Mitigating overhead corrosion

Advanced data handling and sensitivity analysis enable fuller understanding of

the influence of operating changes on salt formation

BRANDON J H PAYNE, KEYURKUMAR PATEL, COLLIN W CROSS, MATTHEW G COLLINS and PABLO A GRIECO
SUEZ Water Technologies & Solutions

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 ously manipulated on a day-to-day
Greater frequency and basis.
medium latency still misses
key corrosion events with
no predictive response High frequency and low
latency enable real-time and types of tramp amines enter-
response to a corrosion event
Salting events
Salt probability index

amines arising from the use of H2S

mitigate overhead salt fouling and

addressed this dilemma by estab-

Low frequency, Medium frequency, High frequency,
high latency medium latency low latency
sample results sample results sample results
Results latency period Salting probability index
Amine speciation performed

Figure 1 Salt precipitation events comprehensively characterised with high frequency a bi-weekly or more frequent basis.
and low latency amine speciation in a column overhead system

10% of the time in operation. Due the amount of data generated by

ble of a rigorous sensitivity analy-

sion (see Figure 1

identify the proverbial 10% of time long laboratory turnaround time

possible.
enough to allow for broad based
be performed autonomously on

above. This ability has enabled

operators to evaluate a wide range

into the industry’s monitoring pro-

in time. Corrosion loss is, there-

mitigation programs, the data upon

ously been available.
events that were previously missed

spots in the evaluation of asset

allow both unit operations and the

56 PTQ Q4 2018 www.eptq.com

q4 suez.indd 2 13/09/2018 17:47 cat

 described above. With use of the
high concentrations
SafeZone technique, of theH2new
S (>30 000
com- When to stop injection and gasoil hydrodesulphurisation units
ppmv) because of potential dam- 250 equipment
disconnect DMDS and naphtha hydrotreaters.

Boot water amines,

putational framework allows con- NH3
age to metallurgy
tinuous and quantitativeand tosensitivity
the recy- Once more 200 than the stoichiomet- e ser ice o ers
CHXA
cle compressor.
computations, But stabilisation
leading to the rapid of ric amount of DMDS is injected, • Safe equipment: workers have
MEA
H2S concentration at typically 10 000 how can one150 be sure that the cat- never been exposed to any H2S leak.

ppm
SafeZone indicated CXHA salting.
ppm is not
corrosion so easy
events because
and their H2S
precise alyst is fully 100sulphided? A con- • High reliability and accuracy:
Discussion with customer initiated.
results from the balance
causes. During an emerging corro- between venient test is as follows: DMDS continuous H2S monitoring has
catalyst consumption (full conver- injection is put 50 on hold for a while been ac ie ed at all t e refineries
sion of and
rapidly metal oxidesdigitally
alerted to sulphides)
while and H2S is observed;
0 since a fresh that commissioned the service, and
and H S formation either from feedstock containing1 2
sulphur 3 is 4con- 5 H S 6concentration
7 8 9 always
has 10 11been
the driving
2 forces of salt formation 2
DMDS or from sulphur species in tinuously introduced, the H2S con- Time, in line with other analytical meth-
days
and their sensitivities are quantita-
the feedstock. Hence, continuous centration in the recycle hydrogen ods (reactive tubes, on-line gas
tively revealed. The demonstrated
measurement of H S concentration should increase due to the conver- chromatography, for instance).
method takes near 2 real-time data Figure 2 Selected overhead accumulator boot water amine concentrations, ppm
and its rate of decrease or growth is sion of sulphur compounds in H2S • A useful tool to better manage
from operating crude units and uses
key information to decide when and by the catalyst and no further H2S the catalyst sulphiding operation
them to compute how changing by SUEZ allows rapid, continuous, Also available is a ‘what if’ inter-
by ow muc t e ow rate consumption by the fully activated according to catalyst manufacturers’
factors, such as crude diet, process- and quantitative computations for face for evaluating potential miti-
needs to be adjusted. Figure 2 illus- catalyst. Figure 2 is an interesting procedures and guidelines.
ing objectives, operations, control amine hydrochloride salt forma- gating options on both current and
trates this optimisation of DMDS demonstration of this test: DMDS • Continuous H2S indication helps
schema, physical constraints, set tion in an operating crude unit to historically recorded events. The
ow rate durin a ydrocrac in injection was stopped after 18 hours to antici ate ow rate
points, and randomly varying be performed easily. When using sophisticated signal processing and
unit sulphiding operation. In addi- and H2S levels stabilised for two changes; DMDS consumption and
amine, and chloride levels, cause the technique, the driving forces of analytics algorithms of the platform
tion to the technical advantages for hours before they began to increase sul idin time can be si nificantly
corrosion events. The practical salt formation and their sensitivi- are then used to make a wide array
catalyst activation, this approach sharply. This test can be achieved reduced.
objective of the methodology is to ties are quantitatively revealed and of valuable capabilities become
minimises the excess of DMDS used safely and e ecti ely wit continu-
drive timely, precise, and proactive deconstructed graphically and in practical, seamless, and potentially
for the activation and leads to some ous H S measurement.
mitigation options in a detailed and tabular2 mode into a group of indi- Francis fully Humblot is NewImportantly,
automated. Business Developer,
the
si nificant sa in s urin t is unit thiochemicals for are
the oil and subject
gas market
systematic
activation, fashion
53.2 tonnesacrossof a DMDS
wide cators which
Conclusion detail potential action- computations done to
with Arkema, Lacq, France. He holds a PhD in
variety of event types
was finally consumed w ic is using graph- able options. The output is available the actual physical and operational
The Arkema analyser has been used heterogeneous catalysis from the University of
ically
only oriented
6% above reports
the and widgets.
stoichiometric to
forallmonitoring
parties dailyH2Sonin their mobile
the recycle Lyon, France.
The SafeZone platform
requirement of the catalyst. developed devices
hydrogen of hydrocracking report.
in a comprehensive units, its daily operation.
Email: francis.humblot@arkema.com

SELECT THE
BEST CATALYST avantium.com/rct

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Catalytic Reforming • Isomerization • Hydrotreating • FCC Pretreat • Hydrocracking • Dewaxing

www.eptq.com
www.eptq.com Catalysis 2018 6357
PTQ Q42018

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17:47
 been detected in time. However, the
TTT-SDT (actual SafeZone optimised)
SafeZone engine’s ability to examine
TTT-SDT (what-if normal operations) multiple variables simultaneously
MET-SDT (actual SafeZone optimised) and quantify the relative impact
50
MET-SDT (what-if normal operations) on the system’s salt point allowed
40
the site to continue to evaluate
30 results and further optimise unit
20 performance and maximise asset
T, ºF

10 protection while production was

0 maintained. The SafeZone program
−10 quantitatively demonstrated that
−20 the unit could further reduce salting
−30 potential by both raising steam rates
−40 and lowering the rate of the top
1 2 3 4 5 6 7 8 9 10 11 pump around (TPA) while corre-
Time, days

Figure 3 Calculated temperature safety margins (°F) in the column overhead system which was normally kept to a mini-

corrective actions have historically setting and balanced duties of these

been prohibitively time consum- changes kept tower temperature at
ing and thus provided only a back- targeted levels while reducing salt
nique was demonstrated in a crude ward-looking perspective to unit point. The reduction of TPA rate,
unit constrained in both its desalter operational controls. The SafeZone however, lessened the duty of asso-
performance and crude overhead platform, on the other hand, rap- ciated cold train exchangers, lead-
safety factors. As is the case with idly alerted the operations team to ing to a slight lowering of desalter
the changing corrosion conditions temperature below target range.
dietary change driven by an unfore- and allowed them to evaluate a list Desalter temperature was normally
seen event rapidly changed both of potential mitigating actions that controlled according to a predeter-
product and operational economics typically fall outside of traditional
as well as the availability of usable evaluation methods (see Figure 2). this case, however, the crude slates
opportunity crude slates. This sit- The amine speciation protocol viscosity and overall good desalter
uation forcibly altered the histori- used by SafeZone, which screens
cal ‘normal’ operating parameters
of the unit. To maintain the deter- species several times each week, few degrees of desalter temperature,
detected the increased concen- along with a slight steam increase,
the TTT was targeted to remain at a tration of cyclohexylamine in the and a slight excess of caustic for
minimum of 15°F higher than the overhead system and determined chloride reduction to obtain a sig-
calculated salt point to help mitigate it to have the most detrimental salt
corrosion in the overhead system. point. Following the automatic eval-
Historically, unit operations had uation of the emerging event by team decided these small projected
allowed for an average TTT safety the SafeZone analytics engine, the
margin of 40°F above the computed quantitative output immediately
salt point. However, due to the rapid mitigation and so tower operations
and unforeseen change of crude diet, several key actions which prevented were successfully adjusted, lead-
several unit operational challenges the system from violating its corro-
sion safety metrics. salt precipitation potentials with no
operation was, therefore, adjusted to The calculations indicated a sub- measured loss of operational per-
accommodate the new performance stantial decrease in both the TTT formance, product distribution, or
envelope so as not to cross the min- safety margin as well as the over- product quality.
imum safety threshold. head chloride safety margin imme- Without the use of the SafeZone
Driven by these changes to crude diately following the crude changes. program, this non-intuitive set of
diet and operations, an additional The analysis reported by the linked actions could not have been
SafeZone engine prompted the site evaluated in a timely manner in
ylamine increased the salt precip- to increase rapidly the caustic injec-
itation potential in the overhead tion rate to counter the detrimental on the unit during the event. The
system, threatening asset integrity daily calculation of these factors
the traditional evaluation method- and the associated ongoing adjust-
point safety margin. Traditional ology, this singular move might ments of these variables allowed
methods of calculating salt point the team to continuously improve
safety margins and determining the TTT safety margin immediately

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 chemical applications including corrosion,
beginning at 3-4°F above the tar- also considering practical equip-
desalting, fouling, and finished fuel additives.
ment challenges and unit constraints. With over 25 years of specialty chemical
As Figure 3 shows, by using the Balancing processing objectives experience, he holds a BS in electrical
on-stream predictive capabilities against corrosion risk to achieve engineering from Texas A&M University.
a customised processing strategy Keyurkumar S Patel is a Lead Products
dynamical salt point safety margin Application Engineer with SUEZ Water
improvements were realised with the corrosion potential for the frac- Technologies & Solutions, and is responsible for
respect to what would have been tionator overhead. Importantly, this the development, deployment and technical
obtained using the previous operat- was done while maintaining pro- support of the company’s corrosion modelling
ing scheme (the dashed lines). cessing targets and optimising the software applications used in refinery corrosion
management. With 10 years of professional
This case demonstrates that it is use of existing corrosion mitigation
experience, he holds a PhD in chemical
often the balanced combination of methods. The automated salt point
engineering from the University of South Florida.
changes to multiple contributing fac- analytics framework engendered by Brandon J H Payne is a Lead Products
tors that provide for the most robust SafeZone provides the ability to opti- Application Engineer with SUEZ Water
Technologies & Solutions and is responsible for
adjustment of only one performance technical support, programme development
parameter, such as temperature, and quantitative way. and application optimisation for the company’s
refinery process chemical programmes used
SafeZone is a mark of SUEZ.
optimise corrosion mitigation with- in refinery corrosion management. With over
out leading to a loss against produc- Pablo Grieco is Senior Regional Engineer with 20 years of experience in the hydrocarbon
tion targets. SafeZone allows for the SUEZ Water Technologies & Solutions and is processing industry, he holds a BSc degree in
responsible for technical support, programme chemical engineering from the University of
rapid, automatic, and comprehen-
development and application optimisation Illinois Urbana-Champaign.
sive evaluation of multiple factors
for the company’s refinery process chemical Collin Cross occupies a role in the Product
that reveal action paths that would programmes used in refinery corrosion Management organisation of SUEZ Water
have otherwise been obscured by management. With over 20 years of experience Technologies & Solutions and leads the global
traditional evaluation paradigms. of specialty chemicals, he holds a BSc degree Center of Excellence for refinery corrosion
By using the SafeZone platform, in chemical engineering from the National control. With specialities in structure activity
- Technological University of Argentina. relationships, formulation, thermophysical
ance corrosive interactions caused by Matt Collins is Site Lead/Process Lead modelling, computer programming, and
an unplanned introduction of new with SUEZ Water Technologies & Solutions, software development, he holds a PhD in physical
crudes and production targets while overseeing and managing numerous process chemistry from University of Oklahoma.

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