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White Paper

pH Control in Crude Desalting

Desalting is a key early-stage process step in the

refining of crude oil. If not conducted correctly, con-
taminants remaining in the crude after desalting
cause fouling and corrosion in downstream process
operations, and reduce the heat transfer efficiency
of furnaces and heat exchangers. Additionally, the
presence of oil in desalter wastewater requires
chemical treatment to meet process and environ-
mental requirements. Changes in crude oil quality
and desalter wash water cause process conditions
to vary constantly, making efficient desalting a
challenge.
Although often overlooked, continuous pH control of
desalter wash water is an essential tool for optimiz-
ing the desalting process. This white paper ad-
dresses key desalting problems pH control can help
address, in particular pH’s influence on the zeta
potential for emulsion stability is reviewed.

Background
Crude oil usually contains a considerable amount of water.
This can be water injected into the well as part of the recov-
ery process or it can be water that is naturally present in the
oil reservoir. The water is actually brine and contains vari-
ous dissolved mineral salts. The crude may also contain
crystalline salts, sediment and corrosion products such as
rust (from cargo holds). All these contaminants need to be
removed before the crude is refined as they cause fouling and
corrosion of downstream equipment. Inorganic salts such as
magnesium chloride and calcium chloride tend to be par-
pH Control in Crude Desalting
ticularly problematic as these salts are so called Lewis acids,
which, under refinery process conditions, hydrolyze and form
extremely corrosive hydrochloric acid. Other contaminants may
also have a direct negative impact on downstream processes, for
example certain metals present in the crude poison catalysts
and render them useless.
Another concern for refineries is oil under-carry in the desalter
effluent as it requires additional treatment and chemical usage
in order to remove it.
The salt content of crude is measured in pounds per thousand
barrels (PTB) and may be as high as 300 PTB. After desalting,
the crude typically has a salt content of 1 – 2 PTB.
Desalting process
To dehydrate and remove the impurities, the crude is heated to
120 – 150 °C and mixed with 2 – 15 % water through a mixing
valve and/or a static mixer. During mixing, the contaminants
transfer to the water phase. The oil/water emulsion is then fed
to one or more large holding tanks or gravity settlers where the
emulsion is allowed to separate into an oil layer and a water
layer. Impurities leave with the water effluent and as sludge from
the bottom of the vessel, and the desalted crude is extracted from
the top.
Emulsion formation
An abundance of emulsifying agents occurs naturally in most
crude oils. These can be resins, asphaltenes and fatty (naph-
thenic) acids or colloidal solids. It is therefore quite common
that when drawn from the reservoir, the water cut of the crude
and the oil are strongly emulsified. These emulsions can be very
tight and difficult to break. The emulsifiers may also bind the
desalter wash water into a stable emulsion with the oil and in-
hibit the separation process.
To help resolve this, several aids are used during the desalting
process. Demulsifying chemicals are injected to promote coagu-
lation and speed up the separation of the two phases. For the
same reason, gravity settlers are equipped with an electric grid
that induces a 5 – 35 kV electrostatic field which concentrates
and flocculates the water droplets. Generally, AC fields are used
to avoid electrolysis of the water phase and to prevent galvanic
corrosion of settling tanks.
2 METTLER TOLEDO White Paper
Frequently, especially in the processing of heavier crudes, emul-
sions can be extremely stable and separation may progress too
slowly, which results in a thick interface or rag layer between
the oil and water phases. If emulsion formation is excessive,
operators often struggle to deal with it. The typical response is
to add more demulsifiers, change mixing valve settings and
reduce wash water flow. This can cause several upsets. A typical
one is desalter grid overload which manifests as a voltage drop,
an increase in current and finally, desalter shut down. In turn,
this leads to massive water over-carry with all its consequences
and to severe oil under-carry which puts an unacceptable load
on effluent treatment facilities.
pH control
Often ignored in the desalting process is pH control, but it is
important for a number of reasons:
• The crude contains different organic acids or acid forming
salts. These are major causes of corrosion in the crude tower,
the overhead condenser tubing and in the desalter itself. Caus-
tic is usually fed to the desalter to neutralize the acidity.
• Often, ex-sour water stripper water is used to wash the crude in
the desalter. This water may already have a low pH (< pH 5.5)
and cause corrosion.
• If the pH is too high (> pH 8), organic acids such as naph-
thenic acid in the crude ionize and produce soaps that form
unbreakable oil/water emulsions.
• There is also the strong influence of the pH value on the speed
of demulsifying and phase separation. This has to do with an
electrokinetic property, the so called zeta “z” potential.
z-potential
In suspensions and emulsions, particles or emulsion droplets
are usually electrically charged. The charge at the droplet sur-
face affects the distribution of ions or charges in the direct
proximity of the droplet. It will attract counter ions or particles
with the opposite charge, which form a double layer around the
droplet: a bound layer attached to the droplet, and a diffuse
layer which decays in concentration as distance from the droplet
increases. Within the diffuse layer a shear plane can be distin-
guished where, when a droplet moves, charges on the inner side
of the diffuse layer stay bound with the droplet. Charges on the
outer side of the diffuse layer remain with the bulk liquid. The
electrical potential at the shear plane in the diffuse layer is
called the ζz-potential.
pH Control in Crude Desalting

The magnitude of the ζz-potential is a measure of the stability
of the emulsion. When the droplets have a large ζz-potential they
will repel each other and the emulsion remains stable. With a
low ζz-potential London-van der Waals forces become effective
and the droplets aggregate and flocculate. Pronounced coagula-
tion occurs when the z-potential equals zero. Probably the most
important factor affecting the surface charge and the ζz-
potential is the pH value. Depending on the charge of the drop-
lets, increasing or decreasing the pH of the emulsion by
adding alkali or acid alters the charge of the droplets,
forcing them towards the isoelectric point where the
charge is zero.
Engineers who have experienced this problem before may not
even install a pH measurement system into a new desalter.
As the pH measurement is often false, or totally absent, this
regularly leads to uncontrolled chemical dosing of, in the main,
caustic. This in itself is costly as the caustic is typically over-
dosed, but also it inhibits proper oil/water separation with all of
its aforementioned consequences.
Bound layer
+
+
– – Diffuse layer

pH control has economic advantages over the use of + – +

+
surfactants, demulsifiers and corrosion inhibitors, as + –
+ –
acids and alkali are much cheaper. Also, less oil is lost – + + +
through under-carry. Process conditions however, are + + +
+ + –
such that pH measurement is very difficult. –
+ –
+ + +
Instrumentation –
+ + –
+ +
Due to the continuously changing process conditions
+ + +
in the desalter, measuring pH by grab sampling does –
–
not really make sense. By the time the results of the –
+
analysis are available, the data will no longer apply to + – Shear plane

the current situation. In-situ measurement of process

pH is the only correct method. It gives a real-time de-
Distribution of ions around particle/droplet
termination and allows for direct process control. How-
ever, the oily conditions, the high temperatures and the
presence of substantial quantities of sulfides cause Bound layer Diffuse layer

most traditional pH probes to fail within a very

short time. mV Surface potential

The causes of failure in most cases are clogging of the Shear plane
sensor reference diaphragm and poisoning of the refer-
ence electrode. It is the presence of crude oil and par-
ticles that rapidly clogs the pores in the diaphragm on Electrostatic
potential
the reference side of the sensor. Poisoning occurs when Zeta potential

sulfides diffuse through the diaphragm and react with

the internal silver/silver chloride reference electrode.
Both events cause a shift of the electrical potential
between the pH electrode and the reference electrode
and have a direct impact on the measured pH value.
The result is a false pH measurement. Therefore, in 0
Distance from droplet surface
practice, the pH measurement is often discarded.
Charge as a function of distance

White Paper METTLER TOLEDO 3

pH Control in Crude Desalting
Electrodes fit for purpose
The InPro 4800i pH electrode with PTFE annular reference dia-
phragm is METTLER TOLEDO’s answer to the toughest refinery
applications. This highly robust electrode has a proven track
record in desalter service. It resists fouling caused by oily hydro-
carbon contaminants and its long helix diffusion path provides
an excellent barrier against poisoning from sulfides, guarantee-
ing high accuracy and fast response throughout many months
of operation. It is designed to operate under high pressures and
batch process temperatures. Featuring Intelligent Senor Man-
agement technology, the sensor provides full diagnostics that
advise when maintenance is needed or when replacement is
required.
ISM
Intelligent Sensor Management (ISM) is a revolutionary plat-
form based on electrodes with embedded digital technology and
sets a new standard in pH management. A circuit board is em-
bedded within the sensor which is powered by and read through
the transmitter. Critical electrode information such as self-iden-
tification, calibration data, time in operation,
and process environment exposure are docu-
mented. The data is utilized to continuously
monitor the condition of the sensor and using this information
recommend appropriate actions based on actual sensor expo-
sure. The adaptive diagnostic information directs maintenance,
thereby reducing downtime and minimizing plant operational
costs (see Diagnostics).
The output signal of the electrode is digital, which guarantees
100 % integrity of the measurement value, even under the tough-
est conditions.
System operation and user benefits of ISM at various stages of
sensor lifecycle include:
• Fast, easy installation
• Ability to pre-calibrate sensors
• Enhanced diagnostics for trouble-shooting
• Dynamic Lifetime Indicator predicts remaining sensor life
• Sensor management software
4 METTLER TOLEDO White Paper
Plug and Measure
Installation of a new pH electrode typically requires calibration
as the first step. This involves bringing pH buffer solutions out to
the field and performing a two-point calibration. This critical
step may need to be conducted outdoors under adverse weather
conditions or when exposed to an uncomfortable and/or hazard-
ous process environment, in addition it is a time consuming
procedure.
One particularly useful ISM function is that electrodes can be
calibrated offline using iSense Asset Suite software via a simple
USB connection to a laptop or desktop computer. This means
electrodes can be pre-calibrated in a convenient, comfortable
environment such as the instrumentation workshop or labora-
tory. Such functionality eliminates the need to carry cleaning
agents and buffer solutions through the plant to do tedious on-
site calibrations. Pre-calibrated sensors carry all configuration
data on an integrated microprocessor and share it with the
transmitter immediately upon connection. This avoids any pos-
sible configuration errors and ensures the electrodes are imme-
diately ready for measuring.
Diagnostics
Advanced diagnostics provide a continuous flow of status and
maintenance information to the transmitter. Along with moni-
toring glass and reference impedance, ISM bases its diagnostics
on actual process exposure history. By constantly keeping track
of process pH value, temperature and operating hours, ISM cal-
culates when sensor calibration, cleaning or replacement is re-
quired. Any maintenance requirement is therefore recognized at
an early stage. All data is easily accessible through the transmit-
ter’s local operator interface. The same data is also available via
HART protocol, on Foundation fieldbus or Profibus networks.
ISM offers true predictive maintenance functionality.
Dynamic Lifetime Indicator
In the end, even the toughest pH electrodes will
show signs of wear and tear. A major advantage DLI
Dynamic Lifetime Indicator
A
Ad
of ISM is sensor lifetime monitoring. The ability
to accurately forecast a sensor’s remaining lifetime, decreases
ment and minimizes unexpected process shutdown due
TTM
maintenance costs associated with unnecessary sensor replace-
Timeto sensor
to Maintenance
C
C
failure.
pH Control in Crude Desalting

Exposure to aggressive process conditions directly impacts the Conclusion

lifetime of a chemical sensor. High, and very low pH values ad-
versely affect pH electrodes, as do elevated temperatures. Since
the pH electrode contains a temperature sensor for compensation
purposes, historical temperature exposure, pH values and other
process conditions can be used to forecast remaining useful life.
Adaptive Calibration Timer
An inadequate desalting operation can have major consequenc-
es in relation to downstream processes in respect of refining the
crude but also in regard to effluent treatment. The importance
of the ζz-potential in desalter emulsion stability is significant, as
the pH level in the desalter has a direct effect on this parameter.
Despite the harsh process conditions, modern process analytics
equipment can be confidently utilized in monitoring desalter pH.
Max. °C
Days of operation

DLI
By continuously monitoring reference im-
pedance, pH glass impedance and temper-
ACT
Adaptive Calibration Timer
Dynamic Lifetime Indicator
MAX
The resulting savings on chemical use, increased speed of desalt-
ing, and subsequent reduction in fouling and corrosion can be
Max. Temperature/ODI

ature exposure, the Adaptive Calibration substantial.

Timer displayed on the transmitter, predicts when calibration is

TTM
Time to Maintenance
CAL
next required in order to maintain measurement reliability.
Calibration History
For more information, go to:
www.mt.com/pro-refining
Transmitter
The corresponding transmitter for the InPro 4800i is the M420,
a two-wire pH analyzer that is fully certified for hazardous area
use which supports HART communication and ISM diagnostics
functionality.

Automated sensor maintenance
In cases of extreme fouling, the EasyClean 400 automatic clean-
ing and calibration system guarantees continuous availability
and maximum reliability of the measurement. Using the
InTrac  777 retractable housing, EasyClean 400 automatically
extracts the pH probe without interrupting the process and with-
out the need for a slipstream. Inside the housing, the probe is
automatically cleaned and subsequently calibrated, after which
it is re-inserted into the process. Even organic solvents can be
used as a cleaning medium. The complete EasyClean 400 system
is certified for use in hazardous areas.

Mettler-Toledo AG www.mt.com/pro
Process Analytics Visit for more information
Im Hackacker 15
CH-8902 Urdorf
Switzerland

© 02/2011