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

I
-
-

- -
-
-
-
-
-

-
-

-
- -
-
-

-
-

- -
-

- - -

-
-
- -

-
-
- -

-
-

www.eptq.com PTQ Q4 2018 55

q4 suez.indd 1 13/09/2018 17:47

 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

WITH CONFIDENCE

Your Feed Reliable Results Cost-Effective Fact-Based

Your Conditions Statistically Significant Comparison Decisions

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

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

q4cat Arkema.indd
suez.indd 3 3 26/02/2018
13/09/2018 16:19
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

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

58 PTQ Q4 2018 www.eptq.com

q4 suez.indd 4 13/09/2018 17:47

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

w
flo
CATALYST PROTECTION /X
om
.c
al
ic
yt

SAVE OVER €250,000/YEAR*

al
an
.p
w
w
w

USE THE EPSILON XFLOW TO:

Save over €250,000/year, compared to using any other analyzer, by using a low-maintenance, highly
reproducible Epsilon Xflow on-line analyzer.

• Extend catalyst life time by simultaneous on-line • Quickly switch between process streams:
analysis of S, Fe, Ni and V : saves €100,000/year saves €50,000/year
• Reduce conflicts between lab and on-line results: • Reduce instrument- and calibration maintenance:
saves €100,000/year. saves €15,000/year

Do you want to know more? Contact your local

representative or visit:
www.panalytical.com/Xflow

*Monetary savings are based on 400,000 bbl/day refining capacity and typical operating costs.
No warrantees or guarantees are given.

www.eptq.com PTQ Q4 2018 59

PN11502.indd 1 21/02/18 12:16

q4 suez.indd 5 13/09/2018 17:47