I NTERNATIONAL J OURNAL OF C HEMICAL

R EACTOR E NGINEERING
Volume 8

2010

Article A130

Coke Formation Reduction in the Steam

Cracking of Naphtha on Industrial Alloy
Steels Using Sulfur-Based Inhibitors

Darioush Salari

Aligholi Niaei

Mohammad Reza Shoja

Reza Nabavi

University of Tabriz, ddsalari@gmail.com

University of Tabriz, niaei@yahoo.com

University of Tabriz, m shoja17@yahoo.com

University of Tabriz, reza.nabavi@gmail.com

ISSN 1542-6580
c
Copyright 2010
The Berkeley Electronic Press. All rights reserved.

Coke Formation Reduction in the Steam Cracking of

Naphtha on Industrial Alloy Steels Using
Sulfur-Based Inhibitors
Darioush Salari, Aligholi Niaei, Mohammad Reza Shoja, and Reza Nabavi

Abstract
Coke formation reduction during naphtha pyrolysis was investigated using
dimethyl disulfide (DMDS) and carbon disulfide (CS2 ) as inhibitors with different
feed stocks. Different industrial nickel alloy steels such as stainless steel 304 and
316 (SS304, SS316), HP-modified (HP-mod) and HP-micro (HP-mic) were used
as coupons in a quartz cylindrical reactor for coke formation studies. Coke formation significantly reduced in the presence of the additives or using feeds with
more sulfur compounds. It was revealed that HP-mic alloy has the least coke
deposition rate between other alloys. Scanning electron microscope (SEM) and
energy dispersive X-ray analyzer (EDAX) were used for morphological and elemental surface analyses, respectively. It was found that cokes formed in presence
of sulfurous inhibitors are softer and have less metal concentrations.
KEYWORDS: thermal cracking, coke formation, naphtha, coke inhibitor, sulfur
compounds, alloy steels, dimethyl disulfide, carbon disulfide

Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

1. INTRODUCTION
Thermal cracking of hydrocarbons ranging from ethane to gas oil is the most
important sources of olefins and aromatics which are the main feedstock of
petrochemical industries. In the steam cracking process, naphtha mixed with the
steam and introduced into tubular reactors with short residence time and high
temperature. The steam used in this process is basically an inert gas and it serves
the purpose to increase olefin selectivity and reduce coke formation by reducing
the naphtha partial pressure (Ullmann, 1992).
During the last few years, investigations have been made on coke
formation during the pyrolysis of various hydrocarbons such as ethane (Glasier
and Pacey, 2001; Towfighi, et al., 2003) propane (Trimm and Turner, 1981), nhexane (Pramanik and Kunzru, 1985), and naphtha (Reyniers and Froment, 1994;
Lee, et al., 2004). These studies have shown that coke deposition depends on
several factors, such as, the aromatic and sulfur content of the feedstock,
hydrocarbon partial pressure, temperature, conversion and materials which are
used in construction of the reactor.
The coke deposits inside the reactor wall affects the operation of pyrolysis
reactor with pressure drop increase (which results in lower ethylene yield) and
heat transfer reduction. With time, accumulation of coke forces the operator to
shut down the unit for a determinable period of time, the furnace is, there fore,
taken offline for coke removal (decoking) (Crynes, et al., 2002).
Coke formation during thermal cracking is a complex phenomenon. First,
there is a catalytic phase in which the properties of the tube skin materials (such
as Fe and Ni) play an important role in this phase (Francoise, et al., 1995). Once
the material surface is covered with coke a second heterogeneous, but
noncatalytic mechanism dominates. In this mechanism coke precursors from the
gas-phase react with the coke surface via radical reaction. Coke can also formed
via a homogeneous noncatalytic mechanism, in which physical condensation
products collide with the surface wall, remain adhered, and become incorporated
in the coke layer (Kumar, 1999).
The development of coke inhibitors has paralleled the various coke
formation mechanisms described above. The techniques commonly used today to
reduce coke formation include the pretreatment of feedstocks, a change in the
materials used in the construction of the reactor, alteration of the surface
chemistry of the reactor, or the addition of coke inhibitors to the feedstock
(Renjun, 1993).
In the last few years, coke deposition, considerably, has been reduced by
producing new nickel alloys and adding special additive to the structure of these
alloys. Furnace tubes up to and through the 1940s were typically fabricated from
wrought chromium steels and/or austenitic stainless steel alloys. To increase tube

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Article A130

life, greater carbon concentrations are required to promote precipitation hardening

upon elevated temperature exposure. In the 1960s , the cast HP alloys (nominally
25wt% chromium, 35 wt% nickel, 0.5 wt% carbon, with iron as the balance) were
developed to provide greater creep strength as compared to stainless steel alloys
(haffman, et al., 2007).
Zhang and Albright (2010) have tested several pretreatment of the coils in
their furnaces have resulted in a major reduction of coke. They have tested several
pretreatments of the different high-alloy steels in their furnaces using several
oxidizing gases (like air, CO2, CO, CO2/H2O and H2/H2O) at 800-1200C. They
concluded that pretreatments of the coils decreased the amount of coke deposited
on the surface.
The development and use of additives appears to be the most effective and
practical method in the coke formation reduction. Coke inhibitors reported in the
literature include salts of alkali metals or alkali-earth metals at parts per million
(ppm) quantities, which are believed to promote coke gasification by steam. There
are some reports in literature for inhibiting the effect of sulfur, carbonate and
phosphor compounds.
Salari, et al., (2009) found that, the coke formation on SS321 is decreased
with increasing carbonate concentration. Na2CO3 and K2CO3 promote coke
gasification by steam.
Triphenyl phosphine oxide (TPPO) and triphenyl phosphine (TPP) tri-otolyl phosphine (TTP) were found to be effective coke inhibitors. With these
inhibitors the coke deposited on SS321 decreased with the increasing
concentration of them in the feed, and also with increasing run time a film of the
phosphorus-metal complex covers the surface and the metal activity is gradually
reduced (Niaei, et al., 2008). The effectiveness of benzyl diethyl phosphite as a
coke inhibitor during naphtha pyrolysis was investigated by Chowdhury and
Kunzru (1993) in a tublar reactor at 1073K and atmospheric pressure. Significant
reduction in the coking rate was achieved by adding benzyl diethyl phosphite to
the feed.
Sulfur addition is believed to minimize the overall coking rate by
suppressing the catalytic activity of the metal wall (Francoise, et al., 1995). The
reduction in the rate of coke formation during naphtha pyrolysis due to the
addition of Dimethyl disulfide (DMDS) has been investigated in a jet stirred
reactor at atmospheric pressure. It was found that coke formation on experimental
coupons is decreased with increasing DMDS concentration (Salari, et al., 2006).
In commercial steam cracking, sulfur components like carbon disulfide (CS2) are
added to the feed. It is reported that the CO yield is thereby reduced and this is
often interpreted as evidence of reduced coking (Reyniers and Froment, 1995). A
pilot unit with cooling section and TLE (Transfer Line Exchanger) was
successfully used by Dhuyvette, et al., (2001) for coke formation studies. They

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Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

found that DMDS was effective in controlling coke formation during pyrolysis of
naphtha, also sulfur addition during thermal cracking of naphtha controls CO
production very well. They concluded that the additive provides a film coating
and passivate the metal surface to prevent it from catalyzing the coke formation.
The influence of DMDS, which is widely used as an additive in ethylene plants,
was investigated by Wang et al., (2007) in a continuous-flow stirred-tank reactor
(CSTR). The n-hexane was used as the feed. The results indicated that continuous
addition of DMDS or presulfidation followed by continuous addition of DMDS
are both effective in suppressing CO production. Presulfidation of the oxidized
Incoloy 800HT surface with DMDS results in a decrease in coke formation by 1020%, while continuous addition of trace amounts of DMDS has no significant
influence on the coke deposition. Wang, et al., (2008) found that the influence of
the combination of two Si-containing additives like bis-trimethylsilyl sulfide
(BTMS) and tetraethyl orthosilicate (TEOS) with S-containing additives like
DMDS on steam cracking of hydrocarbons cause a minimal coke deposition, and
results in a decrease in the rate of coke formation.
The objective of this work is to study the influence of naphtha type (light
and heavy naphtha) in coking rate on different industrial types of alloy steels
which are used in constructing industrial thermal cracking reactors. Different
sulfur compounds, namely CS2 and DMDS are used as coke inhibitors in the
experiments. Coke morphology and their metals content were studied by SEM
and EDAX respectively.
2. EXPERIMENTAL
2.1. MATERIALS
DMDS and CS2 as inhibitors were purchased from Merck (Darmstadt, Germany)
in analytical grade. Light naphtha (LSRG) and heavy naphtha (HSRG) were
purchased from Tabriz petrochemical complex, Tabriz, Iran. LSRG and HSRG
compositions are listed in Table 1.
Table 1. LSRG and HSRG composition (wt%)
Compounds
LSRG
HSRG
Paraffins
Isoparaffins
Naphthenes
Olefins
Aromatics
Total sulfur
Other hydrocarbon
Specific gravity

37.53
36.31
13.86
0.34
3.39
2.72
Balanced
0.67

25.1
27.5
24.69
0.44
12.31
1.2
Balanced
0.73

Published by The Berkeley Electronic Press, 2010

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Article A130

The setup used for the experiments of hydrocarbons thermal cracking is

shown schematically in figure 1. The input stream consists of naphtha and
distillated water for preparing dilute steam that arrives to the preheater from
individual containers using two regulated micro pumps. To study of feed nature
effectiveness on the rate of coke deposition, experiments were carried out with
two types of naphtha. Preheater consists of cupper coils that are heated
electrically. The temperature of preheater is controlled by an electronic control
system in the range of 523-573K. In this temperature, both naphtha and water are
in steam form. They were mixed together completely and arrived at a quartz
cylindrical reactor with a volume about 706.5 cm3 which was placed vertically in
an electrical furnace. The furnace temperature was controlled by a digital control
system in the range of 1073-1173K. The resident time in the reactor was regulated
by feed flow rate.
Evaluation of the amount of precipitated coke could be possible by
measuring the weight of a small coupon with dimensions of 20x5x10 mm
suspended in the cylindrical reactor before and after each pyrolysis run. All
coupons were cut from the industrial cracking tubes. The original tubes had inner
and outer diameter of 117 and 128.5 mm respectively and were purchased from
Tabriz petrochemical complex, Tabriz, Iran. Figure 2 shows a half cross section
of an industrial cracking tube and a coupon which was used in coke formation
studies.

Figure 1. Set up for naphtha steam cracking to study of coke deposition.

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Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

Figure 2. (a) A half cross section of an industrial cracking tube and (b) A coupon which was cut
from (a) and used in the coke formation studies.

By using this system it is possible to obtain a variety of resident times

via changing feedstock flows. Output products are condensed immediately by a
condenser system. Also the gaseous products were analyzed by Shimadzu 2010
gas chromatograph apparatus with a flame ionization detector (FID) system and
RT-QPLOT column (30 meter, ID 0.53 mm, Max Prog. Temp. 583K). To study
of coking rate in the pyrolysis of naphtha, pyrolysis runs, in which inert steam
dilutions with mass ratio of about 0.7 (Kg steam to Kg feed) have been used, were
conducted at atmospheric pressure and the temperature about 1133K. All
pyrolysis runs were conducted under specific conditions as present in Table 2.
Table 2. Operating conditions of naphtha cracking
Temperature(K)
1133
Residence time(s)
0.5
Pressure(Pa)
101325
Duration Time(min)
20
Naphtha flow rate(cm3/min)
2
0.87
Steam flow rate(cm3/min)
Dilution(kg/kg)
0.7

The deposited coke was analyzed using a scanning electron microscope

(VEGA\TESCAN, at Razi Metallurgical Research Center, Karaj, Iran) equipped
with an energy-dispersive X-ray analyzer (EDAX).

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Vol. 8 [2010], Article A130

3. RESIDENCE TIME CALCULATION

The residence time was calculated using the following relationship (Niaei, et al.,
2008):
t

PV r
SR
1
RT ( hc .V hc ).[

]
M w ( hc ) M w ( w )

(1)

Where t is the residence time (s), P is the atmospheric pressure (Pa); Vr

is the volume of the reactor (m3); R is the gas constant (m3.Pa.K-1.kmol-1); T is the
reaction temperature in kelvin; Vhc is the flow of naphtha (m3/se); hc is the
density of naphtha (kg/m3); Mw(hc) is the average molecular mass of naphtha
(kg/kmol); Mw(w) is the molecular mass of water (kg/kmol), and SR is the steam to
naphtha ratio (kg steam/kg naphtha).
4. RESULT AND DISCUSSION
Effect of feed type, alloy type and sulfur inhibitors on coking rate were
investigated at atmospheric pressure. Coke morphology and their metal content
were studied by SEM and EDAX respectively.
4.1. EFFECT OF FEED TYPE ON COKING RATE
All experiments were carried out with two types of naphtha, LSRG and HSRG.
LSRG has higher sulfur content than HSGR. Figure 3 shows effect of feed type
(composition) on the coking rate. It is clear that LSRG has lower coking rate than
HSRG with all alloys.

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Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

2.5

Coking rate (g.cm-2.s -1)

Coking rate (g.cm-2.s-1)

2.5

1.5

1.5

0.5

0.5

0
HSRG

LSRG

2.5

HSRG

LSRG

HSRG

LSRG

2.5

Coking rate (g.cm-2.s -1)

Coking rate (g.cm-2.s -1)

1.5

0.5

2
1.5
1
0.5
0

0
HSRG

LSRG

Figure 3. Effect of feed type on coking rate in different alloys (a) SS304 (b) SS316 (c) HP-mod
(d) HP-mic. Operation temperature: 1133K and naphtha flow: 2 cm3/min.

4.2. EFFECT OF ALLOY TYPE ON COKING RATE

In order to study of alloys, type on coking rate all experiments were carried out
with 4 types of industrial alloys, using two types of feed (figure 4). Results
indicate that by feeding both LSRG and HSRG, high performance micro
(HP-mic) alloy has the least coking rate while stainless steel 316 (SS316) alloy
has the most coking rate.
It is clear that primitive alloys like stainless steel 304 (SS304) (17.72 wt%
chromium, 8.82 wt% nickel, 0.06 wt% carbon, with iron as the balance) and
specially SS316 (16.07 wt% chromium, 10.68 wt% nickel, 0.047 wt% carbon,
with iron as the balance) in comparison with new HP alloys have the most coke
deposition rate because of high Cr and Ni concentration in their construction
(Rajanna, et al., 1996).

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International Journal of Chemical Reactor Engineering

Coking rate (g.cm-2.s -1)

2.5

Coking rate (g.cm-2.s -1)

2.5

Vol. 8 [2010], Article A130

1.5

1.5

0.5

0.5

0
SS316

SS304

HP-mod

HP-mic

SS316

SS304

HP-mod

HP-mic

Figure 4. Coking rate in different alloys with two types of naphtha (a) HSRG (b) LSRG, Operation
temperature: 1133K and naphtha flow: 2 cm3/min.

The high performance modified (HP-modified) alloy had the same

nominal chemistry of HP alloy along with the addition of typically 1 wt%
niobium. The niobium addition results in precipitation of M23C6, M7C3, and MC
type primary carbides (where M is primarily chromium) upon solidification. In
the M23C6 and M7C3 carbides, niobium substitutes for some of the chromium with
the complex niobium-chromium carbides being more stable at elevated
temperatures as compared to chromium carbides. Also HP-micro alloys materials
was based on the HP-modified chemistry with micro additions of alloying
elements. Titanium is the most common micro-alloying addition with other
micro-alloying additions including zirconium, tantalum, or tungsten. The microalloying additions provide a fine dispersion of MC type carbides that are stable at
the temperatures well in excess of 1093C, and enhance micro-alloys resistance
against coke deposition, so the coke deposition rate is reduced in these alloys
(Haffman, et al., 2007).
4.3. EFFECT OF CS2 ON THE COKING RATE
To study the effectiveness of carbon disulfide as a coke inhibitor on the coking
rate, pyrolysis runs were carried out in the presence of a variety of CS2
concentrations that was added to LSRG and HSRG. In all types of alloys coke
formation is decreased with increasing CS2 concentration and it reaches a constant
level in high concentration (figure 5).

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Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

2.5

(a)

SS304

C oking rate ( g .cm -2 .s -1 )

SS316

HP-mod
HP-mic

1.5

0.5

0
0

100

200

300

400

500

600

ppm CS2

2.5

(b)

SS304

C oking rate ( g.cm -2 .s -1 )

SS316
2

HP-mod
HP-mic

1.5

0.5

100

200

300
ppm CS2

400

500

600

Figure 5. Effect of CS2 concentration on coke deposition adding to (a) LSRG and (b) HSRG,
Operation temperature: 1133K and naphtha flow: 2 cm3/min.

As the first step in coil coking involves chemisorption of hydrocarbons, it

is clear that the properties of the metal surface play an important role in the initial
step of coke deposition. It seems as though under the conditions prevailing in the
cracking coil, thermal decomposition of CS2 will occur, with the main
decomposition products being dimethyl sulfide, methanethiol, carbon disulfide,
carbonyl sulfide, thioformaldehyde, hydrogen sulfide, and SH radicals.
Adsorption of sulfur components from the gas phase onto the metal surface
proceeds more readily than the adsorption of either hydrocarbons or water. The
presence of unshared electron pairs in sulfur compounds can lead to very strong

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International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Article A130

chemisorption on the metal surface. This is the main reason for the much decrease
in coke formation. Furthermore, the sulfur present in the feed can react with the
metal surface to form metal sulfides, thus passivate the surface. Because sulfur
adsorption can also influence dehydrogenation reaction, it can be expected that
the characteristics of the coke layer, and in particular its hydrogen content and
also its microstructure (density, porosity), can be altered by addition of sulfur. We
studied the cokes microstructure in section 4.5. (Salari, et al., 2006 and Salari, et
al., 2009).
4.4. EFFECT OF DMDS ON THE COKING RATE
Dimethyl disulfide was found to be an effective coke inhibitor and the coke
deposit in all types of alloys decreases with the increasing concentration of
DMDS in the both LSRG and HSRG (figure 6). Decomposition of DMDS occurs
preferably by breaking C-S bond because of low dissociation energy (182 kJ/mol)
(eq.2). Dissociation energy of S-S is higher than C-S bond (213 kJ/mol), in spite
of this, S-S bond breaking occurs as shown in the eq.3. At higher temperatures
(over 1073K), DMDS decompose to hydrogen sulfide, nevertheless, metanethiol,
thioformaldehyde, carbon disulfide and methane are formed too. The radicals
which are produced through eq.2 and eq.3 may be enter to hydrogen abstraction
reactions (eq.4). SH radicals and/or formed S atoms can react with reactor metal
surface as shown in the eq.5, so that a thin layer of metal sulfide will be formed
that this thin layer will reduce catalytical effect of metal surface (Salari, et al.,
2006).
CH 3 S S CH 3 CH 3 CH 3 S S

(2)

CH 3 S S CH 3 2CH 3 S

(3)

R1 H R2 R1 R2 H

(4)

R2 CH 3 , CH 3 S S , CH 3 S
SH metal metalsulfi de H

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(5)

Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

11

(a)

SS304

Coking rate (g.cm-2.s-1)

SS316
HP-mod

1.5

HP-mic

0.5

100

200

300

400

500

600

ppm DMDS

2.5

(b)

SS304
SS316

Coking rate (g.cm-2.s-1)

HP-mod
HP-mic

1.5

0.5

0
0

100

200

300

400

500

600

ppm DMDS

.
Figure 6. Effect of DMDS concentration on different alloys (a) LSRG feed and (b) HSRG feed.
Operation temperature: 1133K and naphtha flow: 2 cm3/min

The comparison of figure 5 and figure 6 shows that sulfur inhibitory

effects on coking rate is as below:
For the equal sulfur concentration in same feed and on same alloy,
absorbed sulfur on surface for DMDS is greater than CS2 and this cause a
more reduction of coke deposition (figure 7).

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12

Vol. 8 [2010], Article A130

0.76

Coking rate (g.cm-2.s-1)

0.74
0.72
0.7
0.68
0.66
0.64
0.62
0.6
CS2

DMDS

Figure 7. Comparison of inhibiting effect of CS2 and DMDS (200 ppm) adding to LSRG on
HP-mic alloy. Operation temperature: 1133K and naphtha flow: 2 cm3/min

4.5. MORPHOLOGY AND METAL CONTET OF DEPOSITED COKE

To study the morphology and metal content of deposited coke, a number of runs
were taken at the same operating conditions (T=1133 K, t=0.5 s, run time=20
min). Figures 8 and 9 show photomicrographs of coke deposited on 4 types of
alloys, during pyrolysis of LSRG in both cases, without and with DMDS as
inhibitor. All of the microphotographs are of the coke surfaces that were in
contact with the gas side.
Figure 8(a) shows that the main morphology in the absence of inhibitor on
the SS304 is racemose and filament type, while in Figure 8(b) it can be seen that
the coke deposited on the SS316 has constant diameter filament. In figure 8(c) the
major morphology in the coke deposited on HP-mod is amorphous and in some
cases spherical coke, however laminated with low porosity can be seen in the
coke deposited on HP-mic.

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Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

13

Figure 8. Morphology of the deposited coke during pyrolysis of LSRG without inhibitor on
different alloys (a) SS304 (b) SS316 (c) HP-mod (d) HP-mic.

The morphology of the coke in the presence of DMDS as a coking

inhibitor (figure 9) consisted mainly of (a) constant diameter, (b) lumpy and
racemose coke, (c) racemose and lumpy with high density (d) spherical and
coalesced globules with high porosity.

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Vol. 8 [2010], Article A130

Figure 9. Morphology of the deposited coke during pyrolysis of LSRG with DMDS as inhibitor on
different alloys (a) SS304 (b) SS316 (c) HP-mod (d) HP-mic.

Comparing the morphology of deposited cokes in the presence of inhibitor

and deposited coke without inhibitor show that the porosity observation in the
deposited cokes in the presence of inhibitor is more than that without an inhibitor.
So, this coke can be soft. Softer coke in industrial reactors is carried by gas flow,
in other word online decoking can be done.
Figure 10 shows EDAX analysis of the coke surface during pyrolysis of
LSRG without and with DMDS on HP-mic alloy, indicated that the main metal
constituents are iron, nickel, and chromium. It is well documented (Albright and
Mareck, 1988; Francoise, et al., 1995) that metals such as iron, nickel, and
chromium from the reactor wall are incorporated in the coke. These metals,
particularly iron and nickel, are known to catalyze coke formation.

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Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

15

(a)

Cr

Fe

Ni

Energy(keV)

(b)

Cr

Fe

Ni

Energy(keV)

Figure 10. EDAX analysis of deposited coke during pyrolysis of LSRG on HP-mic alloy (a)
without inhibitor and with (b) DMDS as inhibitor.

Table 3 presents concentration of these metals in the deposited coke

during pyrolysis of LSRG in both, without and with DMDS or CS2 as inhibitors.
The results indicate that the concentration of iron, nickel and chromium in the
coke were significantly reduced when either DMDS or CS2 were added to feed.
These EDAX studies suggest that the sulfur compound inhibit the coking rate by
passivating the surface so that the concentration of metals incorporated in the
coke is reduced.

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International Journal of Chemical Reactor Engineering

16

Table 3. Concentration (wt%) of Ni, Cr and Fe in the deposited coke during pyrolysis of
on different alloys without inhibitor and with DMDS and CS2 as inhibitor.
SS304
SS316
HP-mod
HP-mic
Feed
Ni
Cr
Fe
Ni
Cr
Fe
Ni
Cr
Fe
Ni
Cr
2.0 1.9
71.5 0.6 2.7
LSRG
0.0
17.47 2.64 10.01
15.55
1.31
6
8
6
3
0
1
LSRG
+
1.4
1.8 16.5
0.0
43.5 0.2 1.0
1.93 7.12
12.33
200pp
0.26
0
5
1
1
5
2
9
m
DMDS
LSRG
+
0.0
31.5 0.5 2.3
1.6
1.9 17.0
0.44
14.14
2.61 8.98
200pp
1
8
5
7
1
7
9
m CS2

Vol. 8 [2010], Article A130

LSRG
Fe
14.6
7
3.08

14.5
6

4.6. GC ANALYSIS
Table 4 shows the main cracked gas composition. It can be concluded that sulfur
additives does not affect considerably the concentration of the main output
gaseous species.

Feed
HSRG
HSRG +
200ppm DMDS
HSRG+
200ppm CS2
LSRG
LSRG +
200ppm DMDS
LSRG +
200ppm CS2

Table 4. Output gaseous composition.

Products concentration (wt%)
C2H4
C3H6
Butenes
28.12

13.90

5.06

27.97

13.77

5.11

28.08

14.01

5.15

26.40

12.88

4.14

26.22

12.43

4.09

26.29

12.56

4.25

5. CONCLUSION

An experimental system for studying coke deposition in naphtha pyrolysis

was designed and assembled. The system is reliable and feasible for a wide range
of research work.

This study shows that the rate of coke formation during naphtha pyrolysis
can be reduced by using high sulfur content feed. The sulfur present in the feed

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Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

17

can reduce the rate of coking in two ways, it can either react with the metal
surface to form metal sulfides, thus passivating the reactor wall, or it can take part
in the homogeneous gas phase free radical reaction, so LSRG has the least coke
deposition rate in all alloy types because of high sulfur compounds concentration.

HP-mic has lower coke deposition rate on comparison with respect to

HP-mod, SS316 and SS316.

The coking rate can be significantly reduced by adding DMDS or CS2 to

LSRG and HSRG and DMDS can reduce coking rate better than CS2.

The morphology of the coke was studied by SEM, while EDAX was used
to determine the concentration of metals in coke layer. Pronounced changes in
morphology, due to the addition of inhibitors were observed. It was found that the
concentration of metals, such as Fe, Ni, and Cr incorporated in the coke is
significantly reduced due to the addition of these compounds.

Analysis of cracked gases were revealed that gas products composition did
not change noticeable by adding coke inhibitors.
List of Symbols
BTMS: Bis-trimethylsilyl sulfide
Carbon disulfide
CS2:
CSTR: Continuous-flow stirred-tank reactor
DMDS: Dimethyl disulfide
EDAX: Energy-dispersive X-ray analyzer
FID:
Flame ionization detector
HP-mic: High performance micro
HP-mod: High performance modified
SEM:
Scanning electron microscope
SS304: Stainless steel 304
SS316: Stainless steel 316
TEOS: Tetraethyl orthosilicate
TPP:
Triphenyl phosphine
TPPO: Triphenyl phosphine oxide
TTP:
Tri-o-tolyl phosphine

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18

Vol. 8 [2010], Article A130

REFERENCES
Albright, L.F., and Mareck, J.C., Coke formation during pyrolysis: Role of
residence time, reactor geometry, and time of operation, Ind. Eng. Chem.,
1988, 27, 743-751.
Chowdhury, S.N., and Kunzru, D., Benzyl diethyl phosphite as a coke inhibitor
during naphtha pyrolysis. Tublar reactor studies, J. Chem. Eng., 1993, 71,
873-879.
Crynes, B.L., Albright, L.F., Tan, L.F., Thermal Cracking, Encyclopedia of
Physical Science and Technology, 3rd edition, 2002, Vol. 16, 613-626.
Academic Press, New York.
Dhuyvetter, I., Reyniers, M.F., Froment, G.F., and Marin G.B., The influence of
dimethyl disulfide on naphtha steam cracking, Ind. Eng. Chem., 2001,
40, 4353-4362.
Francoise, M.M., Reyners, S.G., and Froment, G.F., Influence of metal surface
and sulfur addition on coke deposition in the thermal cracking of
hydrocarbons, Ind. Eng. Chem., 1995, 34,773-785.
Glasier, G.F., and Pacey, P.D., Formation of pyrolytic carbon during the
pyrolysis of ethane at high conversions, Carbon, 2001, 39, 15-23.
Hoffman, J.J., Schutze, M., and Berghof-hasselbacher, E., Development of an
atlas of microstructures for the latest heat-resistant cast alloys, NACE
international,
2007,
Paper
No.07425,
available
at:
http://www.onepetro.org/mslib/servlet/onepetropreview.
Kumar, SH. Triethyl phosphit additive-based fouling inhibition studies, Ind.
Eng. Chem., 1999, 36, 1364-1368.
Lee, J.H., Kim, K.M., Kim, S.H., and Lee C.S., Effect of steam on coking in the
non-catalytic pyrolysis of naphtha components, Korean. J. Chem. Eng.,
2004, 21, 252-256.
Niaei, A., Salari, D., Towfighi, J., Panahi, P., and Nabavi, R., Effect of
organophosphorous compounds as coke inhibitors on coking rate in the
pyrolysis of naphtha, Pet.Sci.Tech., 2008, 26, 2170-2181.

http://www.bepress.com/ijcre/vol8/A130

Salari et al.: Coke Formation Reduction in the Steam Cracking of Naphtha

19

Paramanik, M., and Kunzru, D., Coke formation in the pyrolysis of n-Hexane,
Ind. Eng. Chem., 1985, 24, 1275-1281.
Ranjanna, K., Pathiraj, B., and Kolster, B.H., X-Ray fractography studies on
austenitic stainless steels, Eng. Fracture. Mechanics, 1996, 54, 155-166.
Renjun, Z., Fundamental of pyrolysis in petrochemistry and technology, CRS
Press: Boca Raton, FL, 1993.
Reyniers, M.F., and Froment G.F., Coke formation in the thermal cracking of
hydrocarbons. 4. Modeling of coke formation in naphtha cracking, Ind.
Eng. Chem., 1994, 33, 2584-2590.
Reyniers, M.F., and Froment G.F., Influence of metal surface and sulfur addition
on coke deposition in the thermal cracking of hydrocarbons, Ind. Eng.
Chem., 1995, 34, 773-785.
Salari, D., Niaei, A. Towfighi, J., Panahi, P., Coke inhibition during naphtha
pyrolysis, Iran. J. Chem. Eng., 2009, 9(1), 1-12.
Salari, D., Niaei, A. Towfighi, J., Panahi, P., Nabavi, R., Investigation of coke
deposition & coke inhibition by organosulfur compounds in the pyrolysis
on naphtha in the jet stirred reactor system, Iran. J. Chem. Eng., 2006, 3,
39-50.
Towfighi, J., Niaei, A., Karimzadeh, R., Saedi, G., Hoseini, S., Modeling and
simulation of the pyrolysis reactions and coke deposition in industrial
ethane cracker, Modarres J. Eng., 2003, 10, 82-90.
Trimm, D.L., and Turner, C.J., The pyrolysis of propane. I. Production of gases,
liquids and carbon, J. Chem. Tech. Biotechnol., 1981, 31, 195-204.
Ullmanns Encyclopedia of Industrial Chemistry, Elvers, B., Hawkin, S., Russy,
W., Eds.; John Wiley and Sons:New York 1992.
Wang, J., Reyniers, M.F., and Marin ,G.B., Influence of Dimethyl Disulfide on
Coke Formation during Steam Cracking of Hydrocarbons, Ind. Eng.
Chem, 2007, 46, 4134-4148.

Published by The Berkeley Electronic Press, 2010

20

International Journal of Chemical Reactor Engineering

Vol. 8 [2010], Article A130

Wang, J., Reyniers, M.F., Van Geem, K.M., and Marin, G.B., Influence of
silicon and silicon/sulfur-containing additives on coke formation during
Steam Cracking of hydrocarbons, Ind. Eng. Chem, 2008, 47(5), 14681482.
Zhang, Z., Albright, L.F., Pretreatments of coils to minimize coke formation in
ethylene furnaces, Ind. Eng. Chem, 2010, ASAP.

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