Petroleum products - Determination of low concentration of sulfur in automotive fuels - Energy-dispersive X-ray fluorescence spectrometric method (ISO 13032:2012)

This European Standard specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the determination of the sulfur content of automotive gasolines, including those containing up to 5 % (m/m) oxygen, and of automotive diesel fuels, including those containing up to 10 % (V/V) fatty acid methylester (FAME), having sulfur contents in the range 2 mg/kg to 50 mg/kg.
Other products may be analysed and other sulfur contents may be determined according to this test method, however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this standard. For reasons of spectral overlap, this standard is not applicable to leaded automotive gasolines, lead replacement gasolines containing greater than 8 mg/kg lead, or to products and feedstocks containing lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.

Mineralölerzeugnisse - Bestimmung niedriger Schwefelgehalte in Kraftstoffen - Energiedispersives Röntgenfluoreszenzspektrometrieverfahren (ISO 13032:2012)

Diese Internationale Norm legt ein energiedispersives Röntgenfluoreszenzverfahren (edRFA) zur Bestimmung des Schwefelgehaltes im Bereich von 8 mg/kg bis 50 mg/kg in Ottokraftstoffen mit einem Sauerstoffgehalt von bis zu 3,7 % (m/m) (einschließlich von bis zu 10 % (V/V) Ethanol), sowie in Dieselkraftstoffen mit bis zu 10 % (V/V) Fettsäure-Methylester (FAME) fest. Andere Produkte auch mit anderen Schwefelgehalten können mit diesem Prüfverfahren ebenfalls untersucht werden; jedoch sind für andere als die hier genannten Kraftstoffe und Bereiche für den Schwefelgehalt keine Präzisionsangaben ermittelt worden. Wegen spektraler Überlagerungen ist das hier festgelegte Prüfverfahren nicht auf verbleite Ottokraftstoffe oder für Bleiersatzkraftstoffe mit Bleigehalten von mehr als 8 mg/kg einsetzbar. Das Prüfverfahren ist ebenfalls nicht auf Produkte oder Rohmaterialien anwendbar, die für die Elemente Blei, Silizium, Phosphor, Calcium, Kalium oder Halogenverbindungen Gehalte von mehr als 1/10 des gemessenen Schwefelgehaltes, oder aber mehr als 10 mg/kg aufweisen. ANMERKUNG Für die Zwecke dieser Internationalen Norm wird zur Angabe des Massenanteils einer Substanz der Ausdruck „% (m/m)“ und für den Volumenanteil einer Substanz der Ausdruck „% (V/V)“ verwendet.

Produits pétroliers - Détermination de la teneur en soufre en faible concentration dans les carburants pour automobiles - Méthode spectrométrique de fluorescence de rayons X dispersive en énergie (ISO 13032:2012)

L'ISO 13032:2012 spécifie une méthode d'essai par fluorescence de rayons X dispersive en énergie (FXDE) pour le dosage du soufre dans l'essence pour automobiles contenant jusqu'à 3,7 % (m/m) d'oxygène [y compris celle contenant de l'éthanol jusqu'à 10 % (V/V)], et dans les carburants diesels [y compris ceux contenant jusqu'à 10 % (V/V) d'esters méthyliques d'acide gras (EMAG)] ayant des teneurs en soufre comprises entre 8 mg/kg et 50 mg/kg.
D'autres produits peuvent être analysés et d'autres teneurs en soufre peuvent être déterminées suivant cette méthode; cependant, il n'a pas été établi de données de fidélité pour des produits autres que les carburants pour automobiles et pour des résultats en dehors du domaine spécifié pour l'ISO 13032:2012.
En raison de recouvrements spectraux, l'ISO 13032:2012 n'est pas applicable à l'essence pour automobiles contenant du plomb, ni à l'essence contenant un substitut de plomb dont la teneur en plomb est supérieure à 8 mg/kg, ni aux produits et charges contenant du plomb, du silicium, du phosphore, du calcium, du potassium ou des halogénures à des concentrations qui dépassent le dixième de la teneur en soufre mesurée, ou plus de 10 mg/kg, en choisissant la plus grande de ces valeurs.

Naftni proizvodi - Določevanje nizke koncentracije žvepla v gorivih za motorna vozila - Metoda z energijsko-disperzivno rentgensko fluorescenčno spektrometrijo (ISO 13032:2012)

Ta evropski standard določa preskusno metodo z energijsko-disperzivno rentgensko fluorescenčno spektrometrijo (EDXRF) za določanje vsebnosti žvepla v gorivih za motorna vozila, vključno s tistimi, ki vsebujejo do 5 % (m/m) kisika, in v dizelskih gorivih za motorna vozila, vključno s tistimi, ki vsebujejo do 10 % (V/V) metilnih estrov maščobnih kislin (FAME) in od 2 do 50 mg/kg žvepla.
Ta preskusna metoda se lahko uporablja za analizo drugih izdelkov in vsebnosti žvepla v drugih izdelkih, vendar za ta standard niso bili določeni podatki o natančnosti za izdelke, ki niso goriva za motorna vozila, in za rezultate zunaj določenega obsega. Zaradi prekrivanja spektra se ta standard ne uporablja za osvinčeni motorni bencin, bencin z nadomestkom svinca, ki vsebuje več kot 8 mg/kg svinca, ali za izdelke in surovine, ki vsebujejo svinec, silicij, fosfor, kalcij, kalij ali halide, katerih koncentracija je večja od ene desetine izmerjene koncentracije žvepla ali večja od 10 mg/kg, pri čemer se upošteva večja vrednost.

General Information

Status
Published
Publication Date
29-Feb-2012
Current Stage
6060 - Definitive text made available (DAV) - Publishing
Due Date
01-Mar-2012
Completion Date
01-Mar-2012

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SLOVENSKI STANDARD
SIST EN ISO 13032:2012
01-maj-2012
1DIWQLSURL]YRGL'RORþHYDQMHQL]NHNRQFHQWUDFLMHåYHSODYJRULYLK]DPRWRUQD
YR]LOD0HWRGD]HQHUJLMVNRGLVSHU]LYQRUHQWJHQVNRIOXRUHVFHQþQRVSHNWURPHWULMR
,62

Petroleum products - Determination of low concentration of sulfur in automotive fuels -

Energy-dispersive X-ray fluorescence spectrometric method (ISO 13032:2012)
Mineralölerzeugnisse - Bestimmung niedriger Schwefelgehalte in Kraftstoffen -
Energiedispersives Röntgenfluoreszenzspektrometrieverfahren (ISO 13032:2012)

Produits pétroliers - Détermination de la teneur en soufre en faible concentration dans

les carburants pour automobiles - Méthode spectrométrique de fluorescence de rayons X

dispersive en énergie (ISO 13032:2012)
Ta slovenski standard je istoveten z: EN ISO 13032:2012
ICS:
75.160.20 7HNRþDJRULYD Liquid fuels
SIST EN ISO 13032:2012 en

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN ISO 13032:2012
---------------------- Page: 2 ----------------------
SIST EN ISO 13032:2012
EUROPEAN STANDARD
EN ISO 13032
NORME EUROPÉENNE
EUROPÄISCHE NORM
March 2012
ICS 75.160.20
English Version
Petroleum products - Determination of low concentration of
sulfur in automotive fuels - Energy-dispersive X-ray fluorescence
spectrometric method (ISO 13032:2012)

Produits pétroliers - Détermination de la teneur en soufre Mineralölerzeugnisse - Bestimmung niedriger

en faible concentration dans les carburants pour Schwefelgehalte in Kraftstoffen - Energiedispersives

automobiles - Méthode spectrométrique de fluorescence de Röntgenfluoreszenzspektrometrieverfahren (ISO

rayons X dispersive en énergie (ISO 13032:2012) 13032:2012)
This European Standard was approved by CEN on 29 February 2012.

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-CENELEC 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-CENELEC Management Centre has the same

status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, 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, Turkey and United Kingdom.

EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: Avenue Marnix 17, B-1000 Brussels

© 2012 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN ISO 13032:2012: E

worldwide for CEN national Members.
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SIST EN ISO 13032:2012
EN ISO 13032:2012 (E)
Contents Page

Foreword ..............................................................................................................................................................3

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SIST EN ISO 13032:2012
EN ISO 13032:2012 (E)
Foreword

This document (EN ISO 13032:2012) has been prepared by 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, in collaboration with Technical Committee ISO/TC 28 " Petroleum products and

lubricants".

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 September 2012, and conflicting national standards shall be

withdrawn at the latest by September 2012.

Attention is drawn to the possibility that some of the elements of this document may be the subject of patent

rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights.

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, Croatia, 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, Turkey and the United Kingdom.
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SIST EN ISO 13032:2012
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SIST EN ISO 13032:2012
INTERNATIONAL ISO
STANDARD 13032
First edition
2012-03-01
Petroleum products — Determination of
low concentration of sulfur in automotive
fuels — Energy-dispersive X-ray
fluorescence spectrometric method
Produits pétroliers — Détermination de la teneur en soufre en faible
concentration dans les carburants pour automobiles — Méthode
spectrométrique de fluorescence de rayons X dispersive en énergie
Reference number
ISO 13032:2012(E)
ISO 2012
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SIST EN ISO 13032:2012
ISO 13032:2012(E)
COPYRIGHT PROTECTED DOCUMENT
© ISO 2012

All rights reserved. Unless otherwise specified, no part of this publication may be reproduced or utilized in any form or by any means,

electronic or mechanical, including photocopying and microfilm, without permission in writing from either ISO at the address below or ISO’s

member body in the country of the requester.
ISO copyright office
Case postale 56 • CH-1211 Geneva 20
Tel. + 41 22 749 01 11
Fax + 41 22 749 09 47
E-mail copyright@iso.org
Web www.iso.org
Published in Switzerland
ii © ISO 2012 – All rights reserved
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SIST EN ISO 13032:2012
ISO 13032:2012(E)
Contents Page

Foreword ............................................................................................................................................................................iv

Introduction ........................................................................................................................................................................ v

1 Scope ...................................................................................................................................................................... 1

2 Normative references ......................................................................................................................................... 1

3 Principle ................................................................................................................................................................. 1

4 Reagents and materials ..................................................................................................................................... 1

4.1 Diluent oil ............................................................................................................................................................... 1

4.2 Sulfur compounds ............................................................................................................................................... 2

4.3 Reference materials (CRMs) ............................................................................................................................. 2

4.4 Quality control samples ..................................................................................................................................... 2

5 Apparatus .............................................................................................................................................................. 2

5.1 Energy-dispersive X-ray fluorescence instrument ..................................................................................... 2

6 Sampling and sample handling ....................................................................................................................... 3

7 Apparatus preparation ....................................................................................................................................... 4

7.1 Analyser ................................................................................................................................................................. 4

7.2 Sample cups ......................................................................................................................................................... 4

8 Calibration ............................................................................................................................................................. 4

8.1 General ................................................................................................................................................................... 4

8.2 Preparation of primary standards ................................................................................................................... 4

8.3 Calibration standards ......................................................................................................................................... 5

8.4 Calibration procedure ........................................................................................................................................ 6

9 Procedure .............................................................................................................................................................. 7

10 Calculation ............................................................................................................................................................ 7

11 Expression of results ......................................................................................................................................... 7

12 Precision ................................................................................................................................................................ 8

12.1 General ................................................................................................................................................................... 8

12.2 Repeatability, r ...................................................................................................................................................... 8

12.3 Reproducibility, R ................................................................................................................................................ 8

13 Test report ............................................................................................................................................................. 8

Annex A (informative) Matrix effects ............................................................................................................................. 9

Annex B (normative) Guidelines for measuring low sulfur concentrations ..................................................... 11

Bibliography .....................................................................................................................................................................12

© ISO 2012 – All rights reserved iii
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SIST EN ISO 13032:2012
ISO 13032:2012(E)
Foreword

ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies

(ISO member bodies). The work of preparing International Standards is normally carried out through ISO

technical committees. Each member body interested in a subject for which a technical committee has been

established has the right to be represented on that committee. International organizations, governmental and

non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International

Electrotechnical Commission (IEC) on all matters of electrotechnical standardization.

International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2.

The main task of technical committees is to prepare International Standards. Draft International Standards

adopted by the technical committees are circulated to the member bodies for voting. Publication as an

International Standard requires approval by at least 75 % of the member bodies casting a vote.

Attention is drawn to the possibility that some of the elements of this document may be the subject of patent

rights. ISO shall not be held responsible for identifying any or all such patent rights.

ISO 13032 was prepared by the European Committee for Standardization (CEN) Technical Committee

CEN/TC 19, Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological

origin, in collaboration with ISO Technical Committee TC 28, Petroleum products and lubricants, in accordance

with the Agreement on technical cooperation between ISO and CEN (Vienna Agreement).

iv © ISO 2012 – All rights reserved
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SIST EN ISO 13032:2012
ISO 13032:2012(E)
Introduction

This International Standard is directed specifically at the lower end of the concentration range covered in

[2]

ISO 20847 . By selecting the instrument type, a better signal-to-background ratio for sulfur K-L emission is

2,3

assured. A knowledge of the general composition of the sample for analysis is advantageous in obtaining the

best test result.

NOTE IUPAC X-ray line notation (S K-L ) is used in this International Standard; the corresponding Siegbahn X-ray

2,3
line notation (S-Ka) is being phased out.

Where matrix matching is not used and where the C:H mass ratio of the test sample is known or can be

determined, accuracy can be improved by the use of Equation (A.1) (see A.2.3) to correct the result to the

C:H mass ratio of the calibration standards, i.e. the reference diluent oil (see 4.1).

Some instruments include the capability for instrument-based matrix correction; notes on the use of this

approach to compensate for matrix effects in the test sample are provided in A.3 for information.

[3]

This International Standard is based on IP test method PM DU developed by the Energy Institute.

© ISO 2012 – All rights reserved v
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SIST EN ISO 13032:2012
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SIST EN ISO 13032:2012
INTERNATIONAL STANDARD ISO 13032:2012(E)
Petroleum products — Determination of low concentration
of sulfur in automotive fuels — Energy-dispersive X-ray
fluorescence spectrometric method

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

This International Standard specifies an energy dispersive X-ray fluorescence (EDXRF) test method for the

determination of sulfur content in automotive gasoline containing up to 3,7 % (m/m) oxygen [including those

blended with ethanol up to 10 % (V/V)], and in diesel fuels [including those containing up to about 10 % (V/V)

fatty acid methylester (FAME)] having sulfur contents in the range 8 mg/kg to 50 mg/kg.

Other products can be analysed and other sulfur contents can be determined according to this test method;

however, no precision data for products other than automotive fuels and for results outside the specified range

have been established for this International Standard.

For reasons of spectral overlap, this International Standard is not applicable to leaded automotive gasoline,

gasoline having a content of greater than 8 mg/kg lead replacement or to product and feedstock containing

lead, silicon, phosphorus, calcium, potassium or halides at concentrations greater than one tenth of the

concentration of sulfur measured or more than 10 mg/kg, whichever is the greater.

NOTE For the purposes of this International Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the

mass fraction, m, and the volume fraction, f, of a material respectively.
2 Normative references

The following referenced documents are indispensable for the application of this document. For dated

references, only the edition cited applies. For undated references, the latest edition of the referenced document

(including any amendments) applies.
ISO 3170:2004, Petroleum liquids — Manual sampling
ISO 3171:1988, Petroleum liquids — Automatic pipeline sampling
3 Principle

The test portion, in a cup fitted with an X-ray transparent window, is placed in a beam of exciting radiation from

an X-ray tube. The intensity of the sulfur K-L characteristic X-radiation is measured and the accumulated

2,3

count is compared with a calibration curve constructed from sulfur standards covering the range of sulfur

contents under examination.

NOTE The exciting radiation can be either direct or indirect via a polarizing or secondary target.

4 Reagents and materials
4.1 Diluent oil

The reference diluent oil is white oil (light paraffin oil) of high purity grade, with a maximum sulfur content of

0,5 mg/kg. However, if only one type of matrix is to be analysed (e.g. motor gasoline), the accuracy of results

© ISO 2012 – All rights reserved 1
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SIST EN ISO 13032:2012
ISO 13032:2012(E)

may be improved by using a matrix-matched diluent. These should match, approximately, the aromatic and

oxygen contents of the material to be analysed and should consist of high-purity components of less than

0,5 mg/kg sulfur content.

NOTE 1 Suitable components for the matched matrix diluent include n-heptane, 2,2,4-trimethylpentane, toluene,

xylenes, ethanol, methyl tertiary butyl ether (MTBE), ethyl tertiary butyl ether (ETBE) and tertiary amyl methyl ether (TAME).

NOTE 2 For the analysis of diesel fuels containing FAME, the accuracy of results can be improved by use of a matched

matrix diluent oil of the white oil with FAME.
4.2 Sulfur compounds
4.2.1 General

Sulfur compounds of known sulfur content shall be used for the preparation of the primary standards. The

compounds given in 4.2.2 to 4.2.5 are suitable and their nominal sulfur contents are given. Where the purity of

these compounds is less than 99 % (m/m), either the concentrations and nature of all impurities are to be known

or certified reference materials (CRMs) shall be used instead.

4.2.2 Dibenzothiophene (DBT), with a nominal sulfur content of 17,399 % (m/m), or

4.2.3 Dibutylsulfide (DBS), with a nominal sulfur content of 21,915 % (m/m), or

4.2.4 Thionaphthene (Benzothiophene) (TNA), with a nominal sulfur content of 23,890 % (m/m), or

4.2.5 Dibutyldisulfide (DBDS), with a nominal sulfur content of 35,950 % (m/m).
4.3 Reference materials (CRMs)

CRMs from accredited suppliers, containing a range of sulfur concentrations, are suitable alternatives to the

compounds listed in 4.2.2 to 4.2.5 for use as calibration standards.
4.4 Quality control samples

Stable samples representative of the materials being analysed, which have a sulfur content that is known by

this test method over a substantial period of time, or are supplied commercially with a certified value. Ensure,

before use, that the material is within its shelf-life.
5 Apparatus
5.1 Energy-dispersive X-ray fluorescence instrument
5.1.1 Performance characteristics.

For a 10 mg/kg sulfur standard (see 8.3), the instrument shall be capable of meeting the following performance

characteristics:
RR− R ≥ 1,3 (1)
sb b
and
CR() < 5% (2)
V s
where
2 © ISO 2012 – All rights reserved
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SIST EN ISO 13032:2012
ISO 13032:2012(E)

R is the gross count rate (counts per second) for the sulfur region of interest for a 10 mg/kg sulfur

standard;

R is the gross count rate (counts per second) for the same region of interest for a blank sample

[diluent oil (4.1)];

C is the coefficient of variation (relative standard deviation) based on 10 individual measurements of

the calibration standard.

The 10 mg/kg sulfur standard shall be a CRM (4.3) or shall be prepared from one of the compounds given in

4.2.2 to 4.2.5 following the procedures described in Clause 8.

5.1.2 Source of X-ray excitation, with significant flux at X-ray energies above 2,5 keV.

For X-ray detectors with a resolution greater than 200 eV at 2,3 keV, all characteristic X-ray lines originating

from the X-ray tube anode shall have an energy above 3,3 keV to ensure minimal background variation due to

scatter from the X-ray tube anode lines.

5.1.3 Removable sample cup, providing a sample depth of at least 5 mm and equipped with replaceable

X-ray transparent film.

NOTE The transparent film is normally polyester or polycarbonate film with a thickness of between 2 µm and 6 µm.

Polyester film is the preferred choice as samples of very high aromatic content can dissolve polycarbonate film. There are

possibly trace amounts of silicon, calcium and sulfur in some types of film. However, the effects are normally cancelled

out where samples and standards are analysed using the same batch of film. It is important that samples, standards and

blanks be measured using the same batch of film to avoid bias.
5.1.4 X-ray detector, with a resolution not exceeding 800 eV at 2,3 keV.
5.1.5 Means of discriminating between sulfur K-L characteri
...

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