Water Technologies & Solutions

technical paper

catalytic coating for reduced coke formation in

ethylene- producing steam crackers: experimental
and model validation
Schietekat, C.M.; Reyniers, P.A.; Sarris, S.A.; addition, presulfidization and dilution) and feeds (both
Van Geem, K.M.; Marin, G.B. Laboratory for ethane and naphtha) was evaluated. The quantities of
Chemical Technology (LCT), University of Ghent coke produced were drastically reduced as compared
to an uncoated reference coil. These pilot
Kool, L.; Peng, W.; Lucas, P.;
experiments showed that the catalyst is robust and
SUEZ Global Research, Niskayuna, NY and Shanghai,
maintains anti-coking activity over multiple cracking-
China
decoking cycles.

abstract 1. introduction
In this paper we describe our four-year research effort
Coke formation on the inner wall of the tubular
that has resulted in the discovery of YieldUp, a robust,
cracking reactors of steam cracking units has a
novel coating technology for the inner wall of furnace
major influence on the energy efficiency and
tubes that prevent the deposition of coke. YieldUp is
economic viability of the steam cracking process.
based upon a family of ceramic catalysts having a
Hence, many efforts have continued to be carried out
unique structure that is designed to convert coke to
in recent years towards the development of
carbon oxides on contact. Thus, when coke forms
technologies to reduce coke formation. One such
during cracking, it is instantaneously gasified on
technology is the application of a coating on the
contact with the wall. The performance of the coating
reactor inner wall. Distinction can be made between
was tested in a Jet Stirred Reactor (JSR) set-up and at
the coatings that passivate the inner coil wall and
1, 2

the UGent pilot plant for steam cracking.

catalytic coatings that convert coke to carbon oxides.
3

The JSR is used to assess the effect of three different Figure 1 shows the effects of different coatings on
coating formulations on both coke formation and coke formation. A so-called barrier coating
product yields, including CO and CO . The JSR 2 passivates the catalytically-active sites of the reactor
apparatus measures the quantity of coke deposited alloy, eliminating catalytic coke formation. However,
over time by means of continuous thermogravimetric the non-catalytic coke formation, often termed
analysis. The measured rates are compared to those of pyrolytic coke, is not prevented. In contrast, catalytic
a reference uncoated alloy. These experiments allowed coatings convert deposited coke to carbon oxides and
optimization of the catalyst activity to reduce coke hydrogen, by reaction with steam, through
formation, while minimizing the production of carbon gasification reactions.
oxides. The coating activity after several
coking/decoking cycles remained stable.
The best-performing coating was also studied on a
larger scale in a pilot plant. This experiment allowed
the coating’s performance to be evaluated under typical
industrial conditions in a well-controlled and monitored
environment. The influence of several process
conditions (coil-outlet-temperature, continuous sulfur

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AICHE_Catalytic_Coating_Apr2014.docx Apr-14
 Barrier Coating Catalytic Coating
Reactor tube Reactor tube
Reactor tube

Figure 1: Effect of different coating types; from left to

right: bare tube, barrier coating and catalytic
coating.

We have developed YieldUp, a new catalytic coating

based on upon a family of ceramic catalysts having Figure 2: Incolloy 800 HT JSR coupons coated with BCZ
unique chemical structures that are capable of slurry catalyst.
converting coke to carbon oxides on contact. The
performance of different formulations of our coating The same slurry formulation was used to coat the
was probed in a Jet Stirred Reactor (JSR) set-up. The 9mm ID of the furnace tubes used in the pilot
optimal coating was further tested in the UGent pilot experiments described above. Typical coating
plant . In addition, the predicted effects of scale-up of
4
thickness ranged from 20 to 50 µm, as shown in
the coating in an industrial ethane cracker were Figure 3.
simulated. In the following sections, the coating,
experimental set-ups, procedures and results are
discussed. Finally, the modeling results are
summarized.

2. description of the coating

The coatings that were studied in the experimental
program were developed at the SUEZ Global Research
centers in Shanghai, China and Niskayuna, New York.
YieldUp consists of an engineered synthetic ceramic.
When exposed to high temperature steam, water
molecules are chemisorbed and deprotonated,
resulting in the formation of highly reactive oxygen
atoms that instantaneously react to form CO and CO 2

upon contact with coke. We have developed a family of
YieldUp catalyst materials that provides a range of anti-
coking activities, as described below.
The ceramic coating was applied to the JSR coupons by
forming an aqueous slurry of catalyst microparticles
and other additives and dip-coat the coupons, followed
by a high-temperature sintering step. Figure 2 shows
typical JSR coupons prepared in this way.
Figure 3: Coating thickness uniformity in pilot plant
tubing ID.
3. description of the experimental set-ups
3.1 Jet stirred reactor
A schematic representation of the jet stirred reactor
(JSR) is shown in Figure 4. It has four nozzles oriented
in symmetrically opposite directions to assure good
mixing of the gas in the reactor, in an attempt to obtain
as close to ideal mixing as possible, and emulating the
concept of a CSTR reactor 5,6. The reactor is entirely
made of quartz, including the nozzles and walls, to limit
coking to the coupon surface.
To study the coke deposition, a small flat coupon (shown
in Figure 4) is inserted into the JSR and is suspended

Page 2 AICHE_Catalytic_Coating_Apr2014.docx
from the arm of an electrobalance. The reference
coupons used were cut by electro-erosion from the
internal surface of the tubes to dimensions 10 mm ´ 8 mm
´ 1 mm. A small hole (diameter 0.6 mm) is drilled 2mm
from the top of the sample so the coupon can be
positioned inside the reactor from a Kanthal wire with a
Outlet
Nozzles
Reactor tubes
Thermowell
a) Inlet
Figure 4: a) Diagram of the JSR Reactor; b) Cut industrial tubes and a JSR coupon.
The reference samples were polished. The surface
roughness values (Ra) of each coupon was measured
for the polished reference coupons in three directions
(vertically, horizontal and diagonally), but for the coated
coupons only in one direction to avoid damaging of the
coating. The measured values oscillated between
0.06 m and 1.49 m. Before placing the reference
samples into the reactor, they were thoroughly cleaned
to remove any contaminants on their surface. First they
underwent a cleaning procedure, which started by
washing them in a small glass with deionized water for
approximately 5 minutes. Then, they were washed with
diisopropyl ether for 2 minutes, and finally with acetone
in an ultrasonic bath for 2 hours. After that, an
electrolytic scouring in diluted H2SO4 (1.5 wt%) took
place for 15 min at a voltage of 8V, with the metallic
sample connected to the cathode and a graphite stick
connected to the anode. Finally, the samples were
briefly rinsed with deionized water, and hung from the
balance, to start a new cracking test.
After cracking, the effluent is cooled immediately
downstream of the reactor, in order to quench the
effluent and impede any further cracking reactions
from taking place after the effluent leaves the reactor.
For the analysis of the effluent composition, two gas
chromatographs are used: a Refinery Gas Analyzer
(RGA), capable of detecting and quantifying permanent
AICHE_Catalytic_Coating_Apr2014.docx
0.25 mm diameter. This Kanthal wire is connected to the
arm of a Cahn D-200 electrobalance, which
continuously measures the weight of the coupon as a
function of time. The balance can measure the weight
with an accuracy of 0.01 mg.
Coupon
gases (up to C4), and a Trace ultra GC, measuring the
effluent from methane up to 2-methyl naphthalene.
Computational fluid dynamics (CFD) simulations have
been performed to verify the uniformity of the JSR in
terms of temperature and species concentration. An
ethane steam cracking experiment was simulated
with operating conditions close to the experimental
process conditions mentioned in paragraph 4.1.
The temperature profiles in several cross sections of
the reactor are shown in Figure 5. In the x-plane and
y-plane cross section, the temperature in the quartz
is also shown, in the xy-plane cross section, only the
temperature of the process gas is shown. The voids
are the locations of the coupon and the thermocouple
well. The temperature gradients in the bulk of the
reactor are quite small with a difference between
highest and lowest bulk temperature of about 20 K.
The temperature of the process gas surrounding the
thermocouple well is close to the temperature of the
process gas near the coupon indicating that the
measured temperature is a reliable value for the
coupon temperature.
Page 3

Figure 5: Temperature [K] in the x-plane (top), xy plane
(middle) and y-plane (bottom).
A similar analysis is made for the mass fraction of
ethene using the same cross- sections of the reactor as
shown in Figure 6. The x-plane cross-section illustrates
the jets where lower ethene mass fractions are
simulated as ethane conversion is still low here. In
general, the concentration gradients in the bulk of the
reactor are small, the regions affected by the jets non-
included. Furthermore, the ethene mass fraction
measured at the reactor outlet is close to the ethene
mass fraction near the coupon.
Figure 6: Ethene weight fraction [wt % wet, i.e. steam
included] in the x-plane (top), xy plane (middle)
and y-plane (bottom).
Page 4
The uniformity near the coupon surface is illustrated
by the distribution functions of temperature and
concentration at the coupon surface shown in
Figure 7. The temperature is narrowly distributed
around 1124 K while the ethene mass fraction is also
distributed around 51.25 wt% with small absolute
deviations of about 1-1.5 wt%.
3.2 Pilot plant
A schematic representation of the pilot plant is shown
in Figure 8. Since the main parts of this unit, the
analytical equipment and the calibration procedure
have been described elsewhere, only a brief
7 8
description, based on Wang et al. , Dhuyvetter et al.
9
and Van Geem et al. will be given. The feed section
controls the supply of the different feedstocks to the
reactor coil. The flow is regulated by the pumping
frequency of a CORI-FLOW pump.
Figure 7: Area-weighted distribution of temperature
[left] and mass fraction ethene [wt% wet, i.e.
steam included] at coupon surface.
The mass flow rate of all feeds is measured
continuously instead of the volume flow in order to
AICHE_Catalytic_Coating_Apr2014.docx
avoid inaccuracies due to volume dependency on
temperature and pressure. The pumping frequency is
automatically adjusted by the controller of the CORI-
FLOW. When the fluid level in the intermediate barrel is
too low, the barrel is automatically refilled with feed
from the storage barrels. Gaseous hydrocarbons are
fed to the reactor directly from the gas bottle by means
of a separate CORI- FLOW. The furnace, built of
silica/alumina brick (Li23), is about 4 m long, 0.7 m wide
and 2.6 m high. It is fired by means of ninety premixed
gas burners, mounted with automatic fire checks and
arranged on the side walls in such a way as to provide
a uniform heat distribution. The fuel supply system
comprises a combustion controller, for the regulation
of the fuel to air ratio, and the usual safety devices. The
furnace is divided into seven separate cells, which can
be fired independently to set any type of temperature
profile. Twenty thermocouples and eight manometers
are located along the reactor coil to measure the
temperature and pressure of the process gas. The
reaction section of the tube is about 12m long, made of
Incoloy 800HT, and has an internal diameter of 9mm.
These dimensions are chosen to achieve turbulent flow
Figure 8: Schematic representation of the pilot plant unit.
AICHE_Catalytic_Coating_Apr2014.docx
conditions in the coil with reasonable feed flow rates
(Re>7000). At the reactor outlet, the injection of
nitrogen provides an internal standard and
contributes to a certain extent to the quenching.
Before the cooling of the effluent, a sample is taken
for the on-lineC analysis. The liquid and the tar are
+
separated from the cooler exit flow by means of a
knock-out vessel and a cyclone. The pressure at the
exit of the reactor is controlled by a reduction valve.
A fraction of the product gas is then withdrawn for on-
line C analysis, while the rest of the effluent is sent
-
directly to the flare.
4. experimental procedures
4.1 Jet stirred reactor
The experiments carried out in the JSR setup had
three main steps. These are pre-oxidation, cracking
and decoking. Each one is described in detail below.
Figure 9 summarizes the timeline of the followed
procedure, and indicates the main parameters of
each stage.
Page 5
Figure 9: Timeline of the coking – decoking experiments in the JSR setup: the blue line represents a typical weight signal.
In the pre-oxidation step, the samples were first
oxidized in-situ prior to the cracking runs to mimic the
surface state of an industrial cracking coil. For that
purpose, the reactor temperature was raised to 1023 K
with a heating ramp of 300 K/h and a constant N2 flow
(6.7·10 Nl/s). Once this temperature was reached, the
-3
feed to the reactor was switched to a constant flow of
air only (6.7·10 Nl/s). This pre-oxidation lasted 12-14
-3
hours, after which, keeping the temperature constant
at 1023 K, N was fed again to the reactor (6.7·10 Nl/s).
2
-3
To start a cracking run, the temperature of the reactor
was raised to 1173 K, with the same N flow as before
2 Finally, and as an “overnight” mode, the reactor was
(6.7·10 Nl/s). This in order to have a reference state in
-3
which the weight of the sample could be measured
before and after every cracking run. After the weight of
the sample was recorded, the reactor was further
heated to 1283 K. As the heating proceeded, water with
DMDS (11 10-6 kg/s) and ethane (0.0275 Nl/s) are being
fed to the evaporators (dilution δ = 0.33 kgH O/kgC H )
2 2
and sent to the vent, in order to get a steady evaporation
and mixing before sending this cracking mixture to the
reactor.
Once the reactor temperature was stable at 1283 K, the
cracking mixture is send to the reactor. The nitrogen
flow is used as internal standard for the
chromatographic analyses. The cracking runs lasted
for 6 hours, throughout which the reactor gas
temperature was controlled to 1159 K yielding an
ethane conversion around 70%. During the cracking
runs, several online injections on the gas
chromatographs were performed to analyze the reactor
effluent gas. For quantification, the internal standard
method was used. 10
When the 6 hours of cracking were completed, the flow
rate of ethane and steam was stopped, leaving only
nitrogen to enter the reactor. At the same time, the
reactor temperature was set to 1173 K. Once the set
temperature was reached, the weight of the sample
was registered, to calculate the weight difference
between the start and the end of the cracking run, thus
verifying that the obtained coking curve provided
reliable data. Afterwards, the reactor was cooled down
to 1023 K with a steam flow rate of 6.7·10 kg/s, and
-6
Page 6
once that temperature was reached, a mix of air
(8.3·10 Nl/s) and nitrogen (8.3·10 Nl/s) was fed to the
3 -3
reactor. At the same time that this mix started
flowing to the reactor, the temperature of the reactor
was set to 1173K again, using a heating ramp of 300
K/h. As soon as the reactor reached 1173 K, the air
flow was maintained, but the nitrogen was switched
off to also mimic the industrial decoking practice.
These conditions were kept for 15 minutes, and then
the feed to the reactor was switched back to only N 2
(6.7·10 Nl/s).
-3
cooled down to 1023 K with N flowing through, and
2
kept like that until the next cracking run would start.
Once the third cycle was completed, the reactor was
cooled down to room temperature instead of going to
the “overnight” mode. The samples were rarely
decoked after 3 coking cycles, to have coupons with
6 coke on their surface for further SEM and EDX
analyses.
4.2 Pilot plant
The experiments carried out in the pilot plant also
consisted of the same three main steps; pre-
oxidation, cracking and decoking. Prior to a cracking
experiment, the reactor was pre-oxidized with a
steam/air mixture. The process conditions of pre-
oxidation are summarized in Table 1.
Table 1: Process conditions during pre-oxidation.
FH O Fair COT COT COT COT COT COT COT
2
Cell 1 Cell 2 Cell 3 Cell 4 Cell 5 Cell 6 Cell 7
(kg/h) (kg/h) (°C) (°C) (°C) (°C) (°C) (°C) (°C)
Pre-ox 1 1 500 550 800 800 800 800 800
Prior to the introduction of the feed, the reactor was
heated under a flow of steam of 2.0 kg/h until the
desired temperature profile is reached. Table 2
summarizes the main process conditions of the
various ethane and naphtha experiments. The effect
of a higher COT was evaluated in one experiment
using the “Ethane COT” conditions.
AICHE_Catalytic_Coating_Apr2014.docx
Table 2: Pyrolysis conditions. feed barrel to provide the desired concentration. For
the ethane experiments, the influence of (steam)
Ethane Ethane COT Naphtha
dilution was investigated. In DIL1, the effect of lower
HC flow rate (g/h) 3000 3000 7500
steam partial pressure was investigated. The water
Steam flow rate (g/h) 1155 1155 3750 mass flow rate of steam was halved to 578 g/h.
COP (bar) 1.7 1.7 1.8 However to provide the same molar dilution and
Duration (h) 6 6 6 space time, nitrogen was added. To maintain the total
CIT cell 3 (°C) 550 550 550 molar inlet flow, a nitrogen flow rate of 1270 g/h was
COT cell 3 (°C) 750 750 700
necessary. In DIL2, the effect of lower total dilution
was investigated. The dilution was halved to 0.1925
COT cell 4 (°C) 790 790 775
kg/kg. To maintain the same total molar inlet flow,
COT cell 5 (°C) 820 820 840
the ethane and steam flow rate were scaled to 3729
COT cell 6 (°C) 840 840 865 and 718 g/h respectively. After 6 hours of cracking,
COT cell 7 (°C) 855 870 875 the temperature of cell 4 to 7 is set to 800°C under a
N flow 1 kg/h. To start decoking, a mixture of
After heating up, the flow rate of steam is set to the
2

steam/air is introduced to the coil. The conditions for

desired value for cracking and the hydrocarbon
decoking are given in Table 3. The CO and CO are
feedstock is introduced. Upon the introduction of
2

continuously measured by means of an infrared

hydrocarbons the temperature of the cracking coil
meter. When the concentration of CO in the effluent
decreases by about 20°C due to the endothermic nature
2

gas is lower than 1 mol %, the temperature from cell

of the cracking reactions. After about 20 minutes the
4 to cell 7 is increased to 850°C. When the
temperature of the cracking coil reaches the set values.
concentration of CO in the effluent gas is lower than
The cracking runs of all experiments lasted for 6 hours
2

0.1 mol %, steam is stopped, only air is used.

starting from hydrocarbon introduction in the reactor.
Furthermore a filter is installed in the condensers
The process conditions used in all tests are specified in
after the reactor (in Figure 8 depicted as (7)), where
Table 2. In the experiments where continuous DMDS
entrained coke is collected. After each experiment,
addition was applied, the DMDS was added in the water
this collected coke is dried and weighed.

Table 3: Decoking conditions.

FH O
2 Fair FN 2 COT COT COT COT COT
Cell 3 Cell 4 Cell 5 Cell 6 Cell 7
Pre-start 0.28 0 0.23 750 800 800 800 800
Start 0.28 0.23 0 750 800 800 800 800
CO <1vol%
2 0.28 0.23 0 750 850 850 850 850
CO <0.1vol%
2 0 0.23 0 750 850 850 850 850

5. experimental results reference experiment. The coking rate is significantly

5.1 Jet stirred reactor
Three different coating formulations were tested and
compared to an uncoated reference alloy, i.e. Incoloy
800HT.
Table 4 summarizes the coke and yield data of the
experiments performed. The BCZ1 coating shows an
reduced for all coating formulations compared to the
reference alloy. For the first cycle the coking rate is
reduced by a factor of 7.8, 3.9 and 3.8 compared to the
reference alloy for BCZ1, BCZ2 and 5BCZ
respectively. This improvement of performance was
obtained by gasification of the cokes by the coating.
Consequently, the effluent during cracking over BCZ1
contained more CO and CO than during the reference
2

increase in ethane conversion and CO and CO yields experiment.

2

compared to the reference alloy, Incoloy 800HT. The

other coatings show similar yields compared to the

AICHE_Catalytic_Coating_Apr2014.docx Page 7
The initial coking rate is taken as an indication of the
deposition of catalytic coke and is calculated as the rate
between cracking times t1 = 15 min and t2 = 30 min. The
asymptotic rate, on the other hand, is calculated
between t1 = 5 hours and t2 = 6 hours, when the mass
increase reaches a stable linear regime. As can be seen
from Figure 10 both the initial and asymptotic coking
rates for all experiments are seen to increase over the
number of cycles, which is attributed to an increase in
surface roughness.
Table 4: Summary of cokes and yield data of jet stirred
reactor experiments.

Incoloy
Coupons BCZ1 BCZ2 5BCZ
800HT
Cycles Coke gain [mg] over 6 hours of cracking
1st 39.0 5.0 10.0 10.2
2nd 42.5 6.5 12.0 11.3 Figure 10: Comparison of the initial and asymptotic
3rd 45.0 9.0 17.2 12.6 coking rates
Species Yield* (wt %)
H 4.28 4.37 4.22 4.21
5.2 Pilot plant
2

CO 2 0.02 0.19 0.02 0.02 As the BCZ1 coating showed the lowest coking rate of
CH 7.06 7.12 7.18 7.10
all tested coating formulations, this coating was
tested in the pilot plant unit. The reactor inner
4

CO 0.17 0.93 0.07 0.06

surface of all tubing used in cell 3 to cell 7 was coated
CH 30.66 29.67 30.56 30.53
2 6
with the BCZ1 coating and compared to a reference
CH
2 4 50.53 50.64 50.67 50.53 reactor made out of Incoloy 800HT.
CH
3 8 0.11 0.11 0.12 0.11
CH
3 6 0.75 0.78 0.81 0.80 5.2.1 Ethane experiments
CH
2 2 1.28 1.41 1.41 1.46 The results of the experiments with ethane as
1,3-C H 4 6 1.11 1.13 1.03 1.03 feedstock are summarized in Table 5. Seven
Benzene 2.42 2.37 2.34 2.33 experiments were performed evaluating the effect of
sulfur addition, coil-outlet temperature and dilution
* Average over all cycles with 10-11 analyses per cycle.
on coking rate and product yields. The total coke has
†
To be performed two contributions: the coke burnt off from the
reactor during decoke measured by the infrared
CO/CO meter and the weighed amount collected in
2

the filter downstream of the reactor after cracking.

Due to the high CO and CO yields, normalization was
2

performed based on the carbon balance instead of

the total mass balance.
Comparing the reference reactor (INC) and the
coated reactor (BCZ1), it is seen that the amount of
coke deposited was reduced by a factor of 4.4 by
application of the BCZ1 coating compared to the
Incoloy 800HT reactor. Consequently, the effluent
contained more hydrogen, CO and CO than during the
2

INC experiment as cokes are gasified to carbon

oxides and hydrogen. The increase in hydrogen and
carbon oxide yields by application of the BCZ1 coating

Page 8 AICHE_Catalytic_Coating_Apr2014.docx
is much higher in the pilot plant experiments than in the conversion, the ethylene and 1,3-butadiene selectivity
JSR experiments due to the larger surface-to- volume are slightly reduced by application of the BCZ1
ratio of the pilot plant reactor. The surface-to-volume coating as was also seen during the JSR experiments.
-1 -1
ratio is 5.1 m and 444.4 m for the JSR and pilot
reactor respectively. Although operated at a similar
Table 5: Summary of cokes and yield data of pilot plant ethane experiments.

Experiment INC BCZ1 DMDS PRES COT DIL1 DIL2

Process conditions

Reactor Incoloy Coated Coated Coated Coated Coated Coated

Feed [g/h] 3000 3000 3000 3000 3000 3000 3729

H2O flow rate [g/h] 1155 1155 1155 1155 1155 578 718

N2 flow rate [g/h] 0 0 0 0 0 898 0

S addition [ppm S/g HC] 50 50 0 50 50 50 50

H2O/HC ratio [g/g] 0.385 0.385 0.385 0.385 0.385 0.193 0.193

(H2O+N2)/HC ratio [g/g] 0.385 0.385 0.385 0.385 0.385 0.492 0.193

(H2O+N2)/HC ratio [mol/mol] 0.642 0.642 0.642 0.642 0.642 0.642 0.321

COT [°C] 856 855 856 856 871 855 855

COP [bar abs] 1.70 1.70 1.70 1.69 1.70 1.68 1.70

Yields* [wt%]

∑C4- 98.9 102.37 104.74 102.60 104.08 101.16 100.76

Ethylene selectivity 80.3 80.0 78.23 79.71 77.93 79.75 80.10
Ethane conversion 63.90 63.21 63.87 64.02 68.58 63.38 61.50

C0-C4 species

H2 4.20 4.54 4.88 4.52 5.03 4.24 4.04

CH 4 3.72 3.48 3.65 3.58 4.18 3.67 3.59

C2H 6
36.10 36.79 36.13 35.98 31.42 36.62 38.50

C2H 4
51.33 50.57 49.97 51.03 53.44 50.55 49.26

1,3-C H 4 CO@ 1.40 1.31 1.20 1.33 1.51 1.41 1.38

CO 0.01 1.75 3.72 2.03 3.31 1.65 0.99

CO2 0.02 2.19 3.61 2.44 3.39 1.02 0.98

Coke formation

From reactor [g coke/6h] 18.5 4.2 1.6 2.4 1.4 3.0 6.1
In filter [g coke/6h] N.D. 0.2 0.5 0.9 0.0 0.5 N.D.
Total coke [g coke/6h] 18.5 4.4 2.1 3.3 1.5 3.5 6.1
* Average over 12-13 analyses per experiment.

AICHE_Catalytic_Coating_Apr2014.docx Page 9
The absence of continuous addition of DMDS was
evaluated in experiment DMDS. The influence on
hydrocarbon species yields is minor. The increase in CO
and CO yield is much more apparent; CO increases
2
from 1.7 to 3.7 wt% and CO2 from 2.2 to 3.6 wt%. Hence
continuous DMDS addition can mitigate CO and CO2
production when the coating is applied. Presulfidization
In experiment DIL2 the steam dilution was also
halved to 0.1925 g steam/g ethane. No nitrogen was
added. To keep the same space time, the mass flow
rate of ethane and steam were scaled to keep the
same molar flow rate. Lower ethane conversion and
resulting lower olefin yields were measured. The CO
and CO yields decreased to 0.99 and 0.98 wt%
2

of the coil with a steam/DMDS solution prior to the
continuous DMDS addition was evaluated in experiment
PRES and shows similar influence on yields compared
to solely continuous DMDS addition in experiment
BCZ1. As expected, higher amounts of cokes were
respectively. In experiment DIL2 a higher coking rate
was measured (6.1 g/h) compared to BCZ1. Higher
coke formation is expected due to higher
hydrocarbons partial pressure and the coating
converting less coke to CO and CO due to the lower
2

measured by continuous DMDS addition. steam partial pressure.

Presulfidization before continuous DMDS addition (3.3
g/6h) shows a coke tendency lower than to solely
continuous DMDS addition (4.4 g/6h).
The increase of the coil-outlet-temperature to 870°C
with continuous DMDS addition (experiment COT)
shows the expected yield results: as ethane conversion
increases, yields of methane, ethylene and 1,3-
butadiene increase. The yields of CO and CO increase
2
5.2.2 Naphtha experiments
The results of the experiments with naphtha as
feedstock are summarized in Table 6. It is seen that
the amount of coke deposited was reduced by a factor
of 2 by application of the BCZ1 coating compared to
the Incoloy 800HT reactor. Consequently, the effluent
contained more CO and CO than during the INC
2

compared to the BCZ1 experiment; CO from 1.75 to 3.3 experiment as coke is gasified. The cracking severity
is lower in experiment BCZ1, although this can mainly
wt% and CO from 2.2 to 3.4 wt%. This can be attributed
2

to higher coke formation and more CO and CO be attributed to a slightly different process gas
2

production by the coating. Surprisingly the higher COT temperature profile.

experiment showed lower coke formation than the
BCZ1 experiment (from 4.4 to 1.4 g/6h). This means that
the coating converts more coke at higher temperatures
as higher coke formation is to be expected at a higher
COT. The higher CO and CO yield in this experiment
2

confirm this argument. This means that longer run

lengths are possible at higher COT in an industrial
cracker.
Finally, the effect of lower dilution was evaluated. The
effect of dilution was evaluated in two experiments:
DIL1 and DIL2. In experiment DIL1 the steam mass flow
rate was halved and nitrogen was added to remain at
the same total mole flow to cancel out the effect of
reduced space time on product yields. As DMDS was
continuously added, comparison is made to the BCZ1
experiment. The yields of CO and CO were lower; CO
2

from 1.75 to 1.65 wt% and CO from 2.4 to 1.0 wt%.

2

Hence, the reduction of steam seems mainly to affect

the conversion of CO to CO . The low dilution experiment
2

DIL1 shows a coking rate similar to BCZ1. Hence, it

seems enough water is present to convert coke to
carbon oxides as in experiment BCZ1.

Page 10 AICHE_Catalytic_Coating_Apr2014.docx
Table 6: Summary of cokes and yield data of pilot plant coils are suspended side by side. Each coil makes
naphtha experiments. eight passes. The coils have a larger diameter in the
two last passes, compared to the first six. The
Experiment INC BCZ1 process gas enters the coils at both end sides and in
Process conditions the middle of the furnace and flows downwards. As
Reactor Incoloy Coated the furnaces is symmetrical, only one half is
Feed [g/h] 7500 7500 simulated. The maximum allowable tube metal
H O flow rate [g/h] 3750 3750
temperature for the reactor alloy is around 1070 °C.
If this temperature is exceeded, production is halted
2

S addition [ppm S/g HC] 50 50

and decoking is started. The characteristics of the
H O/HC ratio [g/g] 0.500 0.500
2
furnace, reactor coils and material properties are
COT [°C] 876 876 summarized in Table 7.
COP [bar abs] 1.81 1.80
Yields [wt%]
∑C4- 83.21 84.89
P/E ratio 0.41 0.46
C0-C4 species
H 2 1.17 1.18
CH 4 21.66 20.27
CH
2 4 33.29 32.26
CH
3 6 13.78 14.73
1,3-C H 4 6 4.32 4.66
CO 0.15 0.35
CO 2 0.006 1.57

C5+ species
Benzene 8.99 9.06
Toluene 2.58 2.79
C5-C9 (BTX excluded) 4.23 4.53
Coke formation
From reactor [g coke/6h] 31.9 15.7
In filter [g coke/6h] N.D. N.D.
Figure 11: Top view of half of the furnace.
Total coke [g coke/6h] 31.9 15.7

In the side walls of the furnace 128 radiation burners

6. simulation of an industrial ethane cracker
To evaluate the effect of application of the BCZ1 coating
on runlength and product yields in an industrial unit,
two coupled reactor-furnace runlength simulations
were performed using the in-house developed
11 12-16
COILSIM1D and FURNACE codes; with and
without application of the coating BCZ1 respectively.
First the industrial unit is described. Afterwards the
main results of both simulations are summarized.
6.1 Description of the industrial ethane cracker
are placed, 64 on each side. The total fuel gas flow for
the 128 burners is adjusted over time to maintain an
ethane conversion of 65% averaged over the four
reactors. The air excess is 2% (i.e. excess to the
stoichiometric combustion). The burner cup
temperature and the temperature of the flue gas
entering the furnace is calculated using the method
14
developed by Plehiers . The composition of the flue
gas is derived from the stoichiometry of the
combustion reactions. The composition of the feed
and the operating conditions of the reactor are listed
in Table 8.

Figure 11 shows a top view of half of the furnace. The

furnace is rectangular. In the center of the furnace four

AICHE_Catalytic_Coating_Apr2014.docx Page 11
Table 7: Characteristics of the furnace. Composition of the feed
Furnace Ethane 100.0 wt%
Length 9.304 m Reactor operating conditions
Height 13.450 m Total hydrocarbon flow 14 ton hr-1
Depth 2.100 m Inlet temperature 600 °C
Thickness refractory material 0.230 m COP 1.8 bar abs
Thickness insulation material 0.050 m Steam dilution 0.35 kg steam/kg feed
Number of burners 128 - Ethane conversion 65 wt%
Reactor coil
Number of reactors 4 - 6.2 Results
Type swaged coils - Table 9 compares the average values over all
# passes 8 - reactors for the uncoated and coated case at start-of-
Total length 100.960 m run (SOR) and end-of-run (EOR) conditions. The most
Internal diameter important differences are discussed here. The
runlength increases from 47 days to 214 days, i.e. by
pass 1-6 0.124 m
a factor 4.55. Assuming 24h for a decoking operation
pass 7-8 0.136 m
of the furnace, 7.6 and 1.7 cracking-decoking cycles
External diameter
are possible within 1 year of operation. Hence, by
pass 1-6 0.140 m adoption of the coating 7.6 - 1.7 = 5.9 extra days of
pass 7-8 0.153 m production are available per year. Moreover the lower
Tube wall thickness 0.008 m energy input need on a yearly basis due to a reduction
of the number coking/decoking cycles will influence
Table 8: Feedstock composition and operating conditions the cracker economics beneficially.
of the reactor coils.

Page 12 AICHE_Catalytic_Coating_Apr2014.docx
Table 9: Average results for the coated and uncoated reactors at SOR and EOR.

Uncoated BCZ1 coated

SOR EOR SOR EOR
Coil-inlet pressure [bar abs] 3.05 3.65 3.05 3.69
Coil-outlet-temperature [°C] 853.6 857.6 853.7 857.8
Residence time [s] 0.67 0.69 0.67 0.70
Maximum tube temperature [°C] 963.5 1070.9 961.9 1070.0
Maximum coke thickness [mm] 1.87 13.93 0.43 13.40
Ethane conversion [wt%] 65.02 65.00 65.02 64.99
Runlength [days] 46.8 213.5
Yields [wt%]
H 2 3.90 3.83 3.96 3.91
CH 4 4.94 5.52 4.87 5.46
CO 0.002 0.003 0.24 0.35
CO 2 0.001 0.002 0.300 0.43
CH
2 2 0.39 0.37 0.40 0.37
CH
2 4 51.16 50.23 50.75 49.58
CH
2 6 34.98 35.01 34.99 35.01
CH
c 6 0.99 1.09 0.96 1.06
CH
3 8 0.18 0.20 0.18 0.19
1,3-C H 4 6 1.50 1.54 1.46 1.50
n-C H10 4 0.45 0.45 0.45 0.45
Benzene 0.54 0.66 0.52 0.64

On the down-side, the yield of carbon oxides increases
by application of the coating. The carbon monoxide yield
increases from 0.002-0.003 wt% for the uncoated
reactor to 0.244-0.349 wt% for the coated reactor. The
carbon dioxide yield increases from 0.001-0.002 wt%
for the uncoated reactor to 0.300-0.429 wt% for the
coated reactor. The yield of carbon oxides by application
of the coating is significantly less than in the pilot plant
experiments due to the lower surface-area-to-volume
ratio in these industrial reactors. Furthermore,
reduced yields of methane and ethylene are simulated
by application of the coating, consistent with the pilot
plant experiments. The loss of ethylene yield is 0.41
wt% and 0.65 wt% at SOR and EOR respectively.
In the following more details are given that allow to
compare the results of the coated and uncoated case.
Comparison is made for Reactor 1. All conclusions for
the other reactors are similar to those for Reactor 1,
unless stated otherwise.
Figure 12 shows the tube external wall temperature
profile of Reactor 1 for the uncoated (top) and coated
(bottom) case. As seen from the top figure, the
maximum allowable temperature of 1070 °C is
reached after 1125 h, i.e. 47 days, of operation. For
the coated reactor, the maximum tube metal
temperature has then only reached 993.3 °C due to
much lower coke formation. Only after 5125h, i.e. 213
days the TMT surpasses 1070 °C.
Figure 13 shows the coke thickness profile for the
uncoated (top) and coated (bottom) case. Obviously,
the coke layer grows much quicker for the uncoated
reactor. At EOR for the uncoated reactor, a maximum
coke thickness of 14 mm is reached. The maximum
coke thickness in the coated reactor is then only
4 mm.

AICHE_Catalytic_Coating_Apr2014.docx Page 13

Figure 12: Heat flux [W/m²] profile to the uncoated Reactor
1 (top) and the coated Reactor 1 (bottom).
Figure 13: Coke thickness [m] profile for the uncoated
Reactor 1 (top) and the coated Reactor 1
(bottom).
Page 14
This slower growth of the coke layer makes that the
pressure drop over the coated reactor increases
slower as seen from Figure 14.
Figure 14: Process gas pressure [bar abs] profile for the
uncoated Reactor 1 (top) and the coated
Reactor 1 (bottom).
Figure 15 shows the ethylene yield for the uncoated
(green) and coated (blue) case. Interestingly, the
ethylene yield for the uncoated reactor decreases
faster due to higher pressure drop because of the
higher coke formation. After about 500h, the ethylene
yield of the uncoated reactor is below the ethylene
yield of the coated reactor. Over the entire runlength,
the average ethylene yield is 51.38 wt% and 50.88 wt%
for the uncoated and coated Reactor 1 respectively.
However, if operation would be halted in the coated
case after 1875h, an average ethylene yield of
51.38 wt% is obtained. This allows an increase in
runlength of a factor 1.67 while keeping the ethylene
yield constant. This analysis shows that although the
coating results in lower ethylene yields at SOR, the
decrease of ethylene yield over time is different for
a coated reactor. Hence, in some cases, a longer
runlength can be obtained while keeping the time-
averaged ethylene yield the same as for an uncoated
reactor.
AICHE_Catalytic_Coating_Apr2014.docx

Figure 15: Ethylene yield [wt%] as a function of run time for
Reactor 1) for the uncoated (green) and coated
(blue) case.
7. conclusions
YieldUp, a robust, novel coating technology for the inner
wall of the furnace tube that prevents coke deposition
was developed. The performance of the coating was
tested in a Jet Stirred Reactor (JSR) set-up and at the
UGent pilot plant for steam cracking.
Three different coating formulations were tested in the
JSR set-up. For all of the coated coupons, a decrease in
coke formation during cracking was observed
compared to Incoloy 800HT. It was shown that by tuning
the coating formulation, the activity and corresponding
CO and CO2 yields can be optimized.
The coating that showed the lowest coking rate during
the JSR experiments was tested in a pilot plant unit
using ethane and naphtha as feedstock. Application of
the coating resulted in a coke reduction by a factor 2 to
4 compared to an uncoated reference reactor.
Consequently, the effluent contained more hydrogen,
CO and CO2 than during the reference experiments as
coke is gasified to carbon oxides and hydrogen. The
effects of continuous sulfur addition and presulfidation,
coil-outlet-temperature and dilution on product yields
and coking tendency were also tested. These pilot
experiments showed that the catalyst is robust and
maintains anti-coking activity even after >10
coking/decoking cycles.
AICHE_Catalytic_Coating_Apr2014.docx
8. references
1. Broutin, P.; Ropital, F.; Reyniers, M. F.; Froment,
G. F., Anticoking coatings for high temperature
petrochemical reactors. Oil & Gas Science and
Technology - Revue d'IFP Energies Nouvelles 1999,
54, (3), 375-385.
2. Ganser, A.; Wynns, K. A.; Kurlekar, A.,
Operational experience with diffusion coatings on
steam cracker tubes. Materials and Corrosion-
Werkstoffe Und Korrosion 1999, 50, (12), 700-705.
3. Petrone, S.; Chen, Y.; Deuis, R.; Benum, L.; Gent,
D.; Saunders, R.; Wong, C. In Catalyzed-assisted
Manufacture of Olefins (CAMOL): Realizing Novel
Operational Benefits from Furnace Coil Surfaces,
AIChE 2008 Spring National Meeting, New
Orleans, Louisiana, 2008; New Orleans,
Louisiana, 2008.
4. Pyl, S. P.; Schietekat, C. M.; Reyniers, M.-F.;
Abhari, R.; Marin, G. B.; Van Geem, K. M.,
Biomass to olefins: Cracking of renewable
naphtha. Chemical Engineering Journal 2011, 176,
178-187.
5. D. Matras, V. J., Continuous reactor perfectly
agitated by gas jets for kinetic study on rapid
chemical reactions. Chem. Eng. Sci 1973, 28, 129-
137.
6. Plehiers, P. M.; Froment, G. F., Firebox
simulation of olefin units.
7. Chemical Engineering Communications 1989, 80,
81-99.
8. Rao, M. V. R.; Plehiers, P. M.; Froment, G. F., The
coupled simulation of heat-transfer and reaction
in a pyrolysis furnace. Chemical Engineering
Science 1988, 43, (6), 1223-1229.
9. Plehiers, P. M.; Reyniers, G. C.; Froment, G. F.,
Simulation of the run length of an ethane
cracking furnace. Industrial & Engineering
Chemistry Research 1990, 29, (4), 636-641.Banded
gas and nongray surface radiation models for
high-emissivity coatings. Aiche J. 2005, 51, (10),
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