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COQA Crude Oil Quality Association


Water Measurement in Crude Oil
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Information Updated - October 2, 2003
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Adverse Components Info INTRODUCTION
Contacts and Members The Crude Oil Quality Association established a subcommittee of members who are
Next Meeting experts in the field of water measurement in crude oil. The purpose of the subcommittee
Meeting Archives was to publish a paper outlining the various methods available to measure water in
Subcommittees
crude oil and to provide an overview of some industrial experiences on the
measurement process. General statements on the advantages and disadvantages of
Canadian Crude Oil
each measurement type are also discussed.
Domestic Trading Centers
Education The basic measurement techniques for water in crude oil are:
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Additives Method Test # Comments
Water Measurement Centrifuge (Lab) ASTM D4007 water and sediment results
Mid-Continent Centrifuge (Field) ASTM D96 water and sediment
Round Robin Centrifuge (Field) API Chapter 10.4 water and sediment
Distillation ASTM D4006 water results only
Capline
Karl Fischer ASTM D4928 water results only
Sponsors and Supporters Online Water Devices API draft standard is in the API publication department
Related Links
Search The following observations apply to the accuracy of water measurement methods:

 Procedure: It is critical that the approved, written procedures be followed for


all test methods.
 Methodology: There are many variations of these tests that apply to
substances other than crude oil. These variations should not be used to
measure water in crude oil, as the results may not be correct.
 Reagents and Solvents: The use of proper Karl Fischer Reagent is
important. Premixed solutions are commercially available or 60 parts reagent
can be mixed with 40 parts xylenes for better solubility. Some manufacturers
may use a different reagent mix even though other ratios are not within the
API/ASTM published Standards/Test Methods. The proper use of solvent in
distillation and centrifuge methods is equally important.
 Audit: Auditing of procedures must be done regularly, in lab and field.
Preparation of the reagents and the handling of them are crucial and should
be included in the auditing process.
 Sampling: Sampling procedures are critical to accurate water
measurements, regardless of the water test method used.

CENTRIFUGE
It is generally accepted that the centrifuge methods, both the lab (D4007) and the field
(D96), are not the most accurate. Disparities between the lab and field methods can
occur due to the differing treatment of the solvent used. The centrifuge can only be
validated by adding a known volume of water to the sample and rerunning the test to
verify the procedure. The Karl Fischer and distillation test methods are easily validated
with a quality control sample.

The centrifuge method does generally not pick up emulsified or dissolved water. Using a
de-emulsifying agent before the test is run (as is noted in the written procedures for the
method) can increase the chance of the centrifuge reading more of the water content.
Aging the sample for several days and allowing the water to settle out will also increase
the chances of the centrifuge method detecting more of the water. However, the
additional time spent aging the crude sample is not advantageous for normal operating
time frames.

The inaccuracies of the centrifuge are well documented. In fact the IP (the Institute of
Petroleum of the United Kingdom) has eliminated the centrifuge method from its set of
standards. It should be noted, however, that centrifuge was not in common use in the
UK in recent years. Also, ASTM has withdrawn D96 from its standards. It is important to
note however, that in the US, the centrifuge method will most likely keep its place in the
industry because of speed, prevalence and ease. Additionally, the method yields results
for both sediment and water, an important consideration in domestic crude production
where sediment can vary from batch to batch. API (API Manual of Petroleum
Measurement Standards, Chapter 10.4) does continue to maintain an equivalent
centrifuge method in its manual at present.

DISTILLATION (ASTM D4006)


Water measurement by distillation is a laboratory procedure. Pipelines or refineries
rarely use ASTM D4006 for day to day operations. The major use of D4006 for refineries

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and pipelines is to resolve a dispute when a number cannot be agreed upon between
delivering and receiving parties. Certain customs agencies require D4006, so it is more
commonly used for imported crudes. ASTM D4006 does not provide sediment results.

KARL FISCHER (ASTM D4928)


Karl Fischer titrimetry is a more accurate moisture measurement method utilizing the
quantitative reaction of water with iodine. The method is becoming recognized as the
standard method of water measurement because of its speed and precision. According
to API/ASTM published standards; Karl Fischer is both more precise and faster than
either centrifuge or distillation. Please see Attachment 1 (at the end of this paper).

Similar to distillation, Karl Fischer results do not include sediment. A separate test would
be necessary to determine the amount of sediment in a sample.

Although the equipment necessary to run a Karl Fischer is not, at $5000 per instrument,
individually high priced, it is not prevalent. There is maintenance involved as well; the
solutions must be maintained properly and changed on a frequent basis. QA/QC
operations must be performed to ensure validity of the results. At present, Karl Fischer
is primarily a laboratory procedure. Although a portable Karl Fischer instrument can be
truck mounted, there are inherent handling problems related to the glass components of
the equipment. Also, maintaining the cell in a manner that precludes intrusion of water
from the atmosphere or other sources can create difficulties.

There have been some studies that indicate Karl Fisher may be susceptible to
interference from naturally occurring species in the crude oil. For example, crudes with
high mercaptans tend to be prone to the interference. A methodology to detect the
extent of the possible interference in a particular crude will be presented to ASTM
shortly.

ONLINE WATER DEVICES


The API has written a draft standard on Online Water Measurement Devices (OWD).
The draft standard is in publication.

There are currently at least 25 different models of online measurement available. The
technology for all the manufacturers falls into one of three categories:

Microwave: generally considered the most consistent


needs to be corrected for temperature and density

Capacitor: oldest technology, still evolving


needs to be corrected for temperature and density

Optical: many different wave lengths, different light sources


up and coming technology
consistent

Some COQA member companies (Arco of California, Enbridge Pipeline) use online
devices with variable successes.

SEDIMENT
There are three main ways of measuring sediment in crude oil:

 Extraction ASTM D473


 Filtration ASTM D4807
 Centrifuge API Manual of Petroleum Measurement Standards, Chapter 10.4

Methods to measure sediment quickly are being researched but are not commercially
available yet. When these methods become available, it is expected that there will be
industry acceptance of separate tests for sediment and water.

When sediment levels are significant, accurate measurement is important for all aspects
of the petroleum industry. It is also critical to properly measure sediment when the level
varies significantly from batch to batch

It was noted that foreign crude cargoes brought into the United States sometimes use
the Karl Fischer method for water determination. Sediment by centrifuge is generally
performed for these crude vessels. When that result indicates a possible problem,
extraction or filtration may be performed to pinpoint the sediment number. Sometimes,
parties agree on a sediment number for each crude and it is used for a set period of
time, such as thirty days. After the agreed time passes, a new sediment number is
negotiated. Although that methodology has worked well for foreign crudes, it is

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perceived to have drawbacks for US lease production where sediment levels vary more
frequently.

In US domestic production, the oil is not "settled" into large tanks but is batched through
with little retention time into the pipeline system. The batches can vary considerably in
sediment content, making a fair, negotiated estimate difficult to ascertain. Sediment at
US lease production is unstable and could be significant.

Sediment as it moves through the transportation system in the US is generally not an


issue, unless the amount is significant and operations are affected. Sediment received
at the refinery, however, can cause serious problems. The material causes fouling
throughout the distillation process and can impact product quality.

SUMMARY/CONCLUSIONS
The importance of water measurement is not disputed. In fact, many companies have
observed a trend of increasing water in crude oil. The use of chemicals to enhance
production or restart wells is a possible cause of higher water. While these phenomenon
may be temporary, they occur often enough to emphasize the necessity of consistent
water measurement.

Water in crude oil must be treated before it can be discharged into a receiving body of
water. All oil industry locations operate under stringent discharge permits. The costs of
treating water to a dischargeable level are expensive. Therefore, accurate water
measurement is crucial to determine the proper economics of a crude oil.

There are economic ramifications to both the pipelines transporting the water and to the
refineries receiving it. Pipelines incur operational costs to move water even though
those costs are not necessarily reimbursable. One of the COQA member companies
estimated that in its 1MMBPD refining system, over 400,000 barrels of material were
annually unaccounted for due to centrifuge readings versus Karl Fischer combined with
sediment by extraction numbers. Please see Attachment 2.

ATTACHMENT 2A - VESSEL CHART - View this Document

ATTACHMENT 2B - REFINERY CHART - View this Document

A Karl Fisher test method is also the method of choice when establishing a refining
value for a particular crude. The difference between the Karl Fischer reading and the
centrifuge reading actually utilized in the transaction has economic ramifications.
Although companies establish and utilize refining values in different ways, there is
consensus that water measurement with Karl Fischer accuracy is critical in arriving at
the proper economics.

Water measurement accuracy is open to interpretation in the context of handling the


crude. A custody transfer is different than refining operations. The observation was
made that Karl Fischer tends to yield higher water-only results than a centrifuge water-
and-sediment number. Perhaps Karl Fisher could be used to obtain the most accurate
water measurement with sediment handled separately for refining operations and those
occasions where the sediment could be high. The Karl Fischer / centrifuge correlation is,
however, very crude specific. The crude itself and the way it is handled (the adding of
de-emulsifying agents at the production location, for example) definitely affect the test
results.

The Karl Fischer method appears to have overwhelming advantages with regards to
speed and precision when compared to the other, currently available water
measurements for crude oil. The COQA, dedicated to quality, endorses efforts on the
part of the industry to use Karl Fischer, noting the disadvantages which include costs
and lack of a sediment determination. It is not expected that, with these drawbacks, the
US oil industry will exclusively use Karl Fischer in the near future. However, individually
establishing a bias between centrifuge and Karl Fischer for each crude can help in the
interim with company specific economic and operational decisions. It may be feasible to
use that same relationship, on a macro level, to show economic incentive for a
commitment to Karl Fischer equipment.

A partial listing of technical references can be found in Appendix A. View Appendix A

Attachment 1

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Test Method Time Required Accuracy @


for Test 0.1% Water
Centrifuge Method Reproducibility
ASTM D4007 30 minutes 0.2
Distillation
ASTM D4006 120 minutes 0.11
Karl Fischer
ASTM D 4928 10 minutes 0.02

*Time estimate is for single analysis after stabilization of equipment. The equipment must also
be
cleaned at a frequency based on the crude types analyzed and the number of samples analyzed.

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