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Predicting catalyst lifetime

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Predicting catalyst lifetime
A simulation model compares accurately with actual operating data to
provide reliable predictions of catalyst lifetime in naphtha reforming
S REZA SEIF MOHADDECY and SEPEHR SADIGHI
RIPI
T
he catalytic reforming of
heavy naphtha (heavy
straight-run gasoline, or
HSRG) is a favoured process in
petroleum refineries for
producing high-octane gaso-
line. From the viewpoint of
process operation, there are
three kinds of widely used
catalytic reforming units:
semi-regenerative, continuous
catalyst regeneration (CCR)
and cyclic regenerative
processes. Semi-regenerative
catalytic naphtha reforming is
the oldest type and it is gener-
ally carried out in three or four
fixed-bed reactors in series
with intermediate preheaters
operated adiabatically at
temperatures between 450°C
and 520°C, total pressure
between 10 and 35 bar, and
molar hydrogen-to-hydrocar-
bon ratios between 3 and 8.
Among all commercial technol-
ogies for the catalytic
reforming process, those using
fixed-bed reactors in series are
the most common configura-
tions due to the relative
simplicity of scaling up an
operation. However, the main
disadvantages of fixed-bed
reactors are coke formation,
www.digitalrefining.com/article/1000840
active phase sintering and
poisoning during the catalyst’s
life cycle. Consequently, the
main problem with fixed-bed
reactors is the loss of catalyst
activity over time, which
reduces the length of continu-
ous operation.
The catalyst’s life cycle is
further complicated by numer-
ous technical, environmental
and organisational issues. In
principle, different companies
can be involved in each of the
life cycle steps. The life cycle of
a catalyst starts with the initial
production of fresh catalyst
oxide, which is pre-sulphided
prior to being used in the refin-
ery process. During its use
when the catalyst deactivates
and it does not meet perfor-
mance targets within the limits
of the reactor’s operating
conditions, the reactor is shut
down. Therefore, the catalyst’s
life cycle typically involves a
long chain of operations,
normally performed by differ-
ent specialised companies.1,2
Catalyst life is dependent
essentially on process condi-
tions and also, to a large extent,
on the distribution of species
such as sulphur and nitrogen
present in the oil, both of
which can change during a
typical commercial run.
Moreover, depending on the
process used, the catalyst’s life
cycle may vary from a few
seconds, as in fluid catalytic
cracking (FCC), to several
years, as in ammonia synthesis;
therefore, a reliable prediction
of catalyst life has been
extremely difficult.
Before the catalyst is loaded
in the reactor, many laboratory
experiments are carried out to
identify its operability. An
accelerated method for a
one-day laboratory test is
proposed here for the progno-
sis of activities and an
estimation of the lifetime of the
catalyst. The method is based
on knowledge of the deactiva-
tion behaviour of catalysts
under different reaction condi-
tions, including extreme
conditions at high liquid hourly
space velocities (LHSV). Hence,
the method enables prediction
of lifetime and performance
using data obtained from a
one-day test in laboratory
conditions. The curve of LHSV
versus lifetime is an individual
property of a given catalyst,
PTQ Q3 2013 1
 Recycle
R
Platcharge
H-1
E-1
Figure 1 Block flow diagram of the catalytic reforming unit of the target oil refinery
which has to be established
experimentally. Any point from
this curve can be used for an
estimation of lifetime.3,4 Since
deactivation of the catalyst
takes place over a long time
scale, it is difficult to mimic this
in a pilot plant or at lab scale.
Consequently, any study on an
industrial scale to predict the
life cycle of a catalyst plays an
important role regarding
economic, operational and
environmental issues.5,6
Works on the life cycle of an
industrial-scale catalytic naph-
tha reforming unit are scarce.
In our present work, the
semi-regenerative catalytic
reforming process of a catalytic bed. For such a unit,
commercial-scale oil refinery
was simulated using the Petro-
Sim simulator (KBC
Profimatics, 2009). After vali-
dating the simulation, the
lifetime of the next cycle was
predicted by the previous
simulated cycle lives, and the
results were compared with
actual test runs of the plant at
the end of the cycle.
2 PTQ Q3 2013
C-1
R-4
R-3
R-2
R-1
H-2 H-3 H-4
E-2 E-3
Air cooler Water cooler
Process description
A commercial fixed-bed cata-
lytic naphtha reforming unit
called Platformer, licensed by
Chevron and with a nominal
capacity of 16 500 b/d, was
chosen as a case study. The
feed to the plant, prior to enter-
ing the catalytic reformer,
should undergo hydrodesul-
phurisation (HDS) in the
hydrotreatment unit. Then, the
produced naphtha, called
Platcharge, is introduced to the
catalytic reforming process.
The most commonly used
types of catalytic reforming
units have three or four reac-
tors, wherein each has a fixed
the activity of the catalyst
reduces during operation due
to deposited coke and loss of
chloride. Hopefully, the activ-
ity of the catalyst can be
periodically regenerated or
restored using in situ high-
temperature oxidation of the
coke followed by a chlorination
process. Therefore, the catalyst
of a semi-regenerative catalytic
Vapour
Purge
Gas to
LPG
V-1
LPG
Stabiliser
column
Reformate
reformer is regenerated during
routine shutdowns of the
process every 18-24 months.
Normally, the catalyst can be
regenerated three or four times.
Then, it must be returned to
the manufacturer for reclama-
tion of platinum and/or
rhenium.
In Figure 1, Platcharge is
preheated by the first furnace
(H-1). It then enters the first
reactor (R-1), where naph-
thenes are dehydrogenated to
aromatics. Next, the product
stream from the first reactor
passes through the second
reactor (R-2), and the outlet
stream of that enters the third
reactor (R-3). Similarly, the
product stream from the third
reactor enters the fourth reac-
tor (R-4). The overall reforming
reactions are endothermic, so a
preheater (H-1, H-2, H-3 and
H-4) is provided ahead of each
reforming reactor.
Next, the product stream
from the fourth reactor enters a
separator, V-1, in which hydro-
gen produced during the
www.digitalrefining.com/article/1000840
reforming process (the gas
stream) is recycled, then mixed
with Platcharge. Finally, the
liquid product leaving the
separator is introduced to the
gasoline stabiliser, in which
LPG and light gases are sepa-
rated from gasoline. The
vapour pressure of the gasoline
can be set according to market
requirements.
The distribution of catalyst in
the reactors is shown in Table
1. The normal operating condi-
tions of the unit are shown in
Table 2.
Process simulation
and validation
Catalytic reforming is often
modelled and simulated based
on the number of reactive
species and the type of kinetic
model used.7,8 The presence of
many components, either as
reactants or as intermediate
products in the reactive
mixture, with resulting new
reactions, creates challenges for
modelling the process. To
reduce these complications,
reactants in the mixture are
classified in certain and limited
groups called pseudo- compo-
nents. Additionally, Arhenius
and Langmuir-Hinshelwood
kinetics are widely used for
kinetic-based catalyst model-
ling and simulation of the
catalytic naphtha reforming
process.9-13 Petro-Sim software
is a simulator capable of simu-
lating commercial-scale
catalytic reforming units,15 and
so enables us to simulate reac-
tors with different catalyst
weights and sizes.16,17 In this
research, Petro-Sim has been
used to simulate and analyse a
catalytic reforming unit.
To simulate a catalytic naph-
tha reforming process using
www.digitalrefining.com/article/1000840
Catalyst distribution in reforming reactors
1st reactor 2nd reactor 3rd reactor 4th reactor
Catalyst weight, kg 5077.25 7615.87 12 693.13 25 386.25
Catalyst distribution, wt% 10 15 25 50
Table 1
gathered. These parameters
Operating conditions in the mainly consist of inlet and
catalytic reforming of the target
outlet reactor temperatures,
oil refinery
catalyst weight, specification of
Process variable Value feed and products, operating
Inlet temperature, °C 490-515 pressures, flow rates of makeup
Hydrogen/hydrocarbon ratio, mol/mol 3-7
LHSV, h-1 1-2
hydrogen, and recycle rates and
Yield, vol% 70-85 flow rates of all gaseous and
liquid products.14 After prepar-
Table 2 ing a test run and running
Ref-Sim, tuning parameters are
Petro-Sim, external calibration sent to the Petro-Sim environ-
for determining the kinetic ment to simulate and optimise
parameters is needed. For this the operating conditions.
unit, the Ref-Sim module is Moreover, the life of the catalyst
provided for the task. For can be predicted in the Petro-
generation of the required Sim environment. It is obvious
parameters, such as frequency that after simulating catalytic
factors, activation energies and naphtha reforming (see Figure
decay constants, by Ref-Sim, 2), the simulated variables
actual test runs from the unit should be compared against
under study should be actual data to validate the
CRU Gas
(R-1 to R-4) H2 product
to LPG
Liquid
Platcharge to LPG
Stabiliser
column
R
Furnace
Reformate
(gasoline)
Air cooler Water cooler
Figure 2 Simulation of catalytic naphtha reforming in the target refinery
PTQ Q3 2013 3
 octane. To represent this
Comparison of outlet temperature of first reactor for previous cycles (first,
second and third cycles) of catalytic reforming of the target oil refinery behaviour, Petro-Sim tracks
catalyst decay by predicting
Variable Unit Test run 1 Test run 2 Test run 3 AAD% decay factors through each
Simulation Actual Simulation Actual Simulation Actual reactor. This calculated decay
1st cycle °C 441.8 446 441 447 440 449 1.44
2nd cycle °C 466 447 471.5 440 473.2 448 5.68 information forms part of the
3rd cycle °C 452.1 451 446 430 458.1 431 3.42 model and is available on the

* Absolute average deviation per cent calibration factor tab for
predicting the life cycle of the
Table 3 catalyst.

Comparison of outlet temperature of second reactor for previous cycles (first, Results and discussion
second and third cycles) of catalytic reforming of the target oil refinery From the start of run to the
end of run, actual test runs
Variable Unit Test run 1 Test run 2 Test run 3 AAD%
were gathered from the target
Actual Simulation Actual Simulation Actual Simulation reforming unit. Since, for a
1st cycle ° C 486.3 487.2 488 486 489 483.6 0.57 specified catalyst life, the simu-
2nd cycle ° C 488 488.2 482 486.5 493.5 488 0.64
3rd cycle ° C 497 466.8 465 474.1 468 474.5 3.14 lator was used for predicting
the steady-state condition of
Table 4 the Platformer, the data used
for calibration should be
Comparison of outlet temperature of third reactor for previous cycles (first, selected from the normal
second and third cycles) of catalytic reforming of the target oil refinery condition when no
abnormalities, such as tower
Variable Unit Test run 1 Test run 2 Test run 3 AAD% flooding, emergency depressur-
Actual Simulation Actual Simulation Actual Simulation
1st cycle ° C 500 510.8 502 509.8 502.5 507.8 1.59 isation and pump or
2nd cycle ° C 502 503.4 498 502 508 505.5 0.54 compressor shutdown, were
3rd cycle ° C 511 483 480 496.9 481 490.5 3.66
happening during the opera-
tion. Before using these data to
Table 5 estimate the tuning parameters,
it was necessary to validate
Comparison of outlet temperature of fourth reactor for previous cycles (first, them. If a reasonable overall
second and third cycles) of catalytic reforming of the target oil refinery mass balance (±5%) cannot be
calculated, the validity of the
Variable Unit Test run 1 Test run 2 Test run 3 ADD% test run is compromised. After
Actual Simulation Actual Simulation Actual Simulation validating the test runs, gener-
1st cycle ° C 509.9 510 511.8 509 511.6 507.1 0.48
2nd cycle ° C 511.8 509.4 507.5 509.4 517.8 511.5 0.69 ating the calibration factors
3rd cycle ° C 520.1 494 490.2 503.3 493 499.7 3.02 and sending them to the Petro-
Sim environment, the
Table 6 comparison of the simulated
outlet temperatures of reform-
process simulation; otherwise, Petro-Sim environment is ing reactors for the first, second
the accuracy of the predictions predominantly a function of and third cycles are shown in
can be compromised. reformer type and severity of Tables 3 to 6. From these
Since the catalyst in catalytic operation. The latter is deter- tables, it can be concluded that
reforming loses activity over mined by the feed — the Petro-Sim can simulate reactor
time, predicting the life cycle of percentage amounts of naph- temperatures with an absolute
a commercial catalyst must thenic, aromatic and paraffinic average deviation percentage
take into account catalyst hydrocarbons — therefore, (AAD%) of less than 4%.
production, sulphidation, during operation, reactor To gain better insight, the
usage and oxidative regenera- temperatures should be raised most important process varia-
tion. The rate of decay in the to achieve the same reformate bles of Platformer — RON of

4 PTQ Q3 2013 www.digitalrefining.com/article/1000840

product, yield of gasoline and
life of catalyst — were also
simulated. The AAD% of each
of the simulation results (for
the first, second and third
cycles) is shown in Tables 7, 8
and 9. It is supposed that the
main source of deviation was
the possibility of errors arising
from measurements in gather-
ing data obtained from faults
such as signal transmission,
calibration and power fluctua-
tion of instruments, which
could not be excluded from the
actual data. However, from the
presented simulation results, it
can be concluded that the
developed simulation program
was reliable enough to be
applied for predicting the
behaviour of the catalytic
reforming unit under study.
After evaluating and vali-
dating the simulation, the
process variables were
predicted for the fourth cycle.
After starting up the process,
predicted results from the
simulator were compared
against actual results versus
days on stream. Figures 3 to 8
show comparisons between
the reactor temperatures, RON
and yields of products against
the actual values. As these
figures show, there are close
mappings between the meas-
ured and the predicted process
variables. It should be
mentioned that the AAD% of
predictions for the first,
second, third and fourth outlet
reactor temperatures were
0.75, 0.58, 0.54 and 0.61,
respectively. Moreover, the
AAD% of the prediction for
product RON and product
volume yield were 1.45 and
0.03, respectively.
The most important parame-
ter of a catalytic reforming
www.digitalrefining.com/article/1000840
Comparison of product RON for previous cycles (first, second and third
cycles) of catalytic reforming of the target oil refinery
Variable Unit Test run 1 Test run 2 Test run 3 AAD%
Actual Simulation Actual Simulation Actual Simulation
1st cycle - 97.3 97.47 97.2 97.25 96.6 96.9 0.18
2nd cycle - 94.2 94.55 92.2 92.22 93.9 92.7 0.29
3rd cycle - 92.3 92.91 95.5 94.9 93.6 93.8 0.08
Table 7
Comparison of product yield for previous cycles (first, second and third
cycles) of catalytic reforming of the target oil refinery
Variable Unit Test run 1 Test run 2 Test run 3 AAD%
Actual Simulation Actual Simulation Actual Simulation
1st cycle vol% 75.8 74.33 75.5 74.8 74 75.3 1.5
2nd cycle vol% 80.2 76.2 80.4 79.8 81.1 79.1 2.8
3rd cycle vol% 79.5 79.22 80.2 76.2 78.8 77.9 2.25
Table 8
Comparison of total life time prediction for previous cycles (first, second
and third cycles) of catalytic reforming of the target oil refinery
Variable Unit Test run 1 Test run 2 Test run 3 AAD%
Actual Simulation Actual Simulation Actual Simulation
1st cycle days 920 895.6 920 889.6 920 904 2.63
2nd cycle days 891 859.6 891 820.2 891 856 5.45
3rd cycle days 591 568.7 591 569.2 591 600 3.08
Table 9
460
Actual
Simulation
455
Temperature, ºC
450
445
440
435
0 100 200 300 400 500 600
Days on stream
Figure 3 Comparison of outlet temperature of first reactor for the current cycle
unit — the life of the next the next cycle, the life of the
cycle — was also studied by cycle (end of run) was
the validated simulation predicted by Petro-Sim for
program. Before starting up different days on stream (see
PTQ Q3 2013 5
 Conclusion
490 Prediction of the process varia-
Actual bles and life of the catalyst in a
Simulation commercial process is vital. To
485
perform such a task, a catalytic
Temperature, ºC

naphtha reforming unit with a

480 nominal capacity of 16 500 b/d
was studied. Data gathered
475 from the first three cycles were
chosen to calibrate the simula-
tor, then the plant was
470
simulated using the Petro-Sim
process simulator. The signifi-
465 cant process variables — outlet
0 100 200 300 400 500 600 temperatures of the first,
Days on stream second, third and fourth reac-
tors, product RON and volume
Figure 4 Comparison of outlet temperature of second reactor for the current yield — were simulated. After
cycle comparing results against
actual data, the accuracy of the
505
simulator was validated due to
Actual the low deviation of the simu-
Simulation lated process variables.
500 In the next step, the simula-
Temperature, ºC

tor was used to predict the

495 process variables correspond-
ing to the next cycle.
Comparing the results with the
490
real outputs showed that the
per cent of absolute average
485 deviation (AAD%) of the main
parameters were about 0.75%,
480 0.58%, 0.54%, 0.61%, 1.45%
0 100 200 300 400 500 600 and 0.03%, respectively.
Days on stream Additionally, before starting
the cycle, the simulated life of
Figure 5 Comparison of outlet temperature of third reactor for the current cycle the catalyst was estimated at
about 679 days and recorded at
Table 10). From this table, it As was expected, on day 719, about 719 days at the end of
can be seen that the average the temperature of the reactor the cycle under study.
life of the catalyst for the needed to be set at values
fourth cycle is about 679 days. higher than 510°C to preserve References
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the reactors to around 510°C cycle of the reforming unit can Ch, Prahov L, Kirkov N, Vasileva M, Filkova
to keep the RON of the prod- be estimated with acceptable D, Dancheva S, Method for Forecasting
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6 PTQ Q3 2013 www.digitalrefining.com/article/1000840

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www.digitalrefining.com/article/1000840 PTQ Q3 2013 7

 Technologist, KBC Profimatic, 2005.
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S Reza Seif Mohaddecy is a Project
Manager in the Catalysis and
Nanotechnology Division, Catalytic
8 PTQ Q3 2013
View publication stats
Reaction Engineering Department,
Research Institute of Petroleum Industry
(RIPI), Tehran, Iran. He holds a MS
in chemical engineering from Sharif
University of Technology.
Email: Seifsr @ripi.ir
Sepehr Sadighi is a Project Manager
in the Catalysis and Nanotechnology
Division, Catalytic Reaction Engineering
Department, Research Institute of
Petroleum Industry (RIPI). He holds a PhD
in chemical engineering from Universiti
Teknologi Malaysia.
Email: Sadighis @ripi.ir
LINKS
More articles from the following
categories:
Catalysts & Additives
Process Modelling & Simulation
Reforming
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