prEN 15553

Petroleum products and related materials - Determination of hydrocarbon types - Fluorescent indicator adsorption method

This document specifies a fluorescent indicator adsorption method for the determination of hydrocarbon types over the concentration ranges from 5 % (V/V) to 99 % (V/V) aromatic hydrocarbons, 0,3 % (V/V) to 55 % (V/V) olefins, and 1 % (V/V) to 95 % (V/V) saturated hydrocarbons in petroleum fractions that distil below 315 °C. This method can apply to concentrations outside these ranges, but the precision has not been determined.
When samples containing oxygenated blending components are analysed, the hydrocarbon type results can be reported on an oxygenate-free basis or, when the oxygenate content is known, the results can be corrected to a total-sample basis.
This test method is for use with full boiling range products. Cooperative data have established that the precision statement does not apply to petroleum fractions with narrow boiling ranges near the 315 °C limit. Such samples are not eluted properly, and results are erratic.
Samples containing dark-coloured components that interfere with reading the chromatographic bands cannot be analysed.
NOTE 1   The oxygenated blending components methanol, ethanol, tert-butyl methyl ether (MTBE), methyl tert-pentyl ether (TAME) and tert-butyl ethyl ether (ETBE) do not interfere with the determination of hydrocarbon types at concentrations normally found in commercial petroleum blends. These oxygenated compounds are not detected since they elute with the alcohol desorbent. The effects of other oxygenated compounds are individually verified.
NOTE 2   For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction and the volume fraction.
WARNING — The use of this document can involve hazardous materials, operations and equipment. This document does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this document to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.

Mineralölerzeugnisse und verwandte Produkte - Bestimmung der Kohlenwasserstofftypen - Adsorptionsverfahren mit Fluoreszenz-Indikator

Dieses Dokument legt ein Adsorptionsverfahren mit Fluoreszenz-Indikator fest für die Bestimmung der nachfolgend genannten Kohlenwasserstofftypen in Mineralölfraktionen, die unterhalb von 315 °C sieden, und zwar für aromatische Kohlenwasserstoffe im Bereich von 5 % (V/V) bis 99 % (V/V), für olefinische Kohlenwasserstoffe im Bereich von 0,3 % (V/V) bis 55 % (V/V) und für gesättigte Kohlenwasserstoffe im Bereich von 1 % (V/V) bis 95 % (V/V). Das Prüfverfahren kann auch auf Produkte mit Gehalten außerhalb der angegebenen Konzentrationsbereiche angewendet werden, jedoch sind für solche Produkte keine Angaben zur Präzision vorhanden.
Für Proben, die sauerstoffhaltige Verbindungen enthalten, können die Kohlenwasserstofftypen ohne Berücksichtigung der sauerstoffhaltigen Verbindungen (d. h. bezogen auf den sauerstoffverbindungsfreien Probenanteil) angegeben werden, oder aber, wenn der Gehalt an sauerstoffhaltigen Verbindungen bekannt ist, auch nach entsprechender Umrechnung mit Bezug auf die Gesamtprobe.
Dieses Prüfverfahren wird auf Proben angewendet, die den gesamten angegebenen Siedebereich überstreichen. Untersuchungen haben gezeigt, dass die Präzisionsangaben nicht gelten für engsiedende Mineralölfraktionen nahe der angegebenen Grenze von 315 °C. Solche Proben werden nicht ordnungsgemäß eluiert und führen daher zu fehlerhaften Ergebnissen.
Proben, die dunkel gefärbte Komponenten enthalten, welche die Auswertung der chromatographischen Zonen stören, können mit diesem Prüfverfahren nicht untersucht werden.
ANMERKUNG 1   Die sauerstoffhaltigen Blendkomponenten Methanol, Ethanol, tert-Butylmethylether (MTBE), Methyl tert pentylether (TAME, tert-Amylmethylether) und tert-Butylethylether (ETBE) stören mit für kommerzielle Mineralölmischungen üblichen Gehalten die Bestimmung nicht. Diese Blendkomponenten werden nicht erfasst, weil sie zusammen mit dem Laufmittel eluieren. Die Einflüsse anderer sauerstoffhaltiger Verbindungen werden im Einzelfall geprüft.
ANMERKUNG 2   Für die Zwecke dieses Dokuments werden die Bezeichnungen „% (m/m)“ und % „(V/V)“ für den Massenanteil in Prozent bzw. für den Volumenanteil in Prozent angewendet.
WARNUNG — Die Anwendung dieses Dokument kann den Einsatz gefährlicher Stoffe, Arbeitsgänge und Geräte mit sich bringen. Dieses Dokument gibt nicht vor, alle mit ihrer Anwendung verbundenen Sicherheitsprobleme anzusprechen. Der Anwender dieses Dokuments ist dafür verantwortlich, vorher angemessene Maßnahmen zu ergreifen und die Anwendbarkeit einschränkender Vorschriften zu ermitteln.

Produits pétroliers et produits connexes - Détermination des groupes d'hydrocarbures - Méthode par adsorption en présence d'indicateur fluorescent

Le présent document spécifie une méthode d’adsorption en présence d’indicateur fluorescent visant à déterminer les groupes d’hydrocarbures sur des plages de concentration comprises entre 5 % (V/V) et 99 % (V/V) pour les hydrocarbures aromatiques, entre 0,3 % (V/V) et 55 % (V/V) pour les oléfines, et entre 1 % (V/V) et 95 % (V/V) pour les hydrocarbures saturés dans des fractions pétrolières distillant en dessous de 315 ºC. La présente méthode peut être applicable à des concentrations en dehors de ces plages, mais la fidélité n’a pas été déterminée.
Lorsque des échantillons contenant des composés oxygénés sont analysés, les résultats de groupes d’hydrocarbures peuvent être notés sans tenir compte des composés oxygénés ou, lorsque la teneur en oxygénés est connue, les résultats peuvent être corrigés sur la base de l’échantillon total.
La présente méthode d’essai est destinée à être utilisée avec des produits à plage d’ébullition large. Des données communes ont établi que la déclaration de fidélité ne s’applique pas aux fractions de pétrole à plage d’ébullition étroite avoisinant le seuil de 315 °C. Ces échantillons ne sont pas correctement élués, ce qui conduit à des résultats erronés.
Les échantillons qui contiennent des composants de couleur foncée pouvant affecter la lecture des bandes chromatographiques ne peuvent pas être analysés.
NOTE 1   Les composés oxygénés comme le méthanol, l’éthanol, le méthyl tertio-butyl éther (MTBE), le methyl tert-pentyl éther (TAME) et l’éthyl-tertio-butyl éther (ETBE) n’affectent pas la détermination des groupes d’hydrocarbures aux concentrations habituellement trouvées dans les mélanges commerciaux de produits pétroliers disponibles. Ces composés oxygénés ne sont pas détectés puisqu’ils éluent avec l’alcool de désorption. Les effets des autres composés oxygénés sont vérifiés individuellement.
NOTE 2   Pour les besoins du présent document, les termes “% (m/m)” et “% (V/V)” sont utilisés pour représenter respectivement la fraction massique et la fraction volumique.
AVERTISSEMENT — L’utilisation du présent document peut impliquer des produits, opérations et équipements à caractère dangereux. Le présent document n’a pas la prétention d’aborder tous les problèmes de sécurité concernés par son usage. Il est de la responsabilité de l’utilisateur de ce document d’établir des règles de sécurité et d’hygiène appropriées et de déterminer l’applicabilité des restrictions réglementaires avant son utilisation.

Naftni proizvodi in sorodni materiali - Določevanje vrste ogljikovodikov - Adsorpcijska metoda s fluorescenčnim indikatorjem

General Information

• Status: Not Published
• ICS: 75.080 - Petroleum products in general
• ICS: 75.160.20 - Liquid fuels
• Technical Committee: CEN/TC 19 - Petroleum products, lubricants and related products
• Drafting Committee: CEN/TC 19/WG 21 - Specification for unleaded petrol
• Current Stage: 4060 - Closure of enquiry - Enquiry
• Due Date: 01-Jul-2021
• Completion Date: 01-Jul-2021
• Ref Project: oSIST prEN 15553:2021 - Petroleum products and related materials - Determination of hydrocarbon types - Fluorescent indicator adsorption method

RELATIONS

• Revised: EN 15553:2007 - Petroleum products and related materials - Determination of hydrocarbon types - Fluorescent indicator adsorption method
• Effective Date: 30-Dec-2020

Standards Content (sample)

SLOVENSKI STANDARD
oSIST prEN 15553:2021
01-april-2021
Naftni proizvodi in sorodni materiali - Določevanje vrste ogljikovodikov -
Adsorpcijska metoda s fluorescenčnim indikatorjem
Petroleum products and related materials - Determination of hydrocarbon types -
Fluorescent indicator adsorption method
Mineralölerzeugnisse und verwandte Produkte - Bestimmung der
Kohlenwasserstofftypen - Adsorptionsverfahren mit Fluoreszenz-Indikator

Produits pétroliers et produits connexes - Détermination des groupes d'hydrocarbures -

Méthode par adsorption en présence d'indicateur fluorescent
Ta slovenski standard je istoveten z: prEN 15553
ICS:
75.080 Naftni proizvodi na splošno Petroleum products in
general
oSIST prEN 15553:2021 en

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

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oSIST prEN 15553:2021
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oSIST prEN 15553:2021
DRAFT
EUROPEAN STANDARD
prEN 15553
NORME EUROPÉENNE
EUROPÄISCHE NORM
April 2021
ICS 75.160.20 Will supersede EN 15553:2007
English Version
Petroleum products and related materials - Determination
of hydrocarbon types - Fluorescent indicator adsorption
method

Produits pétroliers et produits connexes - Mineralölerzeugnisse und verwandte Produkte -

Détermination des groupes d'hydrocarbures - Méthode Bestimmung der Kohlenwasserstofftypen -

par adsorption en présence d'indicateur fluorescent Adsorptionsverfahren mit Fluoreszenz-Indikator

This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee

CEN/TC 19.

If this draft becomes a European Standard, 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.

This draft European Standard was established by CEN 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, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and

United Kingdom.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are

aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without

notice and shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels

© 2021 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 15553:2021 E

worldwide for CEN national Members.
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prEN 15553:2021 (E)
Contents Page

European foreword ....................................................................................................................................................... 3

1 Scope .................................................................................................................................................................... 4

2 Normative references .................................................................................................................................... 4

3 Terms and definitions ................................................................................................................................... 5

4 Principle ............................................................................................................................................................. 5

5 Reagents and materials ................................................................................................................................. 5

6 Apparatus ........................................................................................................................................................... 6

7 Sampling and sample handling .................................................................................................................. 9

8 Apparatus preparation ................................................................................................................................. 9

9 Procedure........................................................................................................................................................... 9

10 Calculation ...................................................................................................................................................... 12

11 Expression of results ................................................................................................................................... 12

12 Precision .......................................................................................................................................................... 13

12.1 General ............................................................................................................................................................. 13

12.2 Repeatability, r .............................................................................................................................................. 13

12.3 Reproducibility, R ........................................................................................................................................ 13

13 Test report ...................................................................................................................................................... 15

Annex A (normative) Specification for silica gel ............................................................................................ 16

Annex B (informative) Standard adsorption column ................................................................................... 17

B.1 General ............................................................................................................................................................. 17

B.2 Analyser section checking ......................................................................................................................... 18

B.3 Column assembly ......................................................................................................................................... 18

Bibliography ................................................................................................................................................................. 19

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oSIST prEN 15553:2021
prEN 15553:2021 (E)
European foreword

This document (prEN 15553:2021) 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.
This document is currently submitted to the CEN Enquiry.

This document will supersede EN 15553:2007. It is originally based on IP 156/06 [1]. It is intended as

an alternative method to ASTM D1319 [2], which requires a de-pentanization step.

In comparison with the previous edition, the following technical modification has been made:

— lot numbers of the to be used reformulated dyed gel (5.2) that are questionable in their use have

been excluded and clarification of correct references to the gel have been included.

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1 Scope

This document specifies a fluorescent indicator adsorption method for the determination of

hydrocarbon types over the concentration ranges from 5 % (V/V) to 99 % (V/V) aromatic

hydrocarbons, 0,3 % (V/V) to 55 % (V/V) olefins, and 1 % (V/V) to 95 % (V/V) saturated hydrocarbons

in petroleum fractions that distil below 315 °C. This method can apply to concentrations outside these

ranges, but the precision has not been determined.

When samples containing oxygenated blending components are analysed, the hydrocarbon type results

can be reported on an oxygenate-free basis or, when the oxygenate content is known, the results can be

corrected to a total-sample basis.

This test method is for use with full boiling range products. Cooperative data have established that the

precision statement does not apply to petroleum fractions with narrow boiling ranges near the 315 °C

limit. Such samples are not eluted properly, and results are erratic.

Samples containing dark-coloured components that interfere with reading the chromatographic bands

cannot be analysed.

NOTE 1 The oxygenated blending components methanol, ethanol, tert-butyl methyl ether (MTBE), methyl tert-

pentyl ether (TAME) and tert-butyl ethyl ether (ETBE) do not interfere with the determination of hydrocarbon

types at concentrations normally found in commercial petroleum blends. These oxygenated compounds are not

detected since they elute with the alcohol desorbent. The effects of other oxygenated compounds are individually

verified.

NOTE 2 For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent

respectively the mass fraction and the volume fraction.

WARNING — The use of this document can involve hazardous materials, operations and equipment.

This document does not purport to address all of the safety problems associated with its use. It is the

responsibility of the user of this document to establish appropriate safety and health practices and

determine the applicability of regulatory limitations prior to use.
2 Normative references

The following documents are referred to in the text in such a way that some or all of their content

constitutes requirements 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.

EN 1601, Liquid petroleum products - Determination of organic oxygenate compounds and total

organically bound oxygen content in unleaded petrol - Method by gas chromatography (O-FID)

EN 13132, Liquid petroleum products - Unleaded petrol - Determination of organic oxygenate compounds

and total organically bound oxygen content by gas chromatography using column switching

EN ISO 3170, Petroleum liquids - Manual sampling (ISO 3170)
EN ISO 3171, Petroleum liquids - Automatic pipeline sampling (ISO 3171)

EN ISO 3696, Water for analytical laboratory use - Specification and test methods (ISO 3696)

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3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.

ISO and IEC maintain terminological databases for use in standardization at the following addresses:

— ISO Online browsing platform: available at https://www.iso.org/obp
— IEC Electropedia: available at http://www.electropedia.org/
3.1
saturates
volume percentage of alkanes plus cycloalkanes
3.2
olefins
volume percentage of alkenes plus cycloalkenes plus some alkadienes
3.3
aromatics

volume percentage of monocyclic and polycyclic aromatic hydrocarbons plus aromatic olefinic

hydrocarbons, some dienes, compounds containing sulfur and nitrogen, or higher-boiling oxygenated

compounds
4 Principle

Approximately 0,75 ml of sample is introduced into a special glass adsorption column packed with

activated silica gel. A small layer of the silica gel contains a mixture of fluorescent dyes. When all the

sample has been adsorbed onto the gel, alcohol is added to desorb the sample down the column. The

hydrocarbons are separated, according to their adsorption affinities, into aromatics, olefins and

saturates. The fluorescent dyes are also separated selectively with the hydrocarbon types, and render

the boundaries of the aromatic, olefin and saturate zones visible under ultraviolet light. The volume

percentage of each hydrocarbon type is calculated from the length of each zone in the column.

NOTE See NOTE 1 under Clause 1 for aromatics that the described method cannot measure.

5 Reagents and materials

Use only chemicals and reagents of recognized analytical grade and water conforming to grade 3 of

EN ISO 3696.
5.1 Silica gel, manufactured to conform to the specifications given in Annex A.

NOTE 1 Grace Davison silica gel Grade 923 meets the requirements of this specification.

Before use, dry the gel in a shallow vessel at 175 °C for at least 3 h. Transfer the dried gel to an airtight

container while still hot, and protect it from atmospheric moisture.

NOTE 2 Some batches of silica gel that otherwise meet specifications have been found to produce olefin-

boundary fading. The exact reason for this phenomenon is unknown but will affect accuracy and precision.

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5.2 Fluorescent indicator dyed gel, a standard dyed gel, consisting of a mixture of re-crystallized

Petrol red AB4 and purified portions of olefin and aromatic dyes obtained by chromatographic

adsorption following a definite, uniform procedure, and deposited on silica gel .

IMPORTANT — In analysing any sample type by this document, users shall not report results obtained

using any of the following lot numbers of fluorescent indicator dyed gel: 3000000975, 3000000976,

3000000977, 3000000978, 3000000979, and 3000000980, 3000000981, 3000000982. Current

production of batches of the dyed gel will have lot numbers starting with 3000000983.

NOTE Early in 2018, a key component of the dyed gel became unavailable. An alternative dye was

substituted, but the reformulated dyed gel was later found to be unsuitable for the analysis of diesel fuel and

spark-ignition engine fuel. See [4] for further details.
Store the dyed gel in a dark place under an atmosphere of nitrogen.

When stored under these conditions, dyed gel can have a shelf life of at least five years. It is

recommended that portions of the dyed gel be transferred as required to a smaller working vial from

which the dyed gel is routinely taken for analyses.
5.3 Propan-2-ol, 99 %
5.4 3-methylbutan-1-ol, 99 % (optional)
5.5 Acetone, reagent grade

5.6 Pressurizing gas, air (or nitrogen) capable of being delivered to the top of the column at

controllable pressures over the range from 0 kPa gauge to 103 kPa gauge.
6 Apparatus

6.1 Adsorption column, with precision bore tubing conforming to the specification given in Table 1

and as shown in Figure 1, part b), made of glass and consisting of a charger section with a capillary

neck, a separator section and an analyser section.

For routine/non-specification compliance analysis adsorption columns with standard wall tubing

conforming to the specification given in Annex B and as shown in Figure 1, part a), may be used.

In addition the length of a thread of liquid approximately 100 mm long shall not vary in length by more

than 0,3 mm in any part of the analyser section.

Glass-sealing of the various sections to each other shall be done with long-taper connections rather than

shouldered connections. The silica gel shall be supported with a small piece of glass wool located

between the ball socket of the 12/2 spherical joint and covering the analyser outlet. The column tip

attached to the 12/2 socket shall be approximately 2 mm inside diameter. The ball and socket joints

shall be clamped together to ensure that the tip does not tend to slide from a position in a direct line

with the analyser section during the packing and subsequent use of the column.

At the moment of publication of this document, Honeywell UOP is the only supplier known of the dyed gel. This

information is given for the convenience of users of this document and does not constitute an endorsement by CEN or

CENELEC of the producer named. Equivalent products may be used if they can be shown to lead to the same results, e.g. by an

interlaboratory study.
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Table 1 — Precision bore column dimensions and tolerance limits
Charger section
Inside diameter 12 mm ± 2 mm
Overall length 150 mm ± 5 mm
Neck section
Inside diameter 2 mm ± 0,5 mm
Overall length 50 mm ± 5 mm
Separator section
Inside diameter 5 mm ± 0,5 mm
Overall length 190 mm ± 5 mm
...