very light or very heavy
crudes without significant (and expensive)
changes. For economic reasons, many refineries
blend LTO and bitumen to achieve the charac-
teristics of a medium type crude. This has intro-
duced yet another fouling problem inside fired
heaters. Blends of LTO with heavy asphaltenic
crude can result in asphaltene instability and
precipitation, resulting in a strong increase in
coking rate when onset of precipitation occurs
early. Crude, vacuum and delayed coker heat-
ers that used to run for years on Arabian crudes
without decoking now show runlengths of sev-
eral months or less before the tubes are too
fouled to continue. Studies show that the par-
affinic character of LTO causes the ashpaltenes
to lose solubility, an instability that is hard to
manage with the daily changes in LTO composi-
tion, and even harder when sourcing many differ-
ent heavy crudes to blend with the LTO. Blending
will have to be done extremely carefully to max-
imise asphaltene stability. Toluene solubility
tests according to ASTM D 7157 (“Standard Test
Method for Determination of Intrinsic Stability
of Asphaltene-Containing Residues, Heavy Fuel
Oils, and Crude Oils”) help the refiner determine
the optimum ratio of crude to shale. Since coking
is a type of reaction fouling, it is strongly depend-
ent on the process film temperature, which in
turn is dependent on the incident flux profile
from the flames.
See Figure 1 for two different kinds of flame
interactions, leading to two very different inci-
dent flux profiles. The flames that merge (on the
left side of the figure) create a long and uniform
flux profile with a peak near the top of the fire-
box. The flame interactions on the right create a
www.digitalrefining.com
much more intense peak near the bottom of the
heater due to flames impinging on the tubes.
Note that the flux profiles are normalised and
that the absolute flux values of the flames on the
right are much higher.
Neither flame behavior is desirable; the long
merging flames will lead to poor fuel efficiency,
while the short impinging flames create hotspots
and very high coking rates. The difference in peak
film temperature between the two cases is well
over 100°F even though they are the same heater
and the same burner design. Flame behavior and
flux profiles from burners can be studied using
CFD and manipulated by changing burner type,
quantity, and/or location.
The mechanism of coking
There are two main types of coking mechanisms.
The first one is catalytic coking which takes place
at the tube wall itself. The shape (‘morphology’)
of catalytic coke is filamentous, which means that
a network of fine carbon threads is formed on
the tube inner wall. Small metal particles can be
found on the ends of these filaments. The process
of catalytic coking is demonstrated in Figure 2.
Catalytic coke is the major form of coke formed
in high temperature processes like gas cracking
(ethane, propane) to produce ethylene. The radi-
ant tubes in these heaters typically contain 35 –
45 % nickel. During operation, the catalytic coke
layer continuously dehydrogenates and changes
into a very hard graphite-like material that is dif-
ficult to spall and gasify. Due to its hardness and
rigidness, it poses a risk of tube rupture during a
thermal shock.
Pyrolytic coke, also called condensation coke, is
softer and less structured than catalytic coke. It is
formed in the bulk of the gas by several mecha-
nisms, including dehydrogenation, polymerisa-
tion, and condensation of aromatic and olefinic
compounds. Pyrolytic coke is the major form of
coke found in crude, vacuum, delayed coker heat-
ers as well in liquid (naphtha, gas oil) crackers. It
has an amorphous structure, is softer, spalls eas-
ily and fouls downstream equipment like transfer
line exchangers.
Like any other kind of fouling, coking has a
major impact on the heat transfer efficiency due
to its low thermal conductivity. Coke thermal
conductivity as a function of its porosity is illus-
trated in Figure 3.
Condensation / pyrolytic coke has a ther-
May 2022 3
 Figure 2

4 May 2022 www.digitalrefining.com

mal conductivity in the range of
1 – 2 W/mK (0.6-1.2 Btu/h°Fft)
whereas catalytic coke thermal
conductivity is in the range of 3 –
4 W/mK (1.8 -2.4 Btu/h°Fft) due
to its structure and lower poros-
ity. Compared with the conductiv-
ity this is an order of magnitude
lower. The impact of coking on
tube temperature can therefore
be profound. For example, con-
sider the outlet tube of a cracking
coil with an absorbed heat flux of
50,000 W/m2. A coke layer of 5
mm thickness and thermal con-
ductivity of 2 W/mK will increase
the tube wall temperature by

So, a modest coke layer of 5 mm Figure 3

(0.2 inch) thickness will increase
the tube wall temperature by 125°C (225°F).
A typical ethylene coil will see a temperature
increase of 100-150°C between Start and End
of Run when the tube has reached its allowable
maximum temperature, all due to coking. This
happens in a span of 30-90 days.
There are other issues associated with cok-
ing besides periodic decoking, like carburisation,
creep, and chrome depletion. These can all dam-
age the tube, resulting in increased maintenance
and replacement cost, and a risk of coil failure
during operation if not properly mitigated.
and the tube material. The presence of coke on
the tube wall increases not only the tube temper-
ature but also increases the total weight of the
tubes dramatically. Deformation due to creep
leads to creep voids inside the material:
Chrome depletion: the surface of the tube
becomes depleted of chrome by the continuous
process of chrome carbide formation and the
removal of the chrome oxide layer. Over time

Carburisation: the process of carbon enrichment

of the material and the subsequent formation
of carbides. The presence of a coke layer greatly
increases the rate of carburisation. Carburisation
results in:
• Local volume increase, leading to tube bulging
• Internal stresses due to volume increase, lead-
ing to intergranular cracking
• Embrittlement, causing loss of thermal shock
resistance
• Reduced weldability
• Rupture of the tube

Creep: the elongation / stretching of a tube due to

its weight. The creep rate depends on tube tem- Figure 4 - local tube bulging and cracking due to
perature, the load bearing cross-sectional area carburisation

www.digitalrefining.com May 2022 5


Figure 5 - creep voids
this diminishes the capability of the tube to form
new chrome oxide layers, which accelerates cat-
alytic coking.
Tube failures: the combined effect of all the dam-
age mechanisms can reduce the life of a tube to
as little as four years in severe services and make
it especially vulnerable to thermal shocks.
Factors that impact coking rate
Temperature and velocity
Since coking is a reaction type fouling, the rate of
coking strongly depends on temperature. A high
process temperature:
• favours all reactions, coking included
• produces more reactive species like dienes
• increases diffusion of carbon into the coil
material
In a crude heater, a 10-40° increase in outlet tem-
perature can lead to 50-400% higher fouling rates.
6 May 2022
The model of Ebert and Panchal was developed
to predict fouling behavior of crude oils in heat
exchangers. The combination of an Arrhenius
type equation with a Reynolds dependent factor
shows that heat transfer and process flow velocity
play important roles in fouling:
In fired heaters, the process mass velocity in
the radiant section should be kept in the range of
300-500 kg/m2s to limit fouling.
Feed composition
In cracking heaters, liquid cracking (naphtha,
diesel, gas oil) produces more coke than gas
cracking. Condensation coking is promoted when
liquid feeds have a high End Boiling Point (EBP),
also called a “heavy tail”.
In any service, coke formation is accelerated if
the feed contains high amounts of asphaltenes,
naphthenes (cyclo-alkanes) and aromatics.
Feed contaminants act as coking catalysts and
change the coil surface characteristics:
Sodium: attacks the protective chrome oxide layer
Iron: coking catalyst
Potassium & Vanadium: attack radiant coil surface
Sulphur: the role of sulphur is complex. It pro-
motes pyrolytic coke reactions but produces
weaker coke structure. At the same time, sulphur
passivates coil surface and prevents catalytic cok-
ing. At high levels it promotes carburisation.
Steam
Steam is used to inhibit coke formation in vari-
ous ways. It is used as ‘dilution steam’ in cracking
furnaces to lower the hydrocarbon partial pres-
sure and to reduce the residence time. Typical
steam to oil ratios are 0.2-0.3 for gas cracking
and 0.3-0.5 for liquid cracking.
In vacuum and coking heaters, steam is typ-
ically used as ‘velocity steam’. Typical steam
quantity is 1-2% of feed flow rate. It is usually
injected at the crossover to change the vaporisa-
tion profile and to increase the process velocity.
Any steam in the feed also inhibits coke accu-
mulation by gasifying the carbon that has been
formed already.
Steam is sometimes used to passivate the coil
surface prior to feed introduction by subject-
www.digitalrefining.com
ing the coil to high temperature steam for sev-
eral hours. A chrome oxide layer is formed under
these conditions, which delays and prevents cat-
alytic coke formation. This method is less effec-
tive for older coils that have been decoked several
times and have a rough surface.
Decoking
The act of decoking also has an impact on cok-
ing rate. As mentioned, repeated cycles of coking
and decoking (spalling, erosion) deplete the chro-
mium content at the coil surface. Lack of chrome
prevents the generation of protective oxide layers.
The rough surface that is created by the spalling of
coke has more sites for surface reactions.
There are three main decoking methods:
1. Steam/air decoking
2. Online spalling
3. Mechanical pigging
Steam/air decoking is a process where a mix-
ture of steam and air is introduced into the coils
to gasify and burn the coke. It is typically applied
in cracking furnaces (on-line), delayed cokers
(off-line) and crude and vacuum heaters (off-
line). The decoking process starts with high tem-
perature steam to gasify the coke:
C + H2O  CO + H2
This reaction is endothermic, the process tem-
perature must be higher than 1500°F (800°C) for
the reaction to occur. This step makes the exist-
ing coke layer porous, which enables the next
step of the decoking process. Air is added to oxi-
dise the coke.
C + O2  CO2
This reaction is exothermic, so air must be
added in a carefully controlled way to prevent a
runaway reaction. The coke burn-off starts as
soon as the oxygen and the coke meet, so this
reaction proceeds from the beginning of the coil
www.digitalrefining.com
to the end. Coke ‘spalling’ is the fragmentation of
the cokes layer into smaller particles. This part
of decoking is an intentional part of the steam/
air decoking process but needs to be controlled
extremely carefully. The entire decoking proce-
dure must be carried out carefully, to avoid
• overheating the tubes, when the reaction pro-
ceeds too rapidly
• breaking the coils, when thermal shocks cause
the tubes to contract faster than the coke
• erosion, due to excessive velocities of spalled
coke particles
• tube plugging due to excessive spalling
• carburisation, oxidation, tube bowing etc.
Online spalling is typically used in delayed
coker heaters. This procedure uses high pressure
(superheated) steam at high velocity (100 – 115
m/s). The intent is to vary the coil temperature
to expand and contract the tubes to dislodge the
coke. The benefit of this method is that it is faster
and easier than steam/air decoke or off-line pig-
ging, but the risk is that tubes can be plugged
during excessive spalling.
Mechanical pigging is the process of propel-
ling a “pig” through a coil with the help of a pig
launcher. A pig is a studded device that trav-
els through the pipe, driven by a motive fluid.
Contrary to steam/air decoking or online
spalling, there is no risk of overheating of over-
pressurising the coils. The downside of this pro-
cedure is that it requires heater shutdown, and
an external company is needed to execute the
work. It is typically the most thorough decoking
method unless tubes are oval. Likewise, special
attention must be paid to heater coils with vary-
ing tube wall thicknesses.
LINKS
More articles from: XRG Technologies
More articles from the following categories:
Fired Heaters, Furnaces and Boilers
Corrosion and Fouling Control
Heavy & Sour Feedstocks
May 2022 7