Sulfur Addition to Cracking Furnaces

ABB Lummus Global Best Operating Practice

INTRODUCTION
The formation of coke in the radiant
coil of pyrolysis furnaces has a negative
impact on the overall operation of the
ethylene plant. Typically the formation of
coke leads to reduced run-lengths or
production cuts due to tube metal
temperature (TMT) or pressure drop
limitations. Additionally, when a furnace is
brought back on-line after decoking, large
quantities of CO and CO2 are produced.
These gases can cause significant
operational problems in the downstream
areas of the ethylene plant, particularly in
plants with a front-end acetylene converter.
Several methods can be employed to try
to control the rate of coke formation. These
methods
include
coil
pretreatment,
additives, and coatings. The use of sulfur
as a pretreatment (injected after decoking
the furnace and prior to the introduction of
hydrocarbon feed) and as an additive
(injected during cracking) is addressed
here.
Sulfur (sulfur compounds) is the most
common additive and pretreatment
chemical. Sulfur also has the benefit of
reducing the formation of CO both at the
start of run (SOR) and to a lesser extent
during steady state operation.
CHEMISTY OF CO FORMATION
During the decoke process, reactive
oxygen atoms are deposited on the coil
surface. When cracking begins and coking
starts, these atoms combine with carbon to
form CO. This leads to a peak production
rate of CO at start of run conditions in
untreated furnaces.
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During steady state operation, CO is

produced when oxygen, released from the
dissociation of dilution steam, reacts with
carbon on the tube surface.

H 2O O + H 2

C + O CO
CHEMISTRY OF COKE FORMATION
Three mechanisms govern the rate of coke
formation in an ethylene furnace:

Catalytic coking
Radical surface coking
Condensation coking

Catalytic Coking
Ni, Fe and their oxides in the coil promote
the initial catalytic coke formation. A reactive
hydrocarbon molecule is adsorbed onto the
surface of a catalyst particle on the tube wall
where it decomposes by carbon transfer to
produce hydrogen and carbon atoms. The
hydrogen atoms combine to release hydrogen.

CH 4 C + 2H 2
C x H y xC +

y
H2
2

Carbon diffuses through the metal to produce

coke. The coke grows in fine filaments as
carbon diffuses into the growing coke from an
active catalyst site. This continues until the
active catalyst site is covered with surface
carbon that has not been able to diffuse into the
metal, effectively blocking the catalyst site.

The impact of sulfur seems to depend on:

Radical Surface Coking

Light hydrocarbons produced in the
vapor phase during cracking react with
radicals on the surface of the catalytic coke
to add carbon and produce further radicals.
Condensation Coking
As the cracking reactions proceed, large
molecules form that are characterized as
polynuclear aromatics (PNA). These
molecules may condense on the tube
surface and dehydrogenate to form coke.
This coking mechanism is not important
when cracking C4 and lighter feedstocks but
is significant in longer residence time coils
with heavier feeds.
EFFECTS OF ADDING SULFUR
CO Formation
Sulfur addition inhibits both of the
mechanisms that produce CO.
Pre-sulfiding, (i.e. the addition of a
sulfur compound to the furnace at hot
standby
conditions
prior
to
the
reintroduction of hydrocarbon feed),
removes the reactive oxygen from the tube
surface, thereby reducing the CO and CO2
generation at start of run. The sulfur reacts
with the oxygen to form SO2.
Sulfur injected during the run, retards
the dissociation of water, thus reducing the
oxygen available to react with carbon. This
reduces the steady state production of CO.
Coke Formation
The impact of sulfur on the rate of coke
formation has been extensively studied in
both pilot and industrial facilities. The
results have varied widely with some being
completely opposite of others. For example,
some researchers have found that DMDS
inhibits coking while others claim that the
coking rate is increased.

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Sulfur species
Concentration
Alloy composition
Operating conditions

Lummus analysis of both the literature and

plant data has caused us to conclude that DMS,
DMDS, and other complex sulfur compounds
used at low dosages (less than 100 wppm
contained sulfur) inhibit coke formation in
ethane, other gas feeds, and desulfurized
naphthas.
At low doses the sulfur may reduce
catalytic coking by blocking active catalyst
sites. At higher doses the sulfur may start to
damage the chromium oxide layer and thereby
enhance coking.
Spalling Reduction
In addition to inhibiting coke and CO
production, the addition of sulfur to ethane
cracking furnaces is believed to help prevent
spalling (i.e. coke breaking loose from the
tubes during operation). This has a positive
effect on the run-length as spalling can plug
TLEs and increase the coil operating pressure.
Convection Section Corrosion
The presence of sulfur can prevent
convection section corrosion by preventing
metal dusting.
Dangers of too Much Sulfur
The addition of sulfur to gas feeds and
desulfurized naphthas at low dosages (up to
100 wppm of contained sulfur) inhibits the
formation of coke.
The addition of sulfur at higher rates (200
wppm and above) can result in sulfur attack
and damage to the internal surface of the tube.
Naphtha and gas oil feeds frequently
contain concentrations of sulfur higher than

200 wppm. The sulfur species that occur

naturally in these feeds does not attack the
coil surface in the same way as added
sulfur does so operation with high sulfur
feeds usually has no negative impact on
coil life.
SULFUR IN THE FEEDSTOCK
Most naphtha and heavier feedstocks
contain sufficient sulfur so that the addition
of sulfur during the run is not required and
has no impact on the run length or
reduction in CO produced.
However, with gas feedstocks (C4 & lighter
that typically contain no sulfur) and
desulfurized naphthas, the addition of
sulfur during the furnace run normally has a
positive effect in decreasing the CO
production and extending the furnace run
length.
SOURCES OF SULFUR
The bulk of the evidence indicates that
H2S must be formed in order for sulfur to
be active in the coking process. However,
use of H2S is not recommended due to the
handling problems that arise. Complex
sulfur compounds that decompose at
cracking temperatures to yield H2S and
other sulfur compounds are preferred.
Numerous complex sulfur compounds
are available for use in the ethylene plant.
These include:

Diethyl Sulfide (DES)

Dimethyl Disulfide (DMDS)
Dimethyl Sulfide (DMS)
Ethyl Mercaptan (EM)
Tertiary Butyl Polysulfide (TBPS)
Tertiary Nonyl Polysulfide (TNPS)

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The data for Figures 1, 2, and 3 was obtained

from www.atofina.com.

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The choice of the sulfur source is

usually based on availability, price and
environmental/safety considerations (odor,
toxicity, high flash point, etc.).
Based on contained sulfur, DMS,
DMDS, and DES are generally the cheapest
although this varies from one geographic
area to another. Polysulfides (TBPS, TNPS)
are the best from environmental and safety
perspectives.
Figure 1 depicts the sulfur content of
some commonly used sulfur compounds.
Figure 2 illustrates the relationship between
temperature and decomposition for sulfur
compounds and Figure 3 shows the odor
threshold.
RECOMMENDATIONS
Determine the most economical source
of
sulfur
that
meets
plant
environmental/safety requirements.
Pre-Sulfiding Step
While the furnace is in hot steam
standby after the furnace has been decoked
and before the introduction of hydrocarbon
feed, sulfur is injected at approximately 125
ppmw contained sulfur, for up to four hours
at relatively low coil outlet temperatures
(COTs) (700-750C). The COT must,
however, be sufficiently high to decompose
the injected sulfur to H2S.
Pre-sulfiding may not be necessary
except for plants that have front-end
acetylene converters. (These plants have
the acetylene converter in the charge gas
compressor area.) CO acts as a temporary
poison to the catalyst and unless the reactor
is operated at elevated temperatures the
ethylene product can go off specification.
Operation at higher temperatures is not
desirable as this shortens the catalyst life
and runs the risk of a runaway reaction

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occurring in the acetylene converters if the CO

content suddenly drops.
During the pretreatment, sulfur is
converted to H2S and SO2, which can
significantly reduce the pH of the quench
water.
Steady State Operation
Add the lowest effective dose of a complex
sulfur for operation of the furnace with gas or
desulfurized liquid feedstocks.
The lowest effective dose can be found by
experimentation. Start with a low sulfur
injection rate and increase the rate until the CO
does not decrease significantly any more. The
minimum amount is typically between 50 and
100 wppm of contained sulfur.
Figure 4 depicts the typical relationship
between
CO
production
and
sulfur
concentration.
Avoid sulfur rates of 200 wppm and higher
as these levels can lead to sulfur attack and
damage to the radiant coils.