Troubleshooting a FCC unit

The source of a fouling problem in a FCC CO boiler was identified by systematic

analysis of fresh catalysts, additives and equilibrium catalysts

Chiranjeevi Thota, Shalini Gupta, Dattatraya Tammanna Gokak, Ravi kumar Voolapalli, P V C Rao
and Viswanathan Poyyamani Swaminathan  Bharat Petroleum Corporation

F
luid catalytic cracking
(FCC) is one of the major
processes in the refining
industry for converting heavier
hydrocarbons to useful middle
distillates. Such a process
demands the continuous addi-
tion of fresh FCC catalyst and
results in the generation of
tonnes of spent equilibrium
FCC catalyst. To understand the
FCC unit’s operation, the proc-
ess can be divided into six
sections: feed preheater, reactor,
regenerator, main fractionator,
gas plant and treating facilities.
The cracking reactions occur in
the reactor zone and this leads
to coking. Coked catalyst is
circulated back to the regenera-
tor to burn the coke at high
temperature in the presence of
air. The regenerator hot flue gas
(containing CO and CO2) holds
an appreciable amount of
energy. In most units, the flue
gas is routed through a steam
generating boiler (referred to as
a CO boiler), where the carbon
monoxide in the flue gas is
burned as fuel to provide steam
for use in the refinery as well as
to comply with any applicable
environmental regulatory limits
on carbon monoxide emissions.
FCC units generally experi-
ence catalyst-related problems
such as circulation, catalyst loss
and activity decline. The FCC
units studied were encountering
low yield problems due to a
decrease in catalyst activity.
During the same period, it was
also observed that the CO boiler
became fouled externally, and a
lot of fines were found in the
CO boiler stack during cleaning.
Subsequent to startup after
cleaning, the CO boiler started
to experience fouling again.
There was also a steady decline
in activity of the e-cat
inventory.
Methodology
The problem of fines deposition
in the CO boiler stack section,
as well as catalyst activity loss,
was investigated systematically
by analysing particle size, attri-
tion index, surface area and
chemical composition in terms
of metals, to arrive at a possible
solution to enable smooth oper-
ation of the plant.
Samples of e-cat, fresh cata-
lysts and CO boiler samples
from FCC units were obtained
from refineries, and these

Particle size distribution of fresh catalysts and additives (ASTM D4513)

Sample code, wt% -180 -150 -106 -90 -75 -63 -53 -45 -32 -20 (APS) µ
Fresh Cat-1 99 98 83 69 34 37 25 12 5 1 72
Fresh Cat-2 100 98 87 75 61 44 31 20 10 3 69
Fresh Cat-3 99 98 88 77 61 41 24 15 3 0.1 69
Fresh Cat-4 100 99 90 75 58 44 25 16 3.5 0.27 71
Fresh Cat-5 99 99 90 77 62 44 28 19 5.7 0.6 67
Fresh Add-1 98 97 81 53 33 19 12 6 1.2 0.1 88

Table 1

www.digitalrefining.com/article/1000354 Catalysis 2012 1

 Attrition index data (ASTM D5757)
78

74 Catalyst Attrition loss, wt%

Fresh Cat-1 5.0
70 Fresh Cat-3 6.9
Fresh Cat-6 9.3
66 Fresh Add-1 10.0
APS

E-cat-1 4.7
62 E-cat-2 5.7
E-cat-3 7.1
58
Table 2
54
45’ increased from 12 to 20 wt%.
50 Particle size distribution was
04

04

04

04

04

04

05

05
determined in accordance with
20

20

20

20

20

20

20

20
the ASTM D4513-97 method
ar

ay

ov

b
Ju

Ja
Au

Se

Fe
M

N
using a sieving procedure.
8
22

27
14

30
11

19
3

Typically, about 50g of FCC

catalyst sample was sieved
Figure 1 APS variation with respect to time through a test sieve column
comprising 180, 150, 106, 90, 75,
samples were analysed in the was carried out by measuring 63, 53, 45, 32, and <20µm sieves
laboratory. The experimental properties such as particle size for 30 minutes using an auto-
techniques used to characterise distribution, attrition index and sieve shaker. After sieving,
the catalyst samples and the magnesium metal concentration fractions collected over each
results are discussed in this for fresh FCC catalysts, additive sieve were weighed and PSD
article. and e-cat samples collected at calculated as per the ASTM
different time intervals. method.
Results Average particle size
In order to understand the Particle size analysis decreased from 72 microns to 67
reasons for CO boiler fouling in In Table 1, it is clear that the microns. This drop corresponds
the FCC unit, a systematic study fraction of the catalyst coded ‘- to an increased amount of fines
in the catalyst. In order to
substantiate this further,
e-cat samples collected at differ-
28
ent time intervals were also
24 characterised for particle size
(see Figures 1 and 2).
20 The average particle size
−45 fraction

distribution of fractions ‘-45’

16
and ‘-63’ were analysed over a
12 period of one year. Figures 1
and 2 show that average parti-
8 cle size is more or less constant
around 64 microns before the
4
addition of additive. After the
0 introduction of additive, the
average particle size increased
04

04

04

04

04

04

05

05
20

20

20

20

20

20

20

20

initially (from 64 to 75 microns),

ar

ay

ov

b
Ju

Ja
Au

Se

Fe
M

then stabilised around 65

N

8
22

27
14

30
11

19
3

micron. This increase in average

Figure 2 Variation in ‘-45’ fraction with respect to time particle size is an indication of

2 Catalysis 2012 www.digitalrefining.com/article/1000354

less retention of fines in the
unit. The ‘-45’ fraction also fluc-
tuated in average particle size
after the introduction of addi-
tive, before stabilising. During
this period, a lot of fluctuation
was noted in the unit with
respect to catalyst. Hence, the
decrease in particle size leads to
less retention of catalyst in the
unit and ultimately leads to
fouling of the boiler.
Attrition index
Attrition index was measured
for fresh FCC catalysts, which
were used at different intervals
of time, and also e-cat samples
and catalyst additive samples
(see Table 2). Attrition index
was measured as per the ASTM
D5757 procedure. It was
observed that the additive attri-
tion index was on the high side
(10 wt%). Table 2 shows that
the attrition loss for fresh cata-
lyst batches was also on the
high side. Further, it was
observed that the attrition
value for the e-cat-1 sample
(4.7%) was in the acceptable
range, while for the e-cat-2 and
e-cat-3 samples attrition losses
(5.7 and 7.1 wt%, respectively)
were on the high side. This
observation was attributed to
attrition-prone catalyst and
additive usage in the unit at
that time.
Surface area measurements
To further understand the
source of fines, the surface areas
of fresh FCC catalyst fines (<40
micron), additive, attrited fresh
catalyst and CO boiler fines
were analysed. The surface
areas of e-cat, fresh catalyst and
fresh additive fines were compa-
rable with those of the original
sample. Fresh additive fines and
attrited fresh catalyst were
www.digitalrefining.com/article/1000354
Surface area data for fresh catalyst, additive, e-cat and CO boiler samples
S.No Catalyst S.A, m2/g
1 Fresh Cat-1 349
3 Fresh Add-1 100
5 E-cat-4 204
7 CO boiler fines surface area 9
8 Additives fresh fines, heated to 1000°C 30
9 Fresh Cat-3, attrited fines, heated to 1000°C 40
Table 3
heated to 1000°C, and the meas- Chemical analysis
ured surface area was found to Chemical analysis was carried
be in the range 30-40 m2/g. A out on various samples to ascer-
sample from the CO boiler was tain the source of CO boiler
found to have a surface area of fines by measuring the magne-
9 m2/g. The very low surface sium content. Additive contains
area of CO boiler fines was due magnesium metal and its
to their exposure to very high concentration should rise with
temperatures (>950°C), which the inventory build-up in the
could have resulted in pore unit. A microwave digestion
sintering and formation of non- procedure has been standard-
porous material; hence, it could ised for quantifying magnesium
not be attributed to either addi- in different fractions of CO
tive or FCC catalyst fines. boiler fines. A microwave diges-
Surface area measurements for tion system equipped with 14
catalyst samples were carried vessels and designed for pres-
out using nitrogen adsorption/ sures up to 800 psi was used.
desorption measurements in Each vessel is charged with 0.2-
an Autosorb-1MP unit. 0.5g of sample, to which is
Nitrogen adsorption/desorption added 10 ml of nitric acid, 3 ml
isotherms were measured at - of distilled water and 1 ml of
196°C after degassing about 50 hydrogen peroxide. After about
mg of sample below 10-3 torr at 15 minutes, when the first vigor-
300°C for three hours. BET ous reaction has taken place, the
specific surface area was esti- pressure vessels are closed and
mated by following ASTM put into a microwave oven to
method D4365 using adsorption complete the one-stage diges-
data in a relative pressure range tion. Metal content is measured
from 0.008 to 0.08 bar. Surface using the ICP technique.
area values for various samples Various parameters of micro-
are shown in Table 3 as per wave digestion system were
ASTM D4365. optimised for obtaining a clear
Microwave system parameters for digestion
Stage Power RAMP minuets Control pressure, psi Hold time, min
Max %
I 1200 W 100 30.00 120 30.00
Table 4
Catalysis 2012 3
 sium content of the e-cat is
0.8 lower than the expected values.
Mass balance
Actual
The mass balance assumes both
0.7
catalyst and additive are
removed from the system
0.6
(either through cyclone losses
Ma, %

0.5
or catalyst purging) at the same
rate. Ideally, the estimated and
0.4
actual Mg concentrations
should be the same. The differ-
0.3 ence suggests that additive
retention is 85% of the main
0.2 catalyst. Perhaps excessive
0 30 60 90 120 generation of fines with addi-
Days tive may be contributing to this
lower retention. Hence, it may
Figure 3 Comparison of actual and calculated Mg content in e-cat be necessary to improve the
attrition resistance of the
solution for sample analysis. balance over a period of four additive.
The optimised program and months was done by analysing Based on magnesium analysis
parameters used in the one- magnesium content at different of CO boiler fines alone, the
stage digestion are shown in time intervals. Figure 3 problem cannot be attributed
Table 4. compares the expected and solely to either catalyst or addi-
To understand additive reten- actual magnesium content of tive, as the fines could have
tion in the unit, an e-cat mass the e-cat. The actual magne- accumulated over a period of
time and the addition of addi-
tive may have started
Mg and RE2O3 analysis of different fractions of e-cat
meanwhile. Magnesium and
rare earth oxide distribution in
different-sized fractions of the
E-cat -2 Mg, wt% RE2O3, wt% e-cat was analysed. Magnesium
32 to 45 µ 0.5850 1.62
45 to 63 µ 0.4855 1.55
and RE2O3 distribution with
63 to 90 µ 0.4384 1.45 different-sized fractions of e-cat
>90 µ 0.2780 1.02 are shown in Table 5. The table
shows that, with respect to
Table 5 particle size, magnesium and
rare earth content decreases,
80
which indicates that a loss of
fines leads to a decrease in
70 activity. The effect is shown in
60 Figure 4.
Systematic analysis of fresh
50
FCC catalyst, equilibrium cata-
Activity

40 lysts and fines collected from

30
the CO boiler at different time
intervals, and analysis of fresh
20 additive samples, was
10 employed to identify problems
and enable corrective actions to
0
Dec May Aug Dec May be recommended for the
smooth operation of the FCC
Figure 4 Activity variation with respect to time unit.

4 Catalysis 2012 www.digitalrefining.com/article/1000354

Conclusions
Systematic studies were
conducted on different refinery
samples to troubleshoot opera-
tional problems in the FCC unit.
The studies led to the following
conclusions:
• The CO boiler fines problem
confirmed that in-use fresh cata-
lysts and additive are more
prone to attrition, so they
contributed more to the fines
loss from the unit and ulti-
mately to the fouling of the
boiler. More fines loss also
affected the conversion loss,
because fines have more zeolite
and additive content
• Even though the attrition
index of additive is on the high
side, which may contribute to
the total fines, the amount of
additive used is relatively small
compared to the catalyst; hence,
the additive alone cannot
contribute to the total fines
generated. This was established
by correlating the magnesium
content of CO boiler fines with
additive
• Since both fresh catalyst and
additive can contribute to fines,
regular monitoring of the
www.digitalrefining.com/article/1000354
attrition index as well as parti-
cle size analysis of the FCC
catalyst and additive would be
good practice
• Systematic physico-chemical
characterisation of fresh catalyst,
e-cat and CO boiler fines helped
to diagnose the CO boiler fines
and fouling problem, and
enabled suitable remedial meas-
ures to be suggested to
operations.
Acknowledgement
The authors gratefully acknowledge
BPCL’s management for encouragement
and permission to publish the paper.
Chiranjeevi Thota is a Deputy Manager
at the Corporate R&D Centre, Bharat
Petroleum Corporation, India. He holds a
MSc in chemistry from Andhra University,
Visakhapatnam, and a PhD from Indian
Institute of Petroleum, Dehradun. Email:
chiranjeevit@bharatpetroelum.in
Shalini Gupta is a Deputy Manager (R&D)
with Bharat Petroleum Corporation. She
holds a master’s in chemistry.
Email: guptashalini@bharatpetroleum.in
Dattatraya Tammanna Gokak is a Senior
Manager at the Corporate R&D Centre,
Bharat Petroleum Corporation. He holds
a MSc in chemistry from Karnatak
University, Dharwad, and a PhD from
University Of Baroda.
Ravi Kumar Voolapalli is a Chief
Manager at Corporate R&D Centre,
Bharat Petroleum Corporation. He holds
a BTech in chemical engineering from
Andhra University, Visakhapatnam, a
MTech in chemical engineering from the
Indian Institute of Technology, Kanpur,
and a PhD in chemical engineering from
Imperial College of Science Technology
and Medicine.
P V C Rao works on refining processes,
biofuels, crude assay and compatibility,
fuel additives and new products
development. He holds a PhD in chemistry
from Indian Institute of Technology,
Bombay.
Viswanathan Poyyamani Swaminathan 
is a Chief Manager and Head of the
Corporate R&D Centre, Bharat Petroleum
Corporation. He holds a MSc and PhD
in chemistry from Indian Institute of
Technology, Delhi.
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