INGOLD

Leading Process Analytics

Corrosion in refinery operations has been, and still
is, the subject of many studies, papers, courses
and web forums. Although a lot of what has been
written shows that significant progress in under-
standing corrosion has been made, it also makes
it clear that the problem continues to exist and that
quite possibly is getting worse.
Battling Corrosion in Refneries
With the Power of In-line Analysis
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It is estimated that the global costs of refinery corrosion are
in the order of 15 billion USD annually. Getting more exact
numbers is not possible as refineries do not make available the
extent of their corrosion problems, which is understandable
considering the ever increasing environmental legislation
they face. It is worth mentioning that in these costs, profit
losses and loss of production uptime have not been taken into
account. An analysis report by NACE International states that
in the USA alone annual profit losses due to refinery corrosion
may be as high as 12 billion USD!
Despite extensive research and vast amounts of available lit-
erature, many of the corrosion mechanisms are not yet fully
understood. The problem with petroleum refining is that
there is not one single source of corrosion, but many. To add
to the problem, some of the corrodents might interact and
increase or inhibit each others corrosivity. Also, physical pro-
cess conditions play a role; so temperature, flow and Reynolds
number have to be taken into account too. Of no less impor-
Digital pH electrode InPro 4260 i
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METTLER TOLEDO
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tance is the refinery infrastructure itself. Pipes, vessels, weldings,
instruments, etc. are obviously also part of the equation. Given
the number of variables then, it becomes clear that corrosion is a
complex problem.
Sulfur
One reason why the situation is not expected to improve soon is
the increased processing of low quality sour crudes. Sour crude
is crude oil with a high sulfur content (as opposed to low sulfur
containing sweet crude). Because it provides a lower feedstock
cost, sour crude is preferred by refineries for economic reasons.
Further, sweet crude is becoming less readily available as the
bulk of its supply is exhausted. In sour crude, sulfur is present in
the form of mercaptans, H2S, sulfide salts, elemental sulfur and
so on. Many of these species are reactive and cause sulfide stress
cracking and sulfuric acid corrosion throughout the refining
process.
Acidity
Besides sulfur, crude contains many species that are quantified
by the total acid number (TAN) of the oil. This number is not
specific to a particular acid but refers to all possible acidic com-
ponents in the crude, and is defined by the amount of potassium
hydroxide required to neutralize the acids in one gram of oil.
Typically found are naphthenic acids, which are organic, but
also mineral acids, H2S, HCN, CO2, etc. can be present, all of
which can contribute significantly to corrosion of equipment.
Even materials suitable for sour service do not escape damage
under such an onslaught of aggressive compounds. Again, be-
cause of cost considerations, a trend towards a preference for
crudes with a higher TAN is noticeable.
Desalting
Desalting of the crude is the first step in refining that has a direct
effect on corrosion and fouling. By mixing and washing the crude
with water, salts and solids transfer to the water phase which
settles out in a tank. An electrostatic field is induced to speed up
the separation of oil and water. In this way, inorganic salts that
could cause fouling or hydrolyze and form corrosive acids are
largely removed. Often, chemicals are added in the form of de-
mulsifiers to break the oil/water emulsion. Also, chemicals such
as caustic soda are introduced to neutralize acidic components.
Uncontrolled feeding of caustic can, however, have a detrimental
effect. An excess of caustic can result in the formation of soap due
to, for instance, the presence of fatty acids. Soap stabilizes the oil
water mixture and obstructs the separation process. Also, too
strong a mixing of crude and water can create an emulsion that
is very difficult to break. Frequently the crude arrives at the re-
finery as an emulsion due to the presence of water that had been
used to maximize the oil extraction from the oil reservoir, or
water might have occurred naturally in the reservoir. It can
happen that emulsions are too strong and prove impossible to
break. When this is the case a lot of the contaminants end up in
downstream processes, which may have serious consequences.
One process parameter that can play a vital role in both neutral-
izing acids and demulsification, is process pH. Carefully moni-
toring pH in the desalter water effluent allows for efficient dosing
of caustic or acid which may result in significant cost savings.
The stability of the oil / water emulsion depends partly on pH.
Maintaining the pH of the mixture within a certain range helps
the demulsifier chemicals in breaking the emulsion by interact-
ing directly with the water droplets. The speed and quality of the
separation process can thus be improved which leads to less
water carry-over, which in turn can result in a significant reduc-
tion in downstream corrosion and fouling.
Distilling
Despite a good desalting operation, an abundance of corrodents
can still appear during downstream processing. A good example
of this is the sour water corrosion that occurs in the crude dis-
tiller. During the process lots of acid gases are formed of which
hydrogen sulfide is notorious. Steam, which is injected into the
crude tower to improve the fractionation, condenses in the upper
part of the unit. The hydrogen sulfide dissolves in the conden-
sate and forms a weak acid which is known to cause stress cor-
rosion cracking in the top section of the tower and in the over-
head condenser. This may lead to frequent retubing of the con-
denser and in severe cases to replacement of the entire crude
tower top.
Although this particular cause of corrosion is well known to
refinery operators, counter measures are not always in place.
Typically, corrosion inhibitors and lots of neutralizers such as
caustic soda or ammonia are injected with the aim of increasing
the pH of the sour water. Although this is an obvious response to
the problem, the cure can be worse than the disease. The pres-
ence of various acid gases and ammonia can result in solid salt
depositing from which ammonium bisulfide is one of the main
causes of alkaline sour water corrosion. pH levels higher than
7.6 dramatically increase ammonium bisulfide corrosion. By
overdosing caustic that level is easily achieved. Hence, as in de-
salting, the key to corrosion reduction is in accurate pH control.
Proper neutralizer dosing through crude distiller overhead con-
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METTLER TOLEDO
denser boot water pH measurement will not only reduce corrosion
but also reduce chemical consumption. Reductions in
the use of corrosion inhibitors of more than 15 % have been re-
ported.
Besides the crude distiller many other downstream operations
involve sour water and accordingly suffer from corrosion issues.
Typically affected operations are:
n Vacuum distilling
n Fluid catalytic cracking
n Hydrocracking
n Hydrotreating
n Coking
n Sour water stripping
Few design engineers actually schedule pH control facilities in
any of these operations. This seems odd and was indeed not al-
ways the case. In fact many units are or were at a certain stage
equipped with pH control loops. However, when it comes to reli-
ability, most pH analyzers show an extremely poor track record
in refinery sour water environments. Not specifically designed for
refinery applications, most pH electrodes suffer from poor perfor-
mance in the presence of high sulfide levels and the substantial
hydrocarbon load. As maintenance personnel and manufactur-
ers are often unable to solve these problems, the majority of pH
analyzers in these less standard applications are ignored by
operators.
When conducted properly however, proper pH control results in
sizeable earnings. Not only because of a reduction in chemical
consumption and equipment corrosion, but also thanks to the
extension of the period between maintenance shut-downs and
the resulting additional operating days.
Xerolyt

Extra
Though available in endless varieties, virtually all pH electrodes
have difficulties with the hostile environment present in sour
water applications. The most common cause of sensor failure is
poisoning and fouling of the reference electrode system. Sulfides
diffuse from the process side into the sensor and react with the
silver / silver chloride reference electrode, changing the electrical
potential at the reference side. This causes drift of the pH mea-
surement. Oily substances and solid contaminants may coat or
clog the diaphragm of the reference junction which obviously has
a negative impact on the sensor performance as well. In order to
overcome these problems, sensor manufacturers have been very
creative in their choice of reference diaphragm. Now it is possible
to find pH electrodes with a ceramic, plastic, rubber or even wood
reference diaphragm. The issues they all share are that in sour
water applications their performance can be severely limited
(some may fail immediately), their maintenance requirement is
high and their lifetime short.
For a long time, pH electrodes with a flowing reference junction
have been giving superior results. A flowing reference is obtained
by pressurizing the electrode. The overpressure forces liquid elec-
trolyte through the diaphragm into the process. This outgoing
flow of electrolyte slows down the diffusion of poisoning sub-
stances into the sensors reference system and retards fouling and
clogging of the diaphragm. These types of electrodes such as the
InPro 2000 i from METTLER TOLEDO are an excellent choice for
petroleum refinery applications. They do, however, require fre-
quent refilling of electrolyte, which from a maintenance point of
view is not always acceptable. METTLER TOLEDO has acknowl-
edged this issue and has designed the InPro 4260 i pH electrode
with Xerolyt

Extra solid polymer electrolyte. The InPro 4260 i

has an open junction, which is in fact a hole that brings the
solid electrolyte in to direct contact with the process medium.
Contrary to the miniscule capillaries of any other type of dia-
phragm in conventional pH electrodes, the diameter of the open
junction is extremely large and much less susceptible to clogging
or fouling. Another significant difference is in the choice of poly-
mer electrolyte. Xerolyt

Extra has been designed specifically for

service in hydrocarbon environments and provides a strong and
lasting barrier against sulfide poisoning at the same time.
Automated cleaning and calibration
Despite innovative design, even the best pH electrode needs fre-
quent maintenance. Of any process instrument, the pH electrode
probably has the widest rangeability and an extraordinary sensi-
tivity that covers it. Depending on the process application, after a
certain time in operation a calibration is required to make sure
the instrument will maintain its reliability and accuracy. Obvi-
ously its service in the previously discussed sour water applica-
tions is about as tough as it can get. So no matter how good the
sensor is, the need for cleaning and calibrating will occur more
frequently than in a boiler feedwater application, for example.
Experience shows that on many occasions, manual cleaning and
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Digital pH electrode InPro 2000 i
Visit for more information
Mettler-Toledo AG
Process Analytics
Im Hackacker 15
CH-8902 Urdorf
Switzerland
www.mt.com/pro
calibrating every two to four weeks will suffice. When very sour
crudes are refined however, or when the overhead hydrocarbon /
water separation is not optimal, sensor maintenance may be re-
quired to an extent where it becomes problematic and the value
of the measurement is no longer considered an asset. In such
applications the implementation of an automated cleaning and
calibration system is the answer.
Proven to be of great value in numerous dirty applications is
METTLER TOLEDOs EasyClean 400 system. Fully certified for
use in hazardous areas, this unit enables the most difficult pH
measurement tasks. When necessary, EasyClean 400 pneumati-
cally retracts the electrode and gives it a thorough cleaning fol-
lowed by a two-point calibration, without any human interven-
tion. The standalone unit carries cleaning and buffer solutions
on board and requires no more than instrument air and water
supplies to carry out its tasks. An extra valve is available in case
an additional cleaning liquid is needed. For instance, in petro-
leum refinery applications, naphtha is often used to remove or-
ganic fouling from the sensor surface followed by nitric acid as a
secondary cleaning agent to remove corrosion products such as
iron sulfide. Using EasyClean 400 greatly extends sensor life and
allows virtually one hundred percent measurement availability
without compromising reliability. Maintenance activities are
limited to an occasional sensor replacement and refilling of the
cleaning and buffer solutions. Since only minimal quantities
of liquid per cleaning / calibration sequence are used, and
EasyClean 400 is equipped with 3.5 liter canisters, refilling should
be a rare event.
Intelligent Sensor Management
In the end, all pH electrodes will show signs of aging and perfor-
mance will start to fall below the reliability required. METTLER
TOLEDO pH electrodes with Intelligent Sensor Management
(ISM) communicate their remaining operating life through a
digital signal that also carries measurement values, temperature
and enhanced sensor diagnostics. Based on actual process condi-
tions and history, the Dynamic Lifetime Indicator will predict
when sensor replacement is due. This is one of many interesting
features of the ISM platform that truly enables predictive main-
tenance.
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Conclusions
Corrosion costs the world refinery industry billions of dollars an-
nually. Although one of the major contributors to corrosion is the
pH value of process water, pH measurements in oil refinery ser-
vice have acquired a bad reputation due to their poor ability to
measure in the aggressive environment they have to contend
with. When the correct equipment is chosen however, in-line pH
measurement and control facilities have proven to be of great
value in reducing plant-wide corrosion, and the consumption of
chemicals such as pH control reagents and corrosion inhibitors.
This not only results in significant cost savings but also in in-
creased earnings through increased process uptime.
Advances in sensor technology and intelligent automation of the
measurement point, enable pH measurement in the most chal-
lenging refinery sour water environments. From that perspective
an investment in pH control is highly recommended. The gain in
refinery operating days and substantial savings allow for quick
pay back of the pH control loop. Furthermore, partly eliminating
one of the variables from the complex corrosion equation is a leap
toward better understanding of the corrosion mechanism.
Automated cleaning and calibration
system EasyClean 400