Real-time crude and desalter monitoring

An analyser array supports corrosion management through continuous insights into

changes in crude quality

ALBERT MOURIS and ETIENNE HUNT Hobré Instruments

KEVIN CLARKE CREAS Energy Consulting

T
o maximise profits and remain
competitive, refineries regu-
larly reoptimise their crude Crude oil tanks
Cold
slate with changing market condi- preheat train
exchangers Mix valve
tions. As a result, crudes change Crude oil
frequently, and the plant is driven
towards processing cheaper, heav-
ier, and lower quality crudes. Many Wash water Wash water
Desalter

of these lower quality crude oils

contain higher levels of salts (chlo- Desalted
crude oil
rides), organic chlorides, sulphur,
nitrogen, metals, tramp amines, as Brine
well as high solids and acidity. All
of these factors can drive up corro- Figure 1 Typical crude unit cold preheat train and desalter configuration
sion within the crude processing
complex without proper condition- transportation. The salts in crude oil $0.45-0.50/bbl of total global crude
ing which, in turn, can be hampered consist primarily of sodium, magne- oil processed. Processing of these
by the difficulty in determining the sium, and calcium chlorides. lower quality crude oils is concen-
precise crude mix hour-by-hour While some of these lower qual- trated within a subset of the global
(inadequate tankage for proper ity crudes can be priced at a $2-$3/ refining population, so there is
segregation, layering, tank heels bbl discount to Brent, most refin- clearly considerable commercial risk
of unknown composition, slops ers would not be able to process to processing these crudes without
reprocessing, tight crude oil inven- these at more than 25% of their adequate monitoring of contam-
tory controls to minimise working total crude slate – implying a com- inants, operations, and corrosion
capital, and the frequency of crude mercial incentive of approximately rates to mitigate the potential for
tank changes). Many refiners report $0.50-$0.75/bbl or $37-55 million/y integrity problems.
crude changes as often as every two for a typical 200 000 b/d refinery. Magnesium and calcium chlorides
to three days. Recent studies have suggested that have a higher tendency to remain
A critical element of corrosion the annual cost of corrosion in refin- in the oil phase than sodium chlo-
control within the crude complex ing is approximately $15 billion or ride, so sodium chloride removal by
is the desalter (see Figure 1). The
desalter serves several purposes:
• Reduces the salt (inorganic chlo- 100
ride) content of the crude oil 90 Magnesium chloride
• Dehydration 80 Calcium chloride

• Solid separation
% of chloride hydrolysed

70
• Recovery of phenols from
60
wastewater
50
Salt occurs naturally in crude
oil, so a certain amount of brine is 40
produced with crude which is sep- 30
arated in the field and relatively 20
dry crude oil is sent to the refin- 10
ery. Chlorides introduced into an 0
oil well during a workover or well 200 300 400 500 600 700 800
stimulation will also appear in the Temperature, ˚F
produced crude. Salt can also enter
crude oil from seawater during Figure 2 Hydrolysis of magnesium chloride and calcium chloride with temperature

www.digitalrefining.com/article/1002501 PTQ Q3 2020 49

 ride content of the desalter efflu-
90 ent crude oil is therefore critical
to mitigating corrosion. Chlorides
(NaCl, MgCl2 and CaCl2) in excess
FACT, wt%

80
of 20 ppm are known to cause seri-
70 ous corrosion issues due to the
liberation of chloride ions which
60
0 2000 4000 6000 8000 10000 12000 travel to the top of the crude tower
V+Na, ppm (see Figure 5) and condense with
the first drop of water at the water
dewpoint, with a very low pH (1-3).
Figure 3 FCC catalyst activity, Ecat wt% vs Ecat V+Na Source: BASF This highly localised point of cor-
rosion can move around within the
effective desalting is usually nearly heat exchanger train and oil con- overhead system, depending on
complete. In most cases, magnesium tent of the desalter effluent water. the water content, top temperature,
and calcium chloride levels in crude However, many refineries have functioning of the condensers, and
are low. increased processing capacity over vapour flow rate. Refiners inject
As crude is processed through time and are running a progres- ammonia or amines into the over-
the crude tower and then the vac- sively heavier crude slate, without head system to neutralise the acid,
uum unit and downstream residue making the corresponding mod- as well as filming amines which
upgrading units such as delayed ifications to their desalters, with cover the internal surfaces of the
cokers, residual magnesium or cal- the result that desalting and dehy- exchanger tubes to prevent the acid
cium chlorides will hydrolyse in the dration efficiencies have declined, from reaching the metal surface.
presence of trace water, releasing thereby driving up the risk of Frequent crude changes and vari-
hydrogen chloride. The hydrolysis downstream reliability issues. ations in desalter performance can
to temperature relationship is illus- In addition, normal build-up result in under-dosing of neutralis-
trated in Figure 2. of sediments in the bottom of the ing amine. Filming amines can also
Sodium chloride will not decom- desalter during the run (see Figure be stripped by high vapour veloc-
pose to any significant extent, but 4 for typical desalter internals) can ities or may fail to coat all surfaces
passes into the atmospheric residue also serve to reduce residence time, evenly. As a result, dewpoint cor-
where it can accelerate coking in the so desalting efficiency can reduce rosion remains an ongoing issue
vacuum unit and downstream res- across the cycle. Within these tight within many crude towers.
idue conversion units (visbreaker, net margin environments, it is sur- This difficult situation is further
delayed coker, and so on), shorten- prising that the operation of many exacerbated by two other factors:
ing the run length between heater crude oil desalters is not rigorously • The declining demand for gaso-
decokes. In addition, sodium in the adjusted following changes in the line, particularly in European and
FCC feed serves to exaggerate the crude slate, and there has been lim- Asian economies where refiners
conversion impact of any vanadium ited investment in tracking desalter typically aim to maximise middle
in the FCC feed, with implications operating performance in real- distillate (jet fuel and diesel) pro-
for fresh catalyst use and yield per- time to provide advance warning duction. This drives down the opti-
formance (see Figure 3). of sub-optimal performance and mum temperature for the crude
Hydrogen chloride generated potential downstream issues. tower overhead, further raising the
from the magnesium and calcium Clear understanding of the chlo- risk of dew point corrosion, as well
salts will move upwards as the exposure of larger
in the distillation columns areas of the crude overhead
until it finds ammonia or system to the potential of
amines to combine with, or dewpoint corrosion, such
until a liquid water phase as the tower dome itself.
forms, or until the hydro- • Presence of organic
gen chloride is drawn into chlorides in the crude oil,
a product. The corrosive from upstream oil produc-
impact of the chlorides tion chemicals, particu-
will then be observed in larly with ageing oil fields.
the crude tower and the Organic chlorides are not
overhead heat exchang- removed in the desalter,
ers. Therefore good con- preferring to remain in the
trol of the desalter can oil phase, but can release
substantially reduce cor- chloride ions in the crude
rosion within the crude distillation tower just
tower overheads, as well the same. These chloride
as fouling in the pre- Figure 4 Desalter schematic ions usually appear in the

50 PTQ Q3 2020 www.digitalrefining.com/article/1002501

naphtha streams and react in the
naphtha hydrotreater(s) to release Offgas
hydrogen chloride, causing corro-
sion and fouling problems. The con- Condensers Air coolers

tamination of the Druzhba crude oil Crude

pipeline network with organic chlo- distillation Crude overhead drum
tower
rides in April 2019 is a case in point (top section)
which caused severe disruption to
refinery operations in Central and Reflux return

Eastern Europe. Water

Naphtha product

Real-time corrosion management

Good single-stage desalter perfor- Figure 5 Typical crude unit overheads configuration
mance achieves a desalting and
dehydration efficiency of more than water. This enables tighter track- ters, and additional measurements
90%. More than 95% salt removal ing of chemical injection rates in for oil-in-water and water-in-oil
can be achieved with double desalt- case of unit upsets, fluctuations, analysis), providing the measure-
ing. Absolute performance depends during start-up, or processing of ment of chlorides in real-time, offer-
on various key parameters such as: crude oil with high organic chloride ing the potential for continuous
• Crude oil properties (API, asphal- content. corrosion control (see Figure 6).
tene content, and so on) In addition, real-time meas- By accurate, sensitive, and con-
• Desalter temperature urement of metals in crude oil tinuous measurement upstream
• Desalter pressure can bring considerable value in (Position 1 in Figure 6) of the
• Wash water pH predicting imminent changes in desalter, the analyser enables oper-
• Oil residence time downstream unit feeds, where con- ators to track changes in total chlo-
• Effectiveness of the demulsifier taminants are either poisons or key ride levels, to proactively adjust
chemical final product quality specifications desalting operating conditions and
• Wash water mixing (such as chloride load to naph- chemical addition rates to ensure
With relatively low levels (>20 tha hydrotreating units, FCC feed good desalting and dewatering
ppm) of chloride content in desalted nickel, vanadium, iron or delayed performance.
crude having the potential to lead coker feed nickel, vanadium, sul- A second analyser downstream of
to significant corrosion issues in phur). The system can also provide the desalter unit (Position 3) tracks
the overhead condensation system insight into incoming iron in crude, the desalted crude chloride content
of the crude distillate unit (Palash which is a problem widely observed to verify desalting performance
Kumar Bhowmik, 2012), the Hobré during processing of light tight and minimum chloride entering the
solution employing the C-Quand oils, to enable optimisation of iron crude tower.
XRF analyser comes into play. The removal chemicals. For systems employing dou-
C-Quand XRF analyser provides With over 40 years’ experience in ble desalting vessels, the desalted
on-line measurements of crude con- designing and engineering online crude C-Quand analyser in Position
taminants (such as total chlorides, process analysers, Hobré Analyzer 3 could be multiplexed to measure
sulphur, magnesium, iron, nickel, Solutions offers a turn-key total chloride entering the second desalter.
vanadium, arsenic, and other ele- package solution tailored to specific To provide a complete picture of
ments) to enable the realisation of layouts. The proposed solution con- desalter performance, installation
a real-time corrosion management sists of a set of C-Quand ED-XRF of a water-in-oil analyser at Position
strategy for the crude distillation non-destructive analysers (and 2 provides early warning of exces-
unit, by: optionally sample handling, shel- sive water levels coming from crude
• Ensuring effective crude desalt-
ing, by enabling reporting of desalt-
ing efficiency in real-time and Water-in-oil
2
alerting any exceptions caused by Crude oil tanks
Multiphase
water-cut
Cold
preheat train
performance degradation during meter exchangers Mix valve
and following crude switches or Crude oil
5
due to slops reprocessing (with an C-Quand Multiphase
undetermined and highly variable
XRF analyser
S, Cl, Ni, V, Fe, As, Si, Pb Desalter water-cut
1 Wash Wash meter
chloride content). water water

• Alerting to changes being Desalted

crude oil
required in overhead chemi- 4
3
cal dosage (ammonia or neu- Mirmorax
Brine
C-Quand
XRF analyser

tralising amines and filmer) by Oil-in-water S, Cl, Ni, V, Fe, As, Si, Pb

real-time measurement of the

chloride content in the overhead Figure 6 System for real-time desalter chloride measurement for corrosion control

www.digitalrefining.com/article/1002501 PTQ Q3 2020 51

 heater and any downstream residue
Offgas conversion units (not evaluated)
Condensers Air coolers
• FCC yield impacts from higher
Na+V in the feed, requiring higher
Crude overhead drum fresh catalyst addition to restore
yields, and/or economic penalty
Reflux return
from yield degradation (≈€100k/
Crude Water year for a 1% increase in fresh cata-
lyst usage)
S, Cl, Ni, V, Fe, As, Si, Pb
distillation
tower C-Quand
(top section) XRF analyser 6
A fully installed and operating
Naphtha product
S, Cl, Ni, V, Fe, As, Si, Pb analyser system, as specified in
Figures 6 and 7, would generate a
Figure 7 Proposed system for real-time desalter chloride measurement for corrosion control payback within just two to three
months of operation, based on the
tankage, in the event that the crude Economic justification operations savings evaluated above.
oil has not had sufficient settling For a mid-sized refinery of 200 000 A much shorter payback would be
time. Operators can use this meas- b/d, the estimated annualised costs achieved if the system prevented
urement to anticipate an increase due to a crude overhead failure an unplanned shutdown caused by
in water by trimming the wash caused by corrosion alone are of the crude overhead corrosion.
water rates to avoid overloading the order of €1 to €2 million/y (five-year C-QUAND is a mark of Hobré Analyzer
desalter and could be incorporated run between turnarounds). A sin- Solutions.
into a closed-loop control scheme. gle 10-day shutdown event would Further reading
A second water-in-oil analyser cost approximately €5-10 million in 1 Xiaohui Li B W, Hazards of Organic Chloride
is proposed for the desalted crude lost processing capacity, replace- to Petroleum Processing in Chinese Refineries
(Position 5) to ensure that the unit is ment equipment (often ordered at and Industrial Countermeasures, Progress
performing to optimal dehydration short notice with premium pricing Petrochem Sci .2, 2018.
levels. Next, an oil-in-water analyser for rapid delivery), subcontract per- 2 American Petroleum Institute, Understanding
is recommended for the desalter sonnel, staff overtime, and crane crude oil and product markets, Digital Media,
2014.
effluent water (‘brine’) to ensure costs. This figure would be further
3 Palash Kumar Bhowmik M E, Corrosion and
that this is minimised (Position 4), to increased by an amount of the order
its control in crude oil refining process, Dhaka:
avoid losses of crude oil to the efflu- of €4.5 million/y, comprising: IMEC&APM- ABS-000, 2012.
ent water treatment system that then • Reduction in crude tower over-
consume crude processing capacity head temperature (≈0.5°C) to Albert Mouris is Chief Technology Officer
when they are later reprocessed. increase jet kerosene production by with Hobré Instruments BV and is responsible
Finally (see Figure 7), a C-Quand 0.1 vol% (at the expense of naphtha) for the R&D programme. He has more than
analyser measuring the chloride without increasing the risk of dew 25 years’ experience in process analysis and
sampling systems and holds a MS degree in
content of the crude overhead drum point corrosion (≈€3.6 million/y for
chemical engineering from the University of
water (Position 6) enables real-time a 200 000 b/d refinery)
Twente, The Netherlands.
tracking of chloride excursions and, • Demulsifier over-dosing costs Email: [email protected]
particularly, any organic chloride (≈€20k/y for a 10% saving) Etienne Hunt is Product Manager of C-Quand
breakthrough, providing guidance • Filming and neutralising amine at Hobré Instruments. He started working for
to optimise filming and neutralis- over-dosing costs (≈€7000/y for a Hobré in the Service team before moving to
ing amine dosages. In addition, the 10% saving) his current role. He holds a bachelor’s degree
analyser provides measurements • Preheat exchanger network foul- in aeronautical engineering and is finalising
of metallic corrosion products such ing increasing energy costs and/or his masters in product development and
as iron. This analyser can be mul- increased preheat train antifoulant management from Cranfield University, UK.
tiplexed to also survey chlorides dosage (≈€300k/°C/y) Email: [email protected]
Kevin Clarke is CEO of CREAS Energy
in the naphtha product, to provide • Costs for reprocessing of recov-
Consulting. CREAS supports downstream
early warning of carry-over into the ered oil from effluent water treat-
industries in digital and energy transitions.
naphtha hydrotreater feed. Tighter ment (≈€300k/500 b/d/y) He has 34 years’ experience in refinery and
understanding of the total chloride • Savings in laboratory analysis, petrochemicals operations, optimisation
balance across the desalter and the equipment and consumables costs and consulting, and holds a MBA and a BEng
tower overheads, in combination (≈€100k/year) degree in chemical engineering and chemical
with an on-line overhead corrosion • Impact of chloride carry-over into technology from Imperial College, London.
monitoring system, allows opera- the naphtha hydrotreater feed from Email: [email protected]
tors to drive the top temperature to a corrosion, heat exchanger fouling,
minimum, thereby driving up com- catalyst fouling and deactivation, LINKS
mercially attractive middle distillate and increased reactor pressure drop More articles from the following
yields at the expenses of naphtha/ (not evaluated) categories:
gasoline, without unnecessarily risk- • Shorter run lengths between Corrosion and Fouling Control
ing increased corrosion rates. heater decokes on the vacuum Instrumentation, Automation and
Process Control

52 PTQ Q3 2020 www.digitalrefining.com/article/1002501