Process Analyzers
D. JOSEPH, Rosemount Analytical, Houston, Texas
Keep liquid analysis invisible in refineries
The hidden heroes of hydrocarbon processing plants are the
liquid analyzers, especially the pH and conductivity loops. Un-
like their flashier cousins in gas analysis, these analyzers operate
behind the scenes to safeguard equipment and prevent down-
time through the prevention of corrosion. Plant operators ig-
nore these invisible workhorses—until they quit operating and
require timely intervention. Operators need to understand that
efficient liquid measurement can optimize effectiveness and re-
duce the chance of failure in a refinery.
Reduce corrosion. Corrosion is the major long-term enemy
for many refinery units, including tail-gas cleanup, crude unit
overhead and cooling towers. The first line of defense against
corrosion is pH measurement and the control which it enables.
In a tail-gas cleanup unit (TGCU), the tail gas is heated in
a reactor to maximize the conversion of sulfide to hydrogen
sulfide (H2S). This hot product gas is then cooled in a heat ex-
changer to produce steam. It is next quenched with water and
then contacted with a selective amine to remove the H2S.
Anywhere you have water and steam, the potential for corro-
sion exists. In this case, maximum removal of the sulfide occurs
at lower temperatures, so the hot gas enters from the bottom
of the tower and recirculating quench water is sprayed from
above. Sulfide compounds tend to accumulate in the quench
water, which increases the suspended solids and drops the pH
of the quench water—a condition that can lead directly to cor-
rosion. To minimize corrosion, the pH of the water should be
maintained between pH 8 and pH 9.
Online process pH feedback is used to control the feedrate
of amines or caustic and to maintain this pH level—obviously
a key function in preventing corrosion. The selection of this
pH sensor, however, is critical to the success of the measure-
ment, because dissolved sulfides and other ions in the quench
water can poison a silver-based reference electrode, resulting
in premature sensor failure. In addition, hard water and sulfur
salts in the quench water produce insoluble coatings that can
plug pH reference junctions. The result can be the need for
replacement of the sensor after only one or two weeks, which
obviously creates a costly maintenance problem. The solution
is to seek out sensors with multiple diffusion barriers to delay
sulfide poisoning of the silver reference. Composite reference
junctions with large surface areas and coating-resistant pore
structures can prevent plugging.
Crude unit. pH measurement plays a vital role in the upper
third of the refinery’s crude tower. This part of the tower pro-
duces light oil with large amounts of water that are dropped
out in the separator vessel. Salt impurities, which are more
soluble in the water than the oil, gather in the distillate (over-
head) and cause the separated water to become highly acidic.
Acidic water causes corrosion on metal process equipment,
particularly the upper part of the crude tower, the overhead
piping, condensers and accumulators. To prevent the cor-
rosion, a sample is drawn at the bottom of the accumulator,
separated, and then measured for pH. Using a proportional
controller, a feed of neutralizing chemical is fed into the over-
head product. A time lag of 15 minutes to 45 minutes between
the neutralizer injection and the measurement of pH at the
sensor is created by the flow system. This can result in slow re-
sponses to large changes and oscillations for periodic changes.
To reduce this effect, the pH is neutralized in two stages. To
neutralize the first 75% to 80% of the acidity, an organic amine
is manually fed into the overhead. Flow-paced control can be
used if flowrates vary. The amine forms a protective coating
on the metal surfaces. Next, the pH is trimmed to within two
units of the desired setpoint (usually between 5.5 and 6.5),
using a proportional control system either from the pH ana-
lyzer or a separate DCS system. Ammonia or other amines are
injected to correct the final 20% to 30% of the acidity.
Cooling tower. A number of different liquid analytical mea-
surements come into play in cooling towers. Cooling towers
work via evaporation of a small quantity of water and heat ex-
change with the air passing through the tower. The evapora-
tion process can lead to scale formation and corrosion in the
heat exchangers. The central analytical measurement in the
tower is contacting conductivity. The concentration of im-
purities in the water is measured by the conductivity sensor.
When the conductivity becomes too high, a conductivity con-
troller opens the blowdown valve, discharges some water and
Amine
Manual valve neutralizer
Reflux tank
Distillation
Accumulator
tower
Cooling water
Water sample
Crude oil
Separator
pH
To drain
FIG. 1. Crude tower pH with two-wire transmitter and pH sensor.
Hydrocarbon Processing | MARCH 201497
 Process Analyzers
causes a demand for makeup water, which dilutes the impuri-
ties. pH analysis also comes into play because most impurities
in the cooling water are alkaline, and they are less soluble at
higher pH values. A small quantity of sulfuric acid is added to
the circulating water to reduce pH and control scale forma-
tion. A general purpose pH sensor is used to monitor the pH
level. In addition, chlorine or oxidation reduction potential
(ORP) sensors may be used in cooling towers for monitoring
the chlorine residual and inhibiting algae growth and slime.
Sour-water stripper. Sour gas and sour water are produced
in any crude processing that involves sulfur. The sulfides must
be removed before the water can be reused or discharged.
Steam stripping is the method that releases the most H2S,
and, therefore, is most frequently used. In addition to the
H2S, other chemicals such as ammonia, phenol and cyanide
can also be present in the water, and may also require removal.
The ideal pH for stripping H2S is below 5, while that for ef-
fective ammonia stripping is above 10. To contain costs, most
plants apply a compromise strategy (rather than two different
strippers) and use a pH of 8 to provide satisfactory removal
of both gases. Ammonia stripping is improved if caustic is
injected at the bottom of the tower, while still allowing H2S
stripping near the top.
The key to this process is the selection of appropriate pH
measurement tools. The temperatures involved in sour-water
stripping are very high, creating a challenge for pH sensors. In
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addition, H2S can poison and plug the reference by precipita-
tion with the silver ion. Ammonia and cyanide can also poison
the reference by forming a complex with the silver ion. The
conditions are so harsh that sour water can degrade pH sen-
sor stability in less than a day—clearly not an acceptable per-
formance standard for any operating refinery. To avoid these
issues, general purpose pH sensors should not be used. These
sensors are usually not designed to withstand thermal stress,
particularly near the tip of the glass electrode. To meet this
thermal challenge, special purpose sensors are being designed
with improved glass technology that allows them to operate
reliably at temperatures over 140°C for months of service. At
the same time, the multiple junction reference electrode design
that isolates the silver electrode from the sulfide ions and am-
monia and cyanide, also contributes significantly to increased
sensor life even under these extremely harsh conditions.
Separator. Wastewater in refineries may contain insoluble oil,
sludge and some soluble components requiring further treat-
ment. Treatment of the wastewater often involves separators
that allow heavier liquids to settle below lighter liquids that
can be skimmed off. While there are a number of measurement
technologies that can distinguish between the oil and water
phases in the separator, the most-cost effective by far is the use
of electrical conductivity. Conductivity analysis is based on the
principle that aqueous solutions are good conductors of elec-
tricity and non-aqueous solutions are not.
To determine the interface between the aqueous and non-
aqueous phases, a conductivity sensor mounted above the
vessel outlet determines a rise in conductivity corresponding
to the aqueous phase. Typically, the conductivity of the “rag”
water layer, adjacent to the organic layer, is very high because
impurities tend to collect there. Since the organic layer will not
conduct, the interface between the high conductivity rag water
and the organic matter is easy to detect. It is a simple matter for
a conductivity transmitter to indicate the increase in conduc-
tivity and open a discharge valve that is then closed when the
conductivity drops back down to zero.
Maintain operation. While new designs have greatly en-
hanced the ability of liquid sensors to withstand the harsh
conditions in a refinery, the operator can further improve both
Sour gas to SRU
Gas flare
Sour water
8.1
Flash drum Tank
Pump around
Stripper cooler
Hydrocarbons NaOH
Process
water or
disposal Stripped Reboiler
Heat
exchanger water
FIG. 2. Sour-water stripper with two-wire transmitter and pH sensor.

efficiency and sensor life through a well-planned maintenance
program. Many new sensors come equipped with built-in sen-
sor diagnostics that can signal impending failure and even pre-
dict when such failure may occur in the future. With the aid
of these diagnostics, plant managers can develop maintenance
schedules that maximize uptime without unnecessary sensor
replacement. In addition, rebuildable or refillable references
that can reduce costs further.
The complete loop. Most liquid analysis problems in refin-
eries result from an incorrect sensor selection or inappropriate
use of sensors. The instrument is required to interface with
the control system and must be compatible with the ambient
environment. Choosing the right instrument can improve the
reliability of the data, the interface with the final control ele-
ment and the communication to the DCS. Plus, such a selec-
tion will aid in the reduction of installation time. Capabilities
such as sensor diagnostics, built-in control and wireless net-
work capability are typical features that can add value to the
liquid analyzer.
Instruments are first selected based on available power, the
environment in which they will be installed, and the network
connectivity requirements. Four-wire transmitters (analyzers)
are generally AC-powered, while two-wire transmitters are
DC-loop powered. Areas of the refinery with hazardous mate-
rials may require intrinsically safe transmitters that are unable
to build up enough power to cause an explosion. Transmitters
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Process Analyzers
that are mounted outside should be rated IP65 or better for
operation even in the harshest environments.
Four-wire analyzers are typically located within control
rooms or in safe areas such as wastewater processing. These an-
alyzers can be extremely sophisticated, multi-parameter instru-
ments with quickstart capabilities, auto recognition of various
types of measurements, color trending displays, USB datalog-
ging, multiple current outputs and alarm contacts for local con-
trol. Despite all these powerful features, simple prompt-based
operation and help screens allow easy training of operators.
Choosing the right liquid instrumentation starts with se-
lecting the right sensor for the job, and then choosing an ana-
lyzer based on power, installation and communication options.
These may include traditional 4-20 mA, HART, digital Field-
bus or wireless. The advent of self-organizing networks has
made wireless operation an excellent choice for environments
where installation of new wiring is not possible or desirable.
Measurement should be straightforward. Operating a
refinery without liquid analysis is like running a car without
enough oil. Keeping liquid measurement analysis straightfor-
ward, efficient and valuable only requires some simple plan-
ning, good choices and informed installation. The results will
be positively invisible.
DAVE JOSEPH is senior industry manager for Rosemount Analytical. He received a
BS degree in chemical engineering from the California Institute of Technology and
an MS degree in chemical engineering at UCLA. He is a member of AIChE.
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