8.

39 Oil in or on Water TO RECEIVER

C. P. BLAKELEY (1974, 1982) B. G. LIPTÁK (1995) I. VERHAPPEN (2003)

AT
OIL
Flow Sheet Symbol

Types of Designs: A. Reflected light oil slick detector (on-off)

B. Capacitance: available in probe form for interface detection or in a flow-through
design or in a floating plate configuration for measuring the thickness of oil
C. Ultraviolet (UV)
D. Microwave (radio frequency): available as an interface probe, as a tape-operated
tank profiler, or as an oil in water content detector
E. Conductivity probes for interface detection
F. Nuclear for interface detection

Range: A. Generally from 0–50 ppm to 0–100%

B. Flow-through dual-concentric detector from 5 to 15% water in oil
C. 0–10 ppm to 0–150 ppm oil in water
D. Oil content detectable from 0 to 100%

Inaccuracy: A. Generally from 1 to 5% of full scale

B. The flow-through dual-concentric detector has a sensitivity of about 0.05 to 0.1%
water
C. 0.1 ppm for a 0 to 10 ppm range
D. Interface is detected to 5%; tank profile, to 1% or 3 cm, and water concentration,
to 0.1%

Costs: For capacitance, conductivity, and ultrasonic level probes, see Section 3.3, 3.4, and
3.20; for conductivity analyzers, see Section 8.17.
C. $12,000 to $20,000 for dual-wavelength unit with auto-zero and 0–10 ppm to
0–150 ppm range

Partial List of Suppliers: For capacitance, conductivity, and ultrasonic level probe suppliers, see Sections 3.3,
3.4, and 3.20; for conductivity analyzer suppliers, see section 8.17.

Agar Corp. (D) (www.agarcorp.com)

Bailey Controls Div. (www.abb.com)
Caldon (D) (www.caldon.net)
Delta C Technologies (B) (www.delta-c.com)
Endress+Hauser Instruments (B) (www.endress.com)
Invensys (Foxboro Co.) (B) (www.invensys.com)
FMC Invalco (C) (www.fmcinvalco.com)
Ohmart/Vega (F) (www.ohmart.com)
Phase Dynamics (D) (www.phasedynamics.com)
SeCap (C) (www.sentech.no)
Synetix (F) (www.synetic.com)
Teledyne Analytical Instruments (C) (www.teledyne-ai.com)

INTRODUCTION PROCESS INDUSTRY MEASUREMENTS

The measurement of oil in or on water is an important require- The most common applications of these sensors are for inter-
ment in both industrial and environmental pollution protection face measurements between the layers of oil and water in tanks
related applications. Both applications are discussed in this sec- and pipelines. Conductivity, capacitance, and ultrasonic level
tion, starting with the industrial process applications. probes (Sections 3.3, 3.4, 3.20) and probe or flow-through

1486
© 2003 by Béla Lipták

OUTER
POTTING COMPOUND INNER ELECTRODE ELECTRODE
BODY WELDMENT
OUTER
INSULATING
MIDDLE SLEEVE
INSULATING
SLEEVE
FIG. 8.39a
Dual-concentric capacitance probe for the detection of water in oil.
conductivity analyzers (Section 8.17) are widely used for
detecting such interfaces. To avoid redundancy, these devices
will not be discussed in this section, but other capacitance
and radio-frequency (microwave) types will be covered in
the paragraphs that follow.
In other applications, it is desirable to detect the amount
of oil that is dispersed in a water stream. Ultraviolet analyz-
ers are well suited for the measurement of oil in water and
are discussed in Section 8.61. When the dispersed oil content
increases, float- and displacement-type level sensors
(Sections 3.7 and 3.8) and density detectors (Chapter 6) can
also be considered. A radio-frequency (RF) type oil concen-
tration detector will also be described below.
Capacitance-Type Water-in-Oil Detectors
The capacitance of water is much higher (its dielectric con-
stant is about 80) than that of oil (about 2), so measuring the
dielectric constant is a convenient way to tell them apart. In
addition to conventional capacitance probes, special dual-
concentric designs (Figure 8.39a) are also available to detect
the interface between water and oil in tanks. In addition, flow-
through sensors are also available for in-pipeline applications.
The flow-through version of the dual-concentric electrode
design is illustrated in Figure 8.39b. Here, the electrodes con-
sist of two concentric pipes that are insulated from each other,
thereby forming the capacitor through which the process
stream flows. The flanged spool piece is available in sizes from
2 to 8 in. (50 to 200 mm) and is designed for operation up to
150 PSIG (10.6 bar) and 212°F (100°C). The unit is available
with switching or transmitting (4 to 20 mA) electronics.
The water-in-oil sensor is most often applied for the pur-
pose of setting the maximum amount of water that is allowed
to be present in the oil. When that concentration is reached,
the flow is diverted or other corrective action is taken.
Radio-Frequency (Microwave) Sensors
When a cup containing water and oil is placed in a microwave
oven, the water will heat up, but the oil will not. This is
because shortwave RF energy is absorbed much more effi-
ciently by water than by oil.
© 2003 by Béla Lipták
8.39 Oil in or on Water 1487
OUTER ELECTRODE
INNER ELECTRODE
FIG. 8.39b
Flow-through water-in-oil detector utilizing two concentric capac-
itance electrodes. (Courtesy of Endress+Hauser.)
In a radio-wave detector, the transmitter produces waves
that are of fixed frequency and contain a constant amount of
energy. The more of this energy that is absorbed by the
process fluid (the more water is in the mixture), the lower
will be the voltage at the detector. The advantages of this
design (relative to capacitance systems) include wider range
(0 to 100%), lower sensitivity to buildup, insensitivity to
temperature and salinity variations, and suitability for higher-
temperature operations (up to 450°F, or 232°C).
Rag Layer and Tank Profiler Sensors The radio-wave oil-
in-water sensors are available as probe-type sensors for
water–oil interface control. A typical application is free water
knockout (Figure 8.39c), in which the probe is installed hor-
izontally at an elevation of one-third of the diameter from
the bottom and is set to open the water dump valve when the
emulsion concentration drops below 20% oil (80% water).
This way, the emulsion (rag layer) will build up above the
probe. These instruments can also provide a 4 to 20 mA
transmitted output signal and can detect water concentration
within an error of about 5%.
A portable tank profiler is also available that uses the
same principle of operation. Here, the tape-supported radio-
wave element is gradually lowered into a tank, which can
be up to 100 ft (30 m) tall. As the sensor is lowered, it
measures both the location of the interface (within an error
of 0.12 in., or 3 mm) and the emulsion concentration
throughout the tank height (from 0 to 100% within an error
of 1%) (Figure 8.39d).
Water-in-Oil Probes A water-in-oil monitoring probe is
also available that can detect the water concentration over a
range of 0 to 100% in tanks or pipelines (Figure 8.39e) within
an error of 0.1%. All of these devices are available in
explosion-proof construction and can be provided with digital
displays.
1488 Analytical Instrumentation

OUTPUT VOLTAGE OIL

OUTLET

DETECTOR
OIL
ANTENNA
EMULSION
SAMPLES D

20% OIL 80% WATER

D/3
115 v SAMPLES WATER
TRANSMITTER AIR

OIL/WATER INLET
WATER DUMP

9-18v DIRECT CURRENT

FIG. 8.39c
Radio-wave oil–water interface detector probe. (Courtesy of Agar Corp.)

USE FLEXIBLE CABLE TO

ALLOW FOR MOVEMENT
ELECTRONICS
MODULE
FRONT
THUMBSCREWS

REEL MODULE 4.20 mA O/P

CRANK POWER
1/2" VALVE SUPPLY
(12 mm)
RELAY
READ TAPE SEAL HOUSING

AIR
OIL SURFACE 115/230 VAC OR
INTERMITTENT 2" BALL VALVE 12-24 VDC
SOUND SIGNAL (50 mm)
BEGINS
TANK OR PIPE WALL
% WATER IN OIL
INDICATED ANTENNA
GUARD

OIL/WATER
INTERFACE WATER
SOUND SIGNAL
BECOMES
CONSTANT
FIG. 8.39d
Tape-type tank profiler using radio-wave oil–water sensor. (Cour-
tesy of Agar Corp.)
When applying this technology to measure oil in water,
one must remember that there is a crossover point, at around
80% water concentration, at which the solution changes from
being water continuous to oil continuous. This crossover
results in a discontinuity in the analyzer output. Therefore,
these devices suffer a significant loss in accuracy around this
measurement point. In addition, many of these sensors are
also sensitive to the salinity of the water phase. This can be
corrected through the use of strapping tables, which should
be selected by the user during calibration.
FIG. 8.39e
Water-in-oil concentration can be detected within a 0.1% error.
(Courtesy of Agar Corp.)
Conductivity and Capacitance Sensors
There is a substantial difference between the conductivities
of water and hydrocarbons. This difference is often used as
the basis for detecting the interface between these two fluids.
Vessel profiles can also be estimated by using an array
of self-contained capacitance cells on a common mounting
frame. If the appropriate software is available, the resultant
capacitance profile of the vessel can be used to signal the
multiple interfaces in that vessel to a resolution as good as
1 cm.
Ultrasonic Sensors
As was illustrated in Figure 6.7b, a flow-through ultrasonic
densitometer is available for mounting between a pair of
pipe flanges. It measures and transmits an analog signal

© 2003 by Béla Lipták


FIG. 8.39f
Wafer-type ultrasonic pipeline interface detector. (Courtesy of Caldon, Inc.)
proportional to the density and, hence, the amount of hydro-
carbon in the flowing stream.
By using a number of pipeline interface detectors
(Figure 8.39f), it is possible to use this meter to estimate fluid
viscosity, thus making it useful as an interface detector
between batches of product in a pipeline. The time of passage
of the ultrasonic pulse and the attenuation of the signal are
used to calculate both the density and the viscosity of the
flowing fluid.
The viscosity is calculated from the slight rarefaction and
compaction of molecules in the liquid, which cause viscous
shearing of the fluid that absorbs acoustic energy. Kinematic
fluid viscosity is determined from the energy loss of the
meters’ acoustic pulses as they pass through the fluid.
The analog outputs, which correspond to relative density
and kinematic viscosity, can be used to detect the passing
of an interface between two liquids in a pipeline. This infor-
mation can be used to properly divert the flow into the
correct tank. Relative density is determined by the change
in sound velocity as a function of density and, because the
object of the measurement is to compare the density of water
against that of oil, an estimate of water or oil content can
be made.
Nuclear Sensors
Several companies use the attenuation of gamma radiation to
measure the density of the fluid between a source and detec-
tor, thus allowing a complete vessel profile and hence an
estimation of the composition inside. One manufacturer of
this technology uses an array of fixed sources and detectors,
and others use a matched source and detector moving up and
down in a well to provide a density profile (Figures 8.39g
and 8.39h).
© 2003 by Béla Lipták
8.39 Oil in or on Water 1489
AMPLIFIER
(LOCAL OR REMOTE)
STRIP
SOURCE
20 FT
CELLS
MAX.
FIG. 8.39g
Strip source and cell receivers can be used for tank profiling.
As was the case for the conductivity array, software is
then used to determine the actual interfaces between the
phases. This interface is normally at the inflection point
between two layers of differing densities.
Ultraviolet Oil-in-Water Analyzer
Figure 8.39i illustrates the sampling system of a continuous
oil-in-water analyzer used for the monitoring of steam con-
densate, recycled cooling water, and refinery or offshore drill-
ing effluents.
The UV analyzer used in this system is a single-beam,
dual-wavelength analyzer. This is superior to the single-
wavelength designs, because it is able to compensate for
variations in sample sediment content, turbidity, and algae
concentration, and for window coatings. The cell operates
1490 Analytical Instrumentation

the sample is sent through a high-speed, high-shear homoge-

nizer, which disperses all suspended oil droplets and the oil,
which is adsorbed onto foreign matter so that the sample sent
to the analyzer becomes a uniform and true solution.
Once per hour, the analyzer is automatically rezeroed. In
this mode, the sample water is sent through a filter that
removes all the oil, and, after sparging, it is sent to the
DETECTOR
analyzer. This oil-free zero-reference sample still contains all
SOURCE
the other compounds as contained in the measurement.
CAN INSERT AN
ISOLATING GATE Therefore, it can be used to zero out this background.
SHUT-OFF VALVE
HERE

ENVIRONMENTAL POLLUTION SENSORS

Oil floating on water forms a mechanical barrier between the

FIG. 8.39h
Backscatter-type traversing detector can detect interface levels
while also drawing a specific gravity profile for the tank. (Courtesy
of Ohmart Corp.)
according to Beer’s law [Equation 8.27(1)], which relates oil
concentrations to UV energy absorption by the fixed length
cell. The UV measuring band is centered at 254 nm, and the
readings are sensitive to 0.1 ppm with a range of 0 to 10 ppm
and provide a 90% response in 1 sec.
The instrument is automatically zeroed by the sample
water being sent to both the measurement and the zeroing sides
of the conditioning system. When in the measurement mode,
air and the water. It prevents oxygenation and kills oxygen-
producing vegetation on the banks of streams. By coating the
gills of fish, these materials also prevent breathing and cause
the fish to suffocate. Outfalls from ships and municipal or
industrial waste treatment plants must therefore be monitored
for oil, and oil must be removed to prevent oil-bearing wastes
from entering the receiving waters.
Continuous monitors are available to detect any hydro-
carbons that are floating on the surface of the water. Oil in
the water is equally undesirable, because it contributes to the
biochemical oxygen demand (BOD) and can also be toxic to
aquatic biota, to the fish food in water, and possibly to the
fish themselves.
Optical methods of detection, when used for both types of
contamination, require regular, conscientious maintenance for
continuous and reliable performance. The capacitance approach
used for the monitoring of oil film thickness on the water
appears to require less maintenance but is limited to detection
of floating oil. Each application must be evaluated separately,
because presently available sensors have limited capabilities.

DEAERATOR
UTILITY SV SV
M
WATER 4 5

20PSIG
OVER- AIR
SAMPLE PURGE
FLOW DRAIN
WATER VALVE
VALVE SV
3 UV
HOMOGENIZER
SAMPLE CELL

SAMPLE
VALVE PUMP
DRAIN
20PSIG
AIR

SV ZEROING
SV 2 VALVE
3 MICRON
OIL
REMOVAL
FILTER
FILTER SPARGER
VALVE

FIG. 8.39i
Ultraviolet oil-in-water analyzer with automatic-zero feature. (Courtesy of Teledyne Analytical Instruments.)

© 2003 by Béla Lipták

 8.39 Oil in or on Water 1491

On-Off Oil-on-Water Detector where

A = effective area of one capacitor plate
The nephelometer is intended to detect visible oil (hydrocar- t = thickness
bon) slicks that are floating on fresh or salt water. It consists
ε = dielectric constant
of two parts: a sensing head and a controller. The sensing
head is inside an explosion-proof housing, which is supported
Because εoil = 1.9 to 2.1, whereas εwater = 80, Equation
on pontoons or floats in the body of water. An S-shaped baffle
8.39(1) can be simplified by eliminating the second term, as
directs the flowing water past the sensing head.
shown in Equation 8.39(2).
A beam of light is focused through a lens onto the surface
of the water. A second lens refocuses the reflected light onto t
1
a photocell. When there is no oil on the water, only a mini- = oil 8.39(2)
C ε oil A
mum amount of reflection occurs. When floating oil is
present, the reflected light intensity increases substantially.
Thus, the inverse of capacitance is detected as a value
The measurement is based on the differential between
that is proportional to the oil thickness. The circuit generates
the outputs of the reflected light photocell and a reference
a DC signal in proportion to the inverse of capacitance and
photocell, which is measuring the output of the light source
is used for remote transmission. The sensor takes advantage
itself. This instrument can provide an output signal that is
of the large differential in dielectric constants between oil
proportional to the intensity of the reflected light, and it can
and water. It is claimed that it is not confused by the presence
also perform alarm functions.
of emulsified sludge (having a large dielectric constant) or
Care must be taken when using such reflected light mea-
by oily froth, which cannot pass under the float.
surements to block out sunlight and/or other stray light
sources because, if they are allowed to be also reflected, they
Oil-in-Water Detector
will introduce an error (typically on the high side).
When UV radiation is sent through an oil-contaminated water
Continuous Oil-on-Water Detector Sensors similar to that sample stream at a peak intensity of 365 nm, visible radiation
deployed in the on-off detectors are also available to estimate is emitted. The intensity of this radiation can be measured
the amount of oil floating on the water. The difference between by a photocell. The intensity of this radiation increases as
the two applications is that, in this case, the Lambert–Beer the concentration of the fluorescent substance rises. At low
–6
law [Equation 8.27(1)] is used to determine the concentration concentrations (below 15 × 10 ), the relationship between
from the detected light intensity. concentration and the visible radiation is essentially linear.
In higher concentrations, some nonlinearity is experienced
Oil-Thickness-on-Water Detector as a result of a saturation effect.
The most common configuration is to pass the process
The previously described devices detect the presence or
sample through the sensing head in an upflow direction
absence of oil floating on the water. This device permits the
(Figure 8.39k). The head is equipped with two windows that
measurement of the thickness of the oil layer. The detector
are set at right angles to each other so as to minimize the
consists of a floating sensing head that is connected by a
intensity of direct radiation from the source striking the pho-
shielded cable to a remote controller. The sensor measures
tocell and also to reduce the effect of multiple scattering of
the thickness of the oil layer on the water by capacitance
the visible radiation. Optical filters at the incident and at the
measurement (Figure 8.39j).
The operating principle is that of a series capacitor. The
formula given is in Equation 8.39(1). SAMPLE OUT

1 t t t
= = oil + water 8.39(1)
C εA ε oil A ε water A
WINDOW WINDOW

∋ t OIL
OIL OUTPUT PHOTOCELL
SIGNAL UV
INVERSE
PROPORTIONAL SOURCE
CAPACITANCE
∋ MEASURING TO OIL
WATER t WATER CIRCUIT THICKNESS

SAMPLE IN

FIG. 8.39j FIG. 8.39k

Parallel-plate capacitor detecting the thickness of an oil layer on water. Oil-in-water detector.

© 2003 by Béla Lipták

1492 Analytical Instrumentation
SAMPLE IN
SHAPING
ORIFICE
UV SOURCE PHOTOCELL
TO WASTE
FIG 8.39l
Falling-stream oil-in-water detector.
emergent windows are used (not shown) to reduce this effect
to a negligible level.
For the detection of oil concentration in water, a falling-
stream type of detector is also available. In this device, the
sample stream is shaped into a rectangle (Figure 8.39l) as it
falls through the viewing field of the ultraviolet beam and
the photocell. Efficient optical filtration is important to over-
come the unavoidable effects of direct reflection of incident
radiation from the surface of the shaped stream.
CONCLUSIONS
The on-off oil-on-water detector is capable of measuring as
little as a few drops of petroleum floating on the surface of
water, thus making it possible to detect those oil pollution
levels that are visible to the human eye. It therefore serves
a useful purpose as an alarm device downstream of plant
outfalls and especially during and immediately after oil load-
ing and unloading operations from tankers and tank trucks.
This device presents the maintenance problems usually asso-
ciated with optical measurements, which is that windows
must be kept clean. The air column between the water sur-
face and the window does reduce fouling due to splashing,
but window cleanliness must be maintained for maximum
sensitivity.
© 2003 by Béla Lipták
The oil-thickness device (Figure 8.39j), being nonoptical,
requires less maintenance. Because both devices can detect
the absence or presence of oil slicks, they might also find
application as oil spill monitors after oil transfer operations.
Floating on the surface of wastewater storage sumps or
lagoons, the output of the oil thickness monitor can be used
to start and stop oil reclamation equipment. These devices
cannot be calibrated for a specific oil fraction, but just respond
to any floating hydrocarbon.
The oil-in-water devices are optical, and even the falling-
stream types require clean windows, although they are less
subject to fouling than the sample chamber types. They must
be calibrated for a specific type of oil, and other oil fractions
will introduce errors. They were originally developed to mon-
itor engine oil contamination in boiler feed water and con-
densate, which can be introduced by steam-driven feed water
pumps.
These devices detect the presence of a specific hydrocar-
bon fraction in well segregated waste streams. Where particle
size is expected to exceed 5 µm, sample preparation prior to
the UV analysis is necessary. Use of a high-shear mixer such
as a blender has been found to produce a well dispersed
suspension suitable for measurement.
Reference
Zanker, K. J., Radio-frequency interface detector, Oil & Gas J., January
30, 1984.
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Adams, V., Water and Wastewater Examination Manual, Lewis, Chelsea,
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Arashmid, M. et al., Analysis of the Phase Inversion Characteristics of
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Arnold, K. E., Design concepts for offshore produced water treating and
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Basrawi, Y., Oil-water sampling & monitoring devices, their application to
custody transfer, 47th Analysis Division Spring Symposium 2002,
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Casamata, G. et al., Hydrocarbon separation through a liquid water mem-
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Crawford, H. M., Monitors detect oil in water, API Division of Refining
Conference, Houston, May 1966.
Jones, K. W., An optical sensor for the food/water interface in a process
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