EDXRF APPLICATION NOTE

SULFUR IN CRUDE

SCOPE
The analysis of sulfur in crude oil as per ASTM
D4294 is demonstrated. The performance shown
is applicable to:
 light and heavy crude oils
 residual oil
 bunker fuels

BACKGROUND
Sulfur will always be an important element in crude
oils and fuels oils. Sulfur content is regulated in
many products, and plays an important role in fuel
quality and control of polluting emissions. Around
the world regulations are limiting the amount of
sulfur allowable in diesel fuels, kerosene, heating oils, etc., thus affecting the price and quality of crude oil
based on sulfur content of the crude. Reliably characterizing the sulfur content of crudes ensures proper
quality for the various feedstocks at the refinery, and optimum blending ratios when blending different crudes
to meet a desired sulfur concentration. Monitoring sulfur is also very important when characterizing other
similar oils, like residual oils and bunker fuels. To meet the needs of the industry, Koehler offers EDX1000,
a simple and versatile benchtop EDXRF analyzer for the analysis of sulfur and other elements in crude oil,
petroleum oils and fuels.

INSTRUMENTATION
Model: Koehler EDX1000
X-ray tube: 4 W Ag-anode
Detector: Semiconductor
Sample Type: Crude oil
Film: Mylar
Analysis Time: 100 sec
Environment: Air
Optional: Autosampler

SAMPLE PREPARATION
To measure a sample, gently shake the sample bottle, allow bubbles to settle and fill a 32mm XRF sample
cup 3/4 full (5g).

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LOW RANGE: 0.1 - 1.0% Sulfur

CALIBRATION
An empirical calibration was built using a set of commercially available certified crude oil standards.
Goodness-of-fit is optimized by developing separate calibration methods for different sulfur ranges, if needed.
A summary of the calibration for 0.1 – 1.0 S is shown here, using a measurement time of 100 sec.

Correlation Plot
Element: S Std Error of Est: 0.0028
Units: % Correlation: 0.99995 S
Sample Standard Calculated 1.00
I.D. Value Value
Calculated Value
STD 1 0.10 0.098 0.75
STD 2 0.30 0.304
STD 3 0.50 0.499 0.50
STD 4 0.70 0.698
STD 5 1.00 1.001 0.25

0 0 0.00
1.1 1.1 0.00 0.25 0.50 0.75 1.00
Standard Value

REPEATABILITY
To demonstrate repeatability (precision), the select samples were chosen from the set of calibration
standards. Each sample was measured in static position for ten repeat analyses using a total analysis time
of 100 sec per measurement, with typical results shown below.

Element: S Units: %

Standard Average
Sample ID Std Dev % Relative
Value Value
STD 1 0.10 0.0994 0.001 1.0

STD 3 0.50 0.5035 0.003 0.6

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1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.
HIGH RANGE: 0.5 - 5.0% Sulfur

CALIBRATION
An empirical calibration was built using a set of commercially available certified crude oil standards.
Accuracy is optimized by developing separate calibration methods for different sulfur ranges, if needed. A
summary of the calibration for 0.5 – 5.0 S is shown here, using a measurement time of 100 sec.

Correlation Plot
Element: S Std Error of Est: 0.0151
Units: % Correlation: 0.99995 S
5.00
Sample Standard Calculated
I.D. Value Value
4.00

Calculated Value
STD 6 0.50 0.505
STD 7 1.00 0.994 3.00
STD 8 2.50 2.488
STD 9 3.00 3.011 2.00
STD 10 4.00 4.015
STD 11 5.00 4.988 1.00

0.00
0 0
0.00 1.00 2.00 3.00 4.00 5.00
5.1 5.1
Standard Value

REPEATABILITY
To demonstrate repeatability (precision), the select samples were chosen from the set of calibration
standards. Each sample was measured in static position for ten repeat analyses using a total analysis time
of 100 sec per measurement, with typical results shown below.

Element: S Units: %

Standard Average
Sample ID Std Dev % Relative
Value Value
STD 7 1.00 0.993 0.004 0.4

STD 11 5.00 5.006 0.015 0.3

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1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.
MULTI-ELEMENT VERSATILITY
The EDX1000 is capable of measurement more than just sulfur. Multi-element analysis is important for
detecting crude oil contamination or adulteration by the presence of salt and other chlorine-bearing
compounds. Left undetected, the presence of Cl can bias the S reading high and potentially leave the leave
the presence of Cl unnoticed. EDX1000 has the ability to detect Cl and other elements, and correct for the
presence of Cl so that its presence is noticed and does not bias the S reading.

Sweet crude 0.5% S containing no Cl

Sweet crude oil contaminated with Cl

If unnoticed and uncorrected, the Cl will bias the sulfur reading high

1595 SYCAMORE AVENUE • BOHEMIA, NEW YORK 11716-1796

1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.
TYPICAL DETECTION LIMITS
To determine the Lower Limit of Detection (LLD) using the empirical method, ten repeat analyses of mineral
oil containing no S were measured and the standard deviation calculated. The LLD is then defined as three
times the standard deviation.

S LLD @ 100 sec S LLD @ 600 sec

20 ppm 8 ppm

INTERNATIONAL STANDARD TEST METHODS

The Koehler EDX1000 complies with the following international standards test methods for measuring sulfur
in crude and petroleum oils. Note that by weight 1 ppm = 1 mg/kg.

ASTM
ISO 20847 ISO 8754 IP 496 IP336 JIS K 2541-4
D4294
16 ppm – 5% 30 -500 mg/kg 100 mg/kg – 5% 100 mg/kg – 5% 100 mg/kg – 5% 0.01 – 5%

CONCLUSION
The performance shown here demonstrates the ability of the EDX1000 to yield excellent results for the
measurement of crude oil and other heavy petroleum oils in air, without the need for helium purge. Simple,
modern touch screen interface allows for reliable and efficient measurement protocols, and performance
meets the major international norms shown above.

1595 SYCAMORE AVENUE • BOHEMIA, NEW YORK 11716-1796

1-800-878-9070 (in u.s. only) • TEL: +1 631 589 3800 • FAX: +1 631 589 3815
www.koehlerinstrument.com • Email: sales@koehlerinstrument.com
© 2015 Koehler Instrument Company, Inc.