Mitigation of heat exchanger fouling

Detailed analysis of potential contributors identifies the root cause of

fouling in naphtha hydrotreater feed-effluent exchangers

BRUCE WRIGHT Baker Hughes Incorporated

TODD HOCHHEISER Valero Energy Corporation

T
he naphtha hydrotreater
(NHT) feed-effluent
exchangers at a US refin-
ery were experiencing severe
fouling. The heat exchanger
fouling was limiting run length.
As the preheat exchangers
fouled, the heater inlet tempera-
ture declined, resulting in an
increased potential for two-
phase flow in the heater. Unit
throughput was reduced to
manage the minimum required
heater inlet temperature.
A root cause analysis investi-
gation was conducted to
develop a clear understanding
of the fouling source. This anal-
ysis resulted in the development
of an antifoulant additive treat-
ment programme that has
significantly reduced the rate of
fouling. The antifoulant
programme has extended cycle
length and reduced mainte-
nance costs, resulting in a yearly
economic return of over 500%.
This article will review the root
cause investigation steps, results
of the treatment programme
and benefits to the refinery.
Fouling in hydrodesulphuri-
sation (HDS) units can impact
throughput, energy consump-
tion, and shorten catalyst life.
Deposits form in the feed-efflu-
ent heat exchangers and on the
top of the reactor beds. The
economic impact can be severe
from the problems caused by
fouling. Solutions include oper-
ational changes, mechanical
upgrades and antifoulant addi-
tive treatment to control specific
fouling mechanisms.1
Description of unit
This NHT processes straight-
run and coker naphthas from a
combined crude/coker gas
plant. The feed from the gas
Minimum
Surge
temperature
requirement
drum
Crude and
coker naphtha
Purchased
naphtha
Figure 1 NHT unit diagram
plant consists of butane
through jet boiling range mate-
rial. The NHT feed is
supplemented with purchased
naphtha from an intermediate
storage tank. All feed streams
are mixed in a surge drum and
then pumped to the shell side
of the feed-effluent exchangers.
There are four exchangers in
series. Prior to entering the first
exchanger, the naphtha feed is
mixed with hydrogen. The
feed-effluent exchangers are
designed to fully vapourise the
naphtha to prevent two-phase
Hydrogen recycle
compressor
Reactor
Furnace
Feed
effluent
heat
exchangers
Air cooler
Separator

www.digitalrefining.com/article/1000651 PTQ Q4 2012 1


80
75
70
U, BTU/hr / SF / ºF
65
60
55
50
45
40
35
30
0 50
Figure 2 Heat transfer coefficient pre- and post-unit revamp
flow in the fired heater. The
vapourised naphtha and hydro-
gen mixture is heated in the
fired heater to the required
reactor inlet temperature.
Sulphur and nitrogen impuri-
ties are converted to hydrogen
sulphide and ammonia, respec-
tively, in the fixed-bed catalyst
reactor. The reactor effluent
vapour is cooled and partially
condensed in the tube side of
the feed-effluent exchangers
and reactor effluent air fin
cooler. The liquid and vapour
are separated in a product
separator. The hydrogen gas
from the separator is
compressed and recycled to the
shell-side inlet of the feed-efflu-
ent exchangers. The separator
liquid is fractionated in the
NHT gas plant into butane,
light naphtha, reformer feed
and jet fuel. Figure 1 is a sche-
matic diagram of the unit.
Description of problems
A refinery configuration change
altered the boiling range of the
NHT feed from C5 through jet
to C4 through jet. After the
configuration change, the foul-
ing rate of the NHT feed-effluent
2 PTQ Q4 2012
Pre-revamp
Post-revamp
100 150 200 250 300 350 400 450 500
Days
exchangers increased signifi-
cantly. Figure 2 shows the
increased fouling rate after
modifying the NHT feed to
include butanes and butylenes.
The loss of heat transfer resulted
in lower furnace inlet tempera-
ture. A low furnace inlet
temperature is not sustainable
due to heater fouling caused by
two-phase flow. The reactor
outlet temperature was
increased to offset the heat
transfer coefficient reduction by
raising the log mean tempera-
ture difference across the
feed-effluent exchangers. The
reactor temperature increase
was an effective method of
managing the required mini-
mum furnace inlet temperature,
although an energy penalty was
incurred for heat lost through
the reactor effluent air cooler.
As the feed-effluent exchangers
continued to foul, the reactor
temperature could not be
further increased due to sulphur
recombination at a higher reac-
tor temperature. Unit
throughput was reduced and
eventually a shutdown was
required to mechanically clean
the feed-effluent exchangers.
Root cause analysis steps
and results
In order to understand the
causes of fouling in the NHT, a
root cause analysis approach
was employed that consisted of
system and operations reviews,
deposit analyses, feedstock
analyses and laboratory fouling
studies. These pieces of infor-
mation were coupled together
to establish the mechanisms
responsible for fouling and to
develop mitigation options.
System and operations
The NHT is configured so that a
combination of straight-run and
coker naphthas are fed hot to
the unit surge drum. Purchased
naphtha supplements the refin-
ery feeds to keep the NHT
operating at capacity. The
majority of the purchased naph-
tha is delivered to the plant via
barges and is contaminated with
oxygen. The purchased naphtha
is not oxygen stripped.
Coker fluids commonly
contain reactive compounds,
including olefins, amines and
carbonyls, that can lead to poly-
mer formation. Some of these
reactions are auto-catalytic in
the presence of oxygen. The best
practice for processing coker
naphtha through an HDS unit is
to ensure that intermediate
tankage is not utilised, which
would provide time for polymer
reactions to commence. As such,
the configuration and operation
of this unit should help to mini-
mise the formation of polymeric
deposits. Straight-run naphtha
typically has little impact on
HDS fouling unless there is a
significant influx of corrosion
by-products from the crude unit
overhead system.
Feed to this NHT flows
through the shell side of the
www.digitalrefining.com/article/1000651
preheat exchangers, while the
reactor effluent flows through
the tube side. This configuration
is commonly employed in
hydrotreating units because of
the tendency for ammonium
chloride salts to form in the
reactor effluent at sublimation
temperature and pressure.
These salts must be removed
through online water washing
to maintain the heat transfer
performance of the exchangers.
Online water washing of the
tube side of heat exchangers is
easier and more effective than
washing the shell side.
Deposit analyses
Visual inspections of the heat
exchangers prior to cleaning
revealed that the tube side was
clean, while the shell side was
severely fouled. Since the refin-
ery regularly water washes the
tube side of the exchangers to
dissolve and remove ammo-
nium chloride salts, the
cleanliness of the tube side was
expected. The shell-side depos-
its consisted primarily of
hydrocarbon-based materials
coupled with lesser quantities
of iron sulphide.
Table 1 shows the results for
the deposits obtained during
the root cause investigation. The
tube side was quite clean and
the small amount of material
obtained was found to be
primarily iron sulphide and iron
oxide — corrosion by-products
that can form due to the reac-
tion of ammonium chloride salts
with the heat exchanger tubes.
The shell-side deposits were
mostly organic but were
coupled with some iron
compounds and chloride salts.
The organic portion contained
substantial amounts of carbon;
the hydrogen-to-carbon atomic
www.digitalrefining.com/article/1000651
NHT deposit analyses iron sulphide that contribute to
deposit formation.2
Samples of the NHT feed
All results in wt%
Tube deposit Shell deposit components were analysed to
Carbon <1 57 identify possible fouling precur-
Hydrogen Nil 5
Nitrogen Nil 4
sors. The analyses summarised
Oxygen 10 13 in Table 3 revealed that the
Sodium Nil 3 purchased naphtha was rela-
Sulphur 22 11
Chlorine Nil 1 tively free of fouling precursors.
Iron 63 4 Additionally, the handling prac-
Silicon 1 Trace
Composition Primarily Primarily
tices of the purchased naphtha
inorganic organic had not changed from prior
cycles when minimal fouling
Table 1 was observed. After this review
of the purchased naphtha, it
ratio revealed that the deposit was eliminated as a root cause.
was composed of degraded, The combined crude and coker
partially cyclised polymeric naphthas contained components
material. There was also a that lead to polymer formation.
significant amount of nitrogen Olefins, as measured by the
found in the shell-side deposits. bromine number, and
Nitrogen is commonly found in mercaptans are both significant
deposits from coker naphtha fouling contributors. When these
due to the presence of amines components are present in the
and pyrroles, which can take feed stream, they will produce
part in polymer formation. free radical polymers. Elevated
basic nitrogen was also detected
Feedstock analyses in the feed. Basic nitrogen in
Analyses of HDS unit feed combination with organic acids
streams provide insight into the participates in condensation
fouling mechanism root cause. polymerisation.2 The organic
Tests that are utilised to identify acid content was below the
potential contributors to fouling detection limit, so it is unlikely
are shown in Table 2. Several that these nitrogen-based reac-
of the analyses look for tions were the primary cause of
components that can take part the high fouling rate.
in various polymerisation reac-
tions, while other tests identify Laboratory fouling tests
inorganic constituents such as Fouling simulation studies are
Typical HDS feed analyses
Analytical test Fouling concerns
Bromine number, g Br/100 g Olefins
Mercaptan sulphur, ppmw as S Free radical polymerisation
Hydrogen sulphide, ppmw as S Iron sulphide formation
Total acid number, mg KOH/g Condensation polymerisation
Basic nitrogen, ppmw as N Condensation polymerisation
Pyrrole-indole nitrogen, ppmw N Polymerisation
Metals, ppm Inorganic deposits
Filterable solids, ppm Inorganic deposits
Table 2
PTQ Q4 2012 3
 Inhibitor A was used to treat
NHT feed analyses
the coker naphtha stream before
it was mixed with the straight-
Analytical test Purchased naphtha Combined crude and coker naphtha run naphtha. A dispersant was
Filterable solids, ppmw <10 <10
API Gravity 58.3 60.9 injected at the NHT charge
Bromine number, g Br/100 g 1.4 14 pump to provide good mixing
% Saturated H, normalised 94.5 96.2 for treatment of the combined
% Olefinic H, normalised 0.2 1.4
% Aromatic H, normalised 5.3 2.4 feed stream, including
Mercaptan sulphur, ppmw as S 13 308 purchased naphtha. This combi-
H2S, ppmw as S <1 10 nation programme has provided
Total acid number, mg KOH/g <0.05 <0.05
Basic nitrogen, ppmw as N <10 23.6 excellent fouling inhibition
Pyrrole-Indole nitrogen, ppmw as N 0.2 3.7 capability in similar units and
offers the advantage of being
Table 3 able to adjust the treat rates of
the two components as needed.

Gum test results with combined naphtha Unit monitoring tools and
trends
Sample Test Stress Stress Results, Reduction In order to verify the perform-
medium temperature, ˚F (˚C) mg/100 ml %
Combined naphtha Existent gums N/A N/A 11 N/A ance of the chemical treatment
Combined naphtha Stressed Nitrogen 212 (100) 35 programme, a heat exchanger
Polymer Inhibitor A Stressed Nitrogen 212 (100) 11 69
Polymer Inhibitor B Stressed Nitrogen 212 (100) 16 54
monitoring programme was
Combined naphtha Stressed Air 212 (100) 48 utilised to compare current
Polymer Inhibitor A Stressed Air 212 (100) 15 69 operation to prior cycle perform-
Polymer Inhibitor B Stressed Air 212 (100) 23 52
ance. The heat transfer
Table 4 coefficient for the feed-effluent
heat exchanger bank was
used to generate deposits and mixtures are shaken and then trended versus run time. Figure
study the ability of chemical allowed to settle. An effective 3 shows the rate of decline of
additives to control their forma- dispersant will hold the deposit the exchanger heat transfer coef-
tion. For these feed streams, in solution longer than an ficient for the last three cycles.
existent gums3 were used to untreated sample. Dispersion The first two cycles shown are
measure the as-received poly- tests were run on the polymeric prior to chemical treatment,
mer content, and thermally material formed from the gum while the last cycle shown is
stressed gums were used to tests in order to identify an after implementation of the
determine the tendency to effective product for controlling chemical treatment programme.
produce additional polymer. deposition of the foulant mate- During the previous two
The thermal stress test is also rial. A dispersant specifically untreated cycles, the heat trans-
used to select the best-perform- formulated for control of fer capabilities for the preheat
ing polymer inhibitor. Table 4 organic deposits was found to exchangers declined at a rate of
shows a summary of the gum be highly effective for this 0.11 U-coefficient units per day,
tests run on the feeds to this application. resulting in a 202-day run and
NHT unit. 0.06 U-coefficient units per day
Dispersion tests are used to Treatment programme for a 404-day run. For the recent
measure the ability of disper- implementation cycle with the treatment
sant additives to hold deposits Based on the root cause analy- programme in place, the heat
in solution. Samples of the gum sis, a Baker Hughes Lifespan transfer decline was 0.01 U-coef-
deposits from the stress tests or treatment programme was ficient units per day, resulting
deposits from the heat exchang- implemented to control polym- in a 662-day run. The treatment
ers are mixed with a clear erisation of the reactive feeds programme allowed the refinery
organic solvent along with vari- and to disperse the organic and to operate the NHT uninter-
ous dispersant additives. The inorganic particulates. Polymer rupted until the normally

4 PTQ Q4 2012 www.digitalrefining.com/article/1000651

scheduled turnaround for cata-
80
lyst replacement. Cycle 1 − untreated
Figure 4 compares one of the 75
Cycle 2 − untreated
heat exchanger tube bundles 70 Cycle 3 − treated

with and without the antifou-
lant treatment programme. Both
photographs are taken at the
end of run prior to cleaning.
The bundle appearance and
deposits from cycle 2 were
consistent with degraded poly-
mers coupled with iron
sulphide. Clearly, there was
significantly less deposit with
the fouling control treatment
programme in place.
Conclusion
The root cause of the increased
heat exchanger fouling rate was
the shift in the NHT feed qual-
ity. The refinery configuration
change implemented just prior
to the increased heat exchanger
fouling altered the NHT feed to
include C4. The coker butanes
and butylenes contain a high
concentration of mercaptans
and olefins, which lead to free
radical polymerisation.
Identification of the primary
cause of fouling enabled the
development of an antifoulant
additive treatment programme
that was able to control the rate
of heat exchanger fouling. This
programme provided the refin-
ery an economic return of over
500% by permitting the unit to
run at full throughput rates,
preventing unit shutdowns
prior to scheduled catalyst
replacements and reducing
maintenance costs.
LIFESPAN is a trademark of Baker
Hughes.
Acknowledgements
The authors wish to extend their
gratitude to Tomasa Ledesma, Baker
Hughes Antifoulant Chemist, for her
work in conducting the fouling studies;
the analytical group at the Baker Hughes
U, BTU/hr / SF / ºF
65
60
55
50
45
40
35
30
0 100
Figure 3 Heat transfer coefficient trends
After cycle 2
11 months online (untreated)
Figure 4 Heat exchanger tube bundle prior to cleaning
Sugar Land laboratory; and Ralph Kajdasz,
Baker Hughes Account Manager, for his
efforts in keeping the programme running
at the refinery, and for development and
calculation of the monitoring data.
References
1 Wright B E, The causes and control of
fouling in hydrodesulphurization units
— a tutorial, AIChE 2002 Spring National
Meeting, 3rd International Symposium
on Mechanisms and Mitigation of Fouling
in Refining and Upgrading, Mar 2002.
2 Medine G, Wright B E, Distillate
hydrotreater fouling, AIChE 2008 Spring
National Meeting, Apr 2008.
3 ASTM D 381, Standard Test Method for
Gum Content in Fuels by Jet Evaporation.
Bruce Wright is a Senior Technical
Support Engineer in Baker Hughes’s
Industrial Technology department in
Sugar Land, Texas, specialising in the
200 300 400 500 600 700
Days
After cycle 3
21 months online (treated)
hydrocarbon process industries. He
holds a BS in chemical engineering from
Rensselaer Polytechnic Institute, Troy,
New York, a MBA from the University of
Houston, and is a registered professional
engineer in the State of Texas.
Todd Hochheiser is a Refinery
Optimization Manager with Valero
Energy Corporation. He holds a BS
degree in chemical engineering from the
University of Delaware, an MBA from the
University of California, and is a member
of the American Institute of Chemical
Engineers.
Links
More articles from the following
categories:
Corrosion/Fouling Control
Heat Transfer

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