MOISTURE IN HYDROCARBON

STREAMS USING AN ON-LINE ANALYZER

UOP Method 344-87

SCOPE

This method is for determining moisture in gas or liquid hydrocarbon streams with the use of an on-line
analyzer. The method is primarily a summary of available instruments that can be selected. The instrument
and sampling system associated with a UOP process unit is specified by UOP depending on the process unit
and analysis requirements. The actual procedure to be followed is dependent on the specific instrument and
vendor chosen. Moisture concentrations in the range of a few tenths of a ppm to percent (mole or volume)
can be determined.

OUTLINE OF METHOD

An appropriate on-line analyzer is chosen based on the process stream composition, flow rate,
temperature and pressure. Some suppliers of available instrumentation are indicated. The various detectors
discussed include electrolytic, infrared, piezoelectric and thin-film aluminum oxide. The cooled mirror
detector and chromatographic technique are not included. Applicability to gas and/or liquid streams,
operating parameters, interferences and precautionary measures for sampling and calibration are discussed.

APPARATUS

The following list is an extensive but not exhaustive list and, therefore, does not include all available
manufacturers. In addition, the inclusion or exclusion of a particular manufacturer’s equipment should not
be interpreted as either an endorsement or rejection of that manufacturer’s analyzers.

Electrolytic water analyzer, DuPont Process Instruments, Meeco Inc., Beckman Industrial, or equivalent

Infrared water analyzer, Combustion Engineering Inc./Process Analytics, or equivalent

Piezoelectric water analyzer, DuPont Process Instruments, or equivalent

Thin-film aluminum oxide water analyzer, Panametrics, Ondyne, or equivalent

IT IS THE USER’S RESPONSIBILITY TO ESTABLISH APPROPRIATE PRECAUTIONARY PRACTICES AND TO

DETERMINE THE APPLICABILITY OF REGULATORY LIMITATIONS PRIOR TO USE. EFFECTIVE HEALTH AND
SAFETY PRACTICES ARE TO BE FOLLOWED WHEN UTILIZING THIS PROCEDURE. FAILURE TO UTILIZE THIS
PROCEDURE IN THE MANNER PRESCRIBED HEREIN CAN BE HAZARDOUS. MATERIAL SAFETY DATA SHEETS
(MSDS) OR EXPERIMENTAL MATERIAL SAFETY DATA SHEETS (EMSDS) FOR ALL OF THE MATERIALS USED IN
THIS PROCEDURE SHOULD BE REVIEWED FOR SELECTION OF THE APPROPRIATE PERSONAL PROTECTION
EQUIPMENT (PPE).

© COPYRIGHT 1962, 1987 UOP LLC

ALL RIGHTS RESERVED

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SAMPLING

The selection of a sample stream, the sampling technique and the procedure by which the sample
integrity is maintained are critical. Due to its nature, water is readily absorbed and desorbed. Therefore,
great care must be exercised to obtain a representative sample. The analyzer must be located as close as
possible to the sample stream. The analytical sample line should be of 1/8- to 1/4-inch OD tubing. While the
process piping and the first connection to process piping are often carbon steel, the analytical sample line
should be stainless steel. The use of carbon steel, plastic or copper for the analytical sample line should be
avoided. The sample point should be located on the process line in a horizontal, upward angling or vertical
direction; never downward. The analytical sample line must be heat traced and never allowed to fall below
the temperature of the process line. It should be as short as possible, and dead spaces, filters or regulators
upstream of the analytical system are to be avoided, if possible. Flow rates and pressures to the analytical
equipment should be maintained and controlled by by-pass lines and back-pressure regulators. Many of the
manufacturers can supply special sampling systems and can be helpful in their installation.

PROCEDURE

Calibration

The specific calibration procedure used depends on the type of analyzer employed. Instrument
manufacturers may have their own preferred techniques, otherwise, ASTM D 4178 may be appropriate.

Analyzer Descriptions

Electrolytic Water Analyzer

The electrolytic water analyzer works on the principle that the water vapor in a gas stream is
quantitatively absorbed by a thin layer of anhydrous P2O5 that has been sandwiched between two electrodes.
The electrodes have a potential applied to them that is greater than the decomposition potential of water.
Therefore, absorbed water is electrolyzed to oxygen and hydrogen, which allows a current to flow between
the two electrodes. Based on Faraday’s Law, the electrolysis of 0.5 moles of water requires 96,500
coulombs. So, if the flow rate of the sample into the cell is known and the current through the cell can be
determined, the concentration of water can be directly calculated. For convenience, a flow rate of 100 mL
per minute at one atmosphere and 25 C is generally used.

The major limitation to this technique is the precise maintenance of the 100 mL/minute flow rate. Any
variation in the flow rate proportionally affects the result. This equipment operates in the nominal pressure
range of 34-690 kPa gauge (5-100 psig). Higher or lower pressures can be accommodated provided the
appropriate pressure reducers or vacuum pumps are used. The analysis range is generally sub-ppm to 1000-
ppm (volume). Additional, higher ranges are available. Excessive amounts of moisture slow the cell
response and shorten cell life. Also, exceptionally dry atmospheres shorten cell life due to loss of P2O5, but
the cells can be regenerated.

Chemical interferences are as follows: Unsaturated hydrocarbons, except aromatics, can polymerize on
the detector surface and produce incorrect results as well as shorten cell life. Amines and ammonia react
with the P2O5 giving incorrect results. Light alcohols split off water giving high results. Fluorine interferes
with the cell operation while traces of hydrogen fluoride can be tolerated by some cell designs. Chlorine and
hydrogen chloride can be tolerated by the Meeco cell design, but not others. A major interference that has

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plagued these types of detectors has been the presence of oxygen and hydrogen. Molecular oxygen and
hydrogen cause a recombination effect at the electrode giving significantly high results. Meeco, Inc. has
developed a cell design that minimizes this effect and allows compensation to be made for it.

Infrared Water Analyzers

The infrared water analyzer utilizes a single beam, dual wavelength system whereby the wavelengths are
selected by a narrow-band pass filter and detected by a non-selective pyroelectric detector. The two
wavelengths are selected in the following manner: the reference wavelength is selected in the infrared
spectrum of the sample stream where none of the stream components are absorbing. The measuring
wavelength is selected at a wavelength where only water absorbs. The use of a reference wavelength
increases the analyzer stability, because it compensates for background energy changes due to window
fogging and lamp deterioration. The maximum stream pressure is 3450 kPa gauge (500 psig), while the
sample stream temperature must be below the temperature of the sample cell. In addition, it is critical to
maintain constant sample pressure and temperature in the sample cell or inconsistent results will be
obtained.

Advantages of this detector system are: (1) Any slight surface degradation of the cell windows does not
affect the results, and (2) The equipment works equally well for gases as well as liquid samples, provided
material composition and cell design are taken into account.

Disadvantages of this detector are: (1) Because two different wavelengths are being used, any changes in
sample composition require the analyzer to be rezeroed and recalibrated. New band pass filters might need
to be selected to utilize a different portion of the infrared spectrum. (2) Because the analyzer is sample
composition or matrix dependent, it must be zeroed and calibrated using sample containing no water and
with known water concentrations. The lower limit of detection is about 10 ppm.

Piezoelectric Water Analyzer

The piezoelectric water analyzer operates on the following principle: A hygroscopically sensitized
oscillating quartz crystal, sensitized by the application of a coating, is alternately exposed to a “wet” and a
“dried” sample gas stream, at normally, 30-second intervals. During the “wet” interval, moisture is absorbed
by the coating causing the oscillating crystal frequency to change. Following each interval, the frequency of
the vibrating quartz crystal is determined and compared to a sealed local oscillator crystal. Both crystals are
maintained at 60 C, and the difference between the two frequencies is determined. This difference in
frequencies is related to the moisture content of the gas stream through a polynomial expression. The
instrument is calibrated at the factory to read the water content directly.

The instrumental operating parameters are as follows: Either 4 or 7, model dependent, concentration
ranges can be chosen. The lower limit of detection on the most sensitive range is 0.1 volume-ppm. Higher
ranges allow detection up to 9,999 or 99,999 ppm, depending on specific equipment options. The sample
inlet pressure is 207-690 kPa gauge (30-100 psig), while the operating pressure is 103 kPa gauge (15 psig).
The gas flow rate is 250 cm3/min at 103 kPa gauge (15 psig). Either gases or liquids that are fully vaporized
at, or below, 40 C at 206 kPa gauge (30 psig) can be analyzed.

The advantages of this detector, especially compared to electrolytic detectors, are that the detector is
unaffected by molecular hydrogen and oxygen, unsaturated hydrocarbons and organofluorine compounds,
and an optional cell permits the use of the analyzer for streams containing hydrogen sulfide concentrations
as high as 30%. The disadvantages are its cost, its sensitivity to flow rate and the complexity of the
analyzer.

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Interferences of this detector are: Any material that affects the surface of the measuring crystal, other than
water, affects the result. Therefore, glycols, compressor oils and high boiling hydrocarbons produce
incorrect results and reduce cell life. Exposure to excessively high water levels temporarily disables the
detector. Since the analysis is based on a “wet” vs. a “dry” gas stream sample, the water removal must be
accomplished without changing the concentration of any other component. This may be difficult to do in
some cases.

Thin-film Aluminum Oxide Water Analyzer

The detector of the thin-film aluminum oxide water analyzer is a 3-layer sandwich. The first layer is a
base that is made of high purity, 99.99% aluminum. The second layer is a thin film of a special porous
aluminum oxide. The third and outer layer is a thin film of gold. The detector acts like a variable impedance
device. Water vapor passes through the gold film and occupies a portion of the pores of the aluminum
oxide. The presence of water in the pores affects the conductivity of the pores and thereby, the impedance.
The analyzer monitors changes in the impedance of the sensor, which are related to the moisture content of
the gas or liquid stream, through the calibration of the detector.

The instrumental operating parameters are: Either a liquid or gas-phase sample can be analyzed. The
nominal concentration range for a gas at 103 kPa (one atmosphere) is 0.001 to 20,000 volume-ppm, with an
optional special calibration to 200,000 volume-ppm. The sample pressure range is 0.001 to 34,500 kPa
gauge (5 µm to 5,000 psig). The sample temperature range is cyrogenic (special application) to 60 or 70 C
dependent on the probe utilized. The flow rate across the Panametrics probe must be less than 5,000 cm/sec,
linear velocity at 103 kPa (one atmosphere) for a gas, or 5 cm/sec linear velocity, at a density of 1 g/cc for a
liquid.

The advantages of using the thin-film aluminum oxide detector are: A zeroing gas and/or standardizing
apparatus is not needed, because each detector is precalibrated at the factory and the calibration data are
stored in memory. The sensor can be used in either a gas or liquid sample stream. Molecular hydrogen or
oxygen, hydrogen sulfide, mercaptan, sulfides, unsaturated hydrocarbons and some fluorinated compounds
do not interfere.

Disadvantages of this technique include the following: Volume-ppm results for gases require knowledge
of the pressure and temperature of the sample. Otherwise, the result is reported as dew/ice point. If the slope
or break point, for the calibration of the probe change, the factory calibration is no longer valid. The change
may not be detected through the use of a zeroing gas, but can be detected with a calibration gas.
Interpretation of readings for liquid samples depends on the composition, temperature and pressure of the
liquid. Because the probe is measuring or sensing the vapor pressure of water that has diffused through a
gold foil, it is actually determining the fugacity of water vapor in the liquid stream at the measuring
conditions and relating this measurement through Henry’s Law to the concentration of water dissolved in
the liquid stream. Any changes in sample composition, temperature or pressure from those of the probe
calibration will change Henry’s Law constant for that liquid and give incorrect results.

As with other surface effect detectors, the thin-film aluminum oxide detector gives incorrect results if the
sample causes any fouling or alteration of the surface. The presence of species other than water in the
sample stream that can enter the pores of the detector, altering the impedance will produce an interference
in the reading. This surface alteration can be caused, for example, by glycols, acetone, high molecular
weight deposits and materials corrosive to aluminum.

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CALCULATIONS

No calculations are required, since the analyzers are designed to be direct reading, when operated at flow
rates, pressures and temperatures at which the detector was calibrated.

PRECISION

An estimated standard deviation is not reported, since insufficient data are available at present to permit
this calculation with at least 4 degrees of freedom.

TIME FOR ANALYSIS

Time for analysis is dependent on the analyzer used, the sample stream being analyzed and the condition
of the sample stream at the time of analysis. In general, the elapsed time will be less than 0.02 hour and the
labor requirement is 0 hour.

REFERENCE

ASTM Method D 4178, www.astm.org

SUGGESTED SUPPLIERS

Combustion Engineering, Inc., Process Analytics, P.O. Box 831, Lewisburg, WV 24901
E.I. duPont de Nemours and Co., Instrument Systems/Process Instruments, Concord Plaza, Quillen Bldg.,
Wilmington, DE 19898
Meeco, Inc., 250 Titus Ave., P.O. Box 70, Warrington, PA 18976
Ondyne, Inc., P.O. Box 302T, Concord, CA 94524
Panametrics, 221 Crescent Street, Waltham, MA 02254
Beckman Industrial Corp., Process Instruments Div., 2500 Harbor Blvd., Fullerton, CA 92634

344-87