En Iso 14596

IP 447/08 ISO 14596:2007 BS EN ISO 14596 : 2007
BS 2000 : Part 447 : 2007
EUROPEAN STANDARD EN ISO 14596
NORME EUROPÉENNE
EUROPÄISCHE NORM September 2007
ICS 75.080 Supersedes EN ISO 14596:1998
English version
Petroleum products — Determination of sulfur content —

Wavelength-dispersive X-ray fluorescence spectrometry (ISO
14596:2007)
Produits pétroliers — Détermination de la teneur en soufre Mineralölerzeugnisse — Bestimmung des

— Spectrométrie de fluorescence X dispersive en longueur Schwefelgehaltes — Wellenlängendispersive Röntgen-
d'onde (ISO 14596:2007) fluoreszenz-Analyse (ISO 14596:2007)
This European Standard was approved by CEN on 8 September 2007.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions
for giving this European Standard the status of a national standard without any alteration. Up-to-date lists and
bibliographical references concerning such national standards may be obtained on application to the CEN
Management Centre or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other
language made by translation under the responsibility of a CEN member into its own language and notified
to the CEN Management Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic,
Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden,
Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION

COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36 B-1050 Brussels
© 2007 CEN All rights of exploitation in any form and by any means Ref. No. EN ISO 14596:2007 E
reserved worldwide for CEN national Members.
447.1
Issued under licence to 4 Authorised Users within ITS Caleb Brett only
IMPORTANT: This file is subject to a licence agreement issued by the Energy Institute, London, UK. All rights reserved. It may only be used in accordance with
the licence terms and conditions. It must not be forwarded to, or stored or accessed by, any unauthorised user. Enquiries: e: pubs@energyinst.org.uk t: +44 (0)207 467 7100
SULFUR BY WDXRF, IP 447
Foreword
This document (EN ISO 14596:2007) has been prepared by Technical Committee ISO/TC 28 "Petroleum
products and lubricants" in collaboration with Technical Committee CEN/TC 19 "Gaseous and liquid fuels,
lubricants and related products of petroleum, synthetic and biological origin", the secretariat of which is held
by NEN.
This European Standard shall be given the status of a national standard, either by publication of an identical
text or by endorsement, at the latest by March 2008, and conflicting national standards shall be withdrawn
at the latest by March 2008.
This document supersedes EN ISO 14596:1998.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic,
Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden,
Switzerland and the United Kingdom.
Endorsement notice
The text of ISO 14596:2007 has been approved by CEN as a EN ISO 14596:2007 without any modification.
447.2
INTERNATIONAL STANDARD ISO 14596:2007(E)
Petroleum products — Determination of sulfur content —

Wavelength-dispersive X-ray fluorescence spectrometry
WARNING — The use of this International Standard may involve hazardous materials, operations and equipment. This
International Standard does not purport to address all of the safety problems associated with its use. It is the
responsibility of the user of this International Standard to establish appropriate safety and health practices and
determine the applicability of regulatory limitations prior to use.
1 Scope ISO 3170:2004, Petroleum liquids — Manual

sampling
This International Standard specifies a method for
the determination of the sulfur content of liquid ISO 3171:1988, Petroleum liquids — Automatic
petroleum products, additives for petroleum pipeline sampling
products, and semi-solid and solid petroleum
products that are either liquefied by moderate 3 Principle
heating or soluble in organic solvents (see 4.1) of
negligible or accurately known sulfur content. The The test portion and a zirconium solution as internal
method is applicable to products or additives having standard are mixed in a given mass ratio and
sulfur contents in the range 0,001 % (m/m) to exposed, in a sample cell, to the primary radiation of
2,50 % (m/m); higher contents can be determined an X-ray tube.
by appropriate dilution. Other elements do not
interfere at concentrations anticipated in the The count rates of the S-K" at 0,537 3 nm and
materials subject to this analysis. Zr-L"1 at 0,607 0 nm fluorescence thus excited
and the count rate of the background radiation at
NOTE For the purposes of this International Standard, the 0,545 nm are measured and the ratio of these net
term “% (m/m)” is used to represent the mass fraction of count rates calculated. The sulfur content of the
a material. sample is determined from a calibration curve
prepared on the basis of sulfur calibration standards.
High concentrations of phosphorus or chlorine
[typically above 3 % (m/m)] can cause bias in the NOTE The Siegbahn X-ray line notation (S-K") is used in
sulfur result by absorbing Zr-L" and S-K" to this International Standard; the corresponding IUPAC X-
different extents. It is necessary in these cases to ray line notation is S K-L2,3.
carry out studies to determine whether this potential
interference is significant. 4 Reagents and materials
When larger amounts of molybdenum are present 4.1 White oil (light paraffin oil, paraffinum
(typically above 50 mg/kg to 100 mg/kg), increased perliquidum), high-purity grade, sulfur content
background radiation and spectral overlap with the 1 mg/kg maximum.
sulfur signal can occur. It is necessary in these
cases to inspect the relevant spectral regions, for 4.2 Sulfur compounds, of sulfur content
example, to investigate the significance of this accurately known to the nearest 0,01 % (m/m),
potential source of bias. used for the preparation of the primary standards.
2 Normative references The compounds given in 4.2.1 to 4.2.3 are suitable,

and their nominal sulfur contents are given. Where
The following referenced documents are the purity of these compounds is less than 99 %,
indispensable for the application of this document. certified materials are required, or the nature of all
For dated references, only the edition cited applies. impurities and their contents should be accurately
For undated references, the latest edition of the known to the nearest 0,01 % (m/m).
referenced document (including any amendments)
applies.
447.3
4.2.1 Dibenzothiophene (DBT), with a nominal 5.2 Analytical balance, capable of weighing to
sulfur content of 17,399 % (m/m). the nearest 0,1 mg.
4.2.2 Dibutyl sulfide (DBS), with a nominal sulfur 5.3 Homogenizer, non-aerating, high-speed shear
content of 21,915 % (m/m). type, or heatable magnetic stirrer or, for example,
an ultrasonic stirrer.
4.2.3 Thionaphthene (benzothiophene) (TNA), with
a nominal sulfur content of 23,890 % (m/m). 5.4 Flasks, 50 ml capacity, narrow-necked,
conical, made of borosilicate glass and fitted with a
4.3 Certified sulfur reference materials. ground-glass stopper. Use flasks of higher capacity
for stock solutions (7.2).
Use materials from a national standards body or
accredited suppliers, if available. 6 Samples and sampling
4.4 Zirconium solution A. 6.1 Unless otherwise specified, samples shall be
taken in accordance with the procedure described in
Zirconium octoate solution with a zirconium content ISO 3170 or ISO 3171.
in the range of 12 % (m/m) to 18 % (m/m) or
another oil-soluble, sulfur-free zirconium compound 6.2 Test portions from the samples shall be
dissolved in white oil (4.1) to provide a zirconium drawn after thorough mixing and subdivision. Heat
mass fraction in the range of 12 % (m/m) to viscous samples to a temperature that renders the
18 % (m/m). sample liquid and homogenize, using the
homogenizer (5.3) as necessary.
4.5 Zirconium solution B.
NOTE For the purpose of this procedure, the term
Dissolve the zirconium solution A (4.4) with white “sample” also includes solutions prepared from additives,
oil (4.1) to provide a zirconium mass fraction of semisolid or solid petroleum products that have been
approximately 1 % (m/m). appropriately pre-treated and/or diluted.
5 Apparatus 7 Calibration solutions
5.1 Wavelength-dispersive X-ray fluorescence 7.1 General

(WDXRF) spectrometer, consisting of any suitable
spectrometer that incorporates the design features Use either certified reference materials (4.3) or
listed in Table 1. It shall be set up according to the primary standards prepared from sulfur compounds
manufacturer's instructions. (4.2) dissolved in white oil (4.1) as a basis for the
preparation of the appropriate range of sulfur stock
solutions.
Table 1 — General requirements of spectrometer
Component Requirement
Anode Rhodium, scandium or chromium target
a
Voltage 30 kV to 50 kV
a
Current 30 mA to 70 mA
Collimator Coarse
Analysing crystal Germanium, pentaerythritol, or graphite
Optical path Helium
Cell window Polyester or polypropylene film, sulfur-free, thickness 2 :m to 6 :m
Detector Gas-flow proportional counter with a pulse-height analyser
a
A lower-power system may be used, provided that it has been validated to meet the requirements specified in
8.3 and Clause 12.
447.4
7.2 Preparation of stock solutions weigh to the nearest 0,1 mg. Calculate the sulfur
content, wS,3, of the standard solution to the nearest
Weigh, to the nearest 0,1 mg, a quantity of sulfur 0,001 % (m/m), using Equation (2):
compound (4.2) or certified reference material (4.3)
to prepare stock solutions of approximately (m2 − m1 ) w S ,2
2,50 % (m/m) and 0,10 % (m/m) sulfur content, w S ,3 = (2)
calculated to the nearest 0,001 % (m/m), and m3 − m1
dissolve in white oil (4.1) at room temperature. Mix
the contents thoroughly using a homogenizer (5.3). where
The approximate quantities of sulfur compounds m1 is the mass of the flask, expressed in
(4.2) for addition to 100 g of white oil (4.1) to grams;
prepare the stock solutions are as follows: m2 is the mass of the flask plus stock solution,
expressed in grams;
— DBT (4.2.1): 16,75 g [2,5 % (m/m)] and m3 is the mass of the flask plus stock solution
0,5 g [0,1 % (m/m)] plus white oil, expressed in grams;
wS,2 is the sulfur content of the stock solution,
— DBS (4.2.2): 12,85 g [2,5 % (m/m)] and expressed as a percentage by mass.
0,45 g [0,1 % (m/m)]
7.3.2 Low range [0,001 0 % (m/m) to 0,1 %
— TNA (4.2.3): 11,65 g [2,5 % (m/m)] and (m/m)]
0,40 g [0,1 % (m/m)]
Prepare standard solutions in the same manner as
It is recommended that a polytetrafluoroethylene or described in 7.3.1 using the 0,1 % (m/m) stock
glass-coated magnetic stirrer and stirring device be solution (7.2) to give standard solutions of
used to mix the contents of the flask. approximately 0,075 % (m/m), 0,05 % (m/m),
0,025 % (m/m), 0,010 % (m/m), 0,005 % (m/m)
Calculate the exact sulfur content, wS,2, as a and 0,001 % (m/m). Calculate the sulfur content to
percentage by mass, to three decimal places, in the nearest 0,000 1 % (m/m) using the Equation
each case from the amounts of white oil and sulfur (2).
compound used as given in Equation (1):
7.4 Preparation of calibration solutions
mC xw S ,1
w S ,2 = (1) 7.4.1 High range [0,1 % (m/m) to 2,5 % (m/m)]
mC + mO
Weigh 20,00 g ± 0,01 g of each of the standard
where solutions (7.3.1) and the two stock solutions (7.2)
into separate flasks (5.4), and add 5,00 g ± 0,01 g
mC is the mass of the sulfur compound, of the zirconium solution A (4.4). Mix thoroughly at
expressed in grams; room temperature (18 °C to 28 °C) using a
wS,1 is the sulfur content of the sulfur homogenizer (5.3).
compound, expressed as a percentage by
mass; 7.4.2 Low range [0,001 0 % (m/m) to 0,1 %
mO is the mass of white oil, expressed in (m/m)]
grams.
Weigh 20,00 g ± 0,01 g of the low sulfur stock
7.3 Preparation of standard solutions solution and each of the standard solutions (7.3.2)
into separate flasks (5.4) and add 2,00 g ± 0,01 g
7.3.1 High range [0,1 % (m/m) to 2,5 % (m/m)] of the zirconium solution B (4.5). Mix thoroughly at
room temperature (18 °C to 28 °C) using a
Into 50 ml flasks (5.4), weigh to the nearest homogenizer (5.3).
0,1 mg, the appropriate quantity of the 2,5 % (m/m)
stock solution (7.2) to produce approximately 25 g 7.5 Storage of standards
of each standard solution of sulfur contents
approximately 2,0 % (m/m), 1,5 % (m/m), 1,0 % Store certified reference standards in accordance
(m/m), 0,7 % (m/m), and 0,4 % (m/m). Add white with the instructions of the certifying organization,
oil (4.1) to make up to approximately 25 g and re- and use within the time frame specified.
447.5
Store standards prepared from white oil and sulfur 8.3 Low-range calibration curve [0,001 0 %
compounds in dark glass-stoppered bottles in a cool (m/m) to 0,1 % (m/m)]
dark place.
Proceed as in 8.2 using the low range calibration
NOTE The stability of prepared standards, under the solutions (7.4.2), and also measure the background
above storage conditions, is at least six months. radiation, IB, at 0,545 nm. As the fluorescence
radiation is diminished by the sample cell window
8 Calibration (see Table 1), a thin film of approximately 2 :m
thickness (polyester) or approximately 4 :m
8.1 General thickness (polypropylene) shall be used for the
calibration solutions and test portions (9.2) of low
After the spectrometer has been set up and checked sulfur content. The setting of the spectrometer shall
(5.1), purge the optical path thoroughly with helium. be such that at least 50 000 counts are counted for
the Zr-L"1 line over the total measurement period.
8.2 High-range calibration curve [0,1 % (m/m) to
2,5 % (m/m)] Calculate the net count ratio, R0, using Equation (5).
To determine the calibration curve, the relevant net
Transfer each of the calibration solutions (7.4.1) to count ratio, R0, is plotted against the corresponding
a sample cell, and in a sequence of increasing sulfur sulfur content of the calibration solution; the
content, place them in the spectrometer for calibration curve shall then be calculated and stored
exposure to the primary radiation. using the linear model according to Equation (6).
The regression calculation may be carried out either
Measure the count rates, IS and IZr, of the excited separately or using the spectrometer calculator.
S-K" (0,537 3 nm) and Zr-L"1 (0,607 0 nm)
fluorescence radiation. IS − IB
R0 = (5)
Calculate the gross count ratio, R, using Equation I Zr − I B
(3). To determine the calibration curve, the relevant
gross count ratio, R, is plotted against the R0 ( x ) = a + bx (6)
corresponding sulfur content of the calibration
solution; the calibration curve shall then be where
calculated and stored using the linear model
according to Equation (4). The regression calculation R0 is the net count ratio for the relevant
may be carried out either separately or using the determination;
spectrometer calculator. IS is the count rate of the S-K" X-ray
fluorescence radiation at 0,537 3 nm;
IS IZr is the count rate of the Zr-L"1 X-ray
R= (3)
I Zr fluorescence radiation at 0,607 0 nm;
IB is the count rate of the background radiation
at 0,545 nm;
R( x ) = a + bx (4) x is the sulfur content of the relevant
calibration solution, expressed as a
where percentage by mass;
a, b are the parameters from the regression
R is the gross count ratio for the relevant calculation;
determination; R0(x) is the net count ratio computed from the
IS is the count rate of the S-K" X-ray regression calculation for the content, x.
IZr is the count rate of the Zr-L"1 X-ray 8.4 Checking
x is the sulfur content of the relevant Prior to a measurement series (calibration and/or
calibration solution, expressed as a measurement), but in any case at least once daily,
percentage by mass; the manufacturer's specifications shall be used to
a, b are the parameters from the regression check that the spectrometer is operating correctly,
calculation; so that an optimum performance and a consistent
R(x) is the gross count ratio computed from the standard of highest possible quality is ensured.
regression calculation for the content, x.
447.6
NOTE 1 Many modern WDXRF systems use drift analysed (see Note in Clause 6) into a flask (5.4)
monitoring and correction to ensure that systems produce and add 2,00 g ± 0,01 g of the zirconium solution
accurate data over long periods of time without the B (4.5). Homogenize thoroughly, with heating if
requirement to recalibrate. necessary, to a maximum temperature of 80 °C.
After cooling to 18 °C to 28 °C, proceed in
Performance checks should be performed on a accordance with 8.3 and calculate the net count
regular basis, since such checks give valuable ratio, R0.
information about the status and stability of the
spectrometer.
10 Calculation
Check the calibration curves regularly. In regular
Read the sulfur content from the calibration curves
use, check at least two points on each calibration
constructed in 8.2 or 8.3. If the sulfur content is
curve by using quality control samples with known
above 2,5 % (m/m), dilute the sample with white oil
sulfur contents not less frequently than every three
(4.1) and repeat the procedure specified in 9.2.
months. Check immediately when using a new
batch of films. If the check result differs by more
NOTE Many modern instruments contain a
than 0,71 of the reproducibility given in this
microprocessor that retains the calibration curve and
International Standard (see 12.2), execute a produces a digital readout.
recalibration.
11 Expression of results
It is recommended that a control chart analysis be
carried out.
Report the sulfur content, as a percentage by mass,
rounded to the nearest 0,000 1 % (m/m) between
9 Procedure 0,001 0 % (m/m) and 0,009 9 % (m/m), to the
nearest 0,000 1 % (m/m) between 0,010 0 % (m/m)
9.1 General and 0,099 9 % (m/m), and to the nearest 0,01 % (m/m)
between 0,10 % (m/m) and 2,50 % (m/m).
For some products, e.g. residual oils, it can be
necessary to deviate from the provisions given in
12 Precision
9.2 and 9.3, that is, to increase the maximum
temperature from 100 °C to 120 °C in order to
12.1 Repeatability
obtain a homogenous sample. In these cases, this
deviation shall be mentioned in the test report
The difference between two test results, obtained
(Clause 13, item e).
by the same operator with the same apparatus
under constant operating conditions on identical test
9.2 Samples with sulfur contents between
material would, in the long run, in the normal and
0,1 % (m/m) and 2,5 % (m/m)
correct operation of the test method, exceed the
values given in Table 2 in only one case in twenty.
Weigh 20,00 g ± 0,01 g of the sample for analysis
(see Note in Clause 6) into a flask (5.4) and add
12.2 Reproducibility
5,00 g ± 0,01 g of the zirconium solution A (4.4).
Homogenize thoroughly, with heating if necessary,
The difference between two single and independent
to a maximum temperature of 80 °C. After cooling
test results, obtained by different operators working
to 18 °C to 28 °C, proceed in accordance with 8.2
in different laboratories on identical test material
and calculate the gross count ratio, R.
would, in the long run, in the normal and correct
operation of the test method, exceed the values
9.3 Samples with sulfur contents between
given in Table 2 in only one case in twenty.
0,001 0 % (m/m) and 0,1 % (m/m)
Weigh 20,00 g ± 0,01 g of the sample to be
447.7
Table 2 — Precision data
Sulfur content Repeatability limit Reproducibility limit

% (m/m)
0,001 0 to 0,002 9 0,000 3 0,000 5
0,003 0 to 0,004 9 0,000 6 0,001 0
0,005 0 to 0,009 9 0,001 0 0,002 0
0,010 0 to 0,029 9 0,002 0,003
0,030 0 to 0,049 9 0,003 0,005
0,050 0 to 0,099 9 0,005 0,010
0,10 to 0,99 0,01 0,02
1,00 to 2,50 0,02 0,04
13 Test report
The test report shall contain at least the following

information:
a) a reference to this International Standard

(ISO 14596:2007);
b) the type and complete identification of the

product tested;
c) the sampling procedure used (see Clause 6);
d) the result of the test (see Clause 11);
e) any deviation, by agreement or otherwise,

from the procedure specified (e.g. see 9.1);
f) the date of the test.
447.8

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IP 447/08 ISO 14596:2007 BS EN ISO 14596 : 2007

BS 2000 : Part 447 : 2007

EUROPEAN STANDARD EN ISO 14596

EUROPÄISCHE NORM September 2007

ICS 75.080 Supersedes EN ISO 14596:1998

Petroleum products — Determination of sulfur content —

Produits pétroliers — Détermination de la teneur en soufre Mineralölerzeugnisse — Bestimmung des

This European Standard was approved by CEN on 8 September 2007.

EUROPEAN COMMITTEE FOR STANDARDIZATION

Management Centre: rue de Stassart, 36 B-1050 Brussels

This document supersedes EN ISO 14596:1998.

Petroleum products — Determination of sulfur content —

1 Scope ISO 3170:2004, Petroleum liquids — Manual

2 Normative references The compounds given in 4.2.1 to 4.2.3 are suitable,

5 Apparatus 7 Calibration solutions

5.1 Wavelength-dispersive X-ray fluorescence 7.1 General

Table 1 — General requirements of spectrometer

Weigh 20,00 g ± 0,01 g of the sample to be

Table 2 — Precision data

Sulfur content Repeatability limit Reproducibility limit

The test report shall contain at least the following

a) a reference to this International Standard

b) the type and complete identification of the

c) the sampling procedure used (see Clause 6);

d) the result of the test (see Clause 11);

e) any deviation, by agreement or otherwise,

f) the date of the test.

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