SIST EN 12916:2016
(Main)Petroleum products - Determination of aromatic hydrocarbon types in middle distillates - High performance liquid chromatography method with refractive index detection
Petroleum products - Determination of aromatic hydrocarbon types in middle distillates - High performance liquid chromatography method with refractive index detection
This European Standard specifies a test method for the determination of the content of mono-aromatic,
di-aromatic and tri+-aromatic hydrocarbons in diesel fuels that may contain fatty acid methyl esters
(FAME) up to 30 % (V/V) and petroleum distillates in the boiling range from 150 °C to 400 °C. The
polycyclic aromatic hydrocarbons content is calculated from the sum of di-aromatic and tri+-aromatic
hydrocarbons and the total content of aromatic compounds is calculated from the sum of the individual
aromatic hydrocarbon types.
Compounds containing sulfur, nitrogen and oxygen can interfere in the determination; mono-alkenes do
not interfere, but conjugated di-alkenes and poly-alkenes, if present, may do so.
The precision statement of the test method has been established for diesel fuels with and without FAME
blending components, with a mono-aromatic content in the range from 6 % (m/m) to 30 % (m/m), a diaromatic
content from 1 % (m/m) to 10 % (m/m), a tri+-aromatic content from 0 % (m/m) to
2 % (m/m), a polycyclic aromatic content from 1 % (m/m) to 12 % (m/m), and a total aromatic content
from 7 % (m/m) to 42 % (m/m).
NOTE 1 For the purpose of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent
the mass fraction and the volume fraction of a material respectively.
NOTE 2 By convention, the aromatic hydrocarbon types are defined on the basis of their elution characteristics
from the specified liquid chromatography column relative to model aromatic compounds. Their quantification is
performed using an external calibration with a single aromatic compound for each of them, which may or may not
be representative of the aromatics present in the sample. Alternative techniques and test methods may classify
and quantify individual aromatic hydrocarbon types differently.
WARNING — The use of this Standard can involve hazardous materials, operations and
equipment. This Standard does not purport to address all of the safety problems associated with
its use. It is the responsibility of users of this standard to take appropriate measures to ensure
the safety and health of personnel prior to application of the standard, and fulfil statutory and
regulatory requirements for this purpose.
Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppe in Mitteldestillaten - Hochleistungsflüssigkeitschromatografisches Verfahren (HPLC) mit Brechzahl-Detektion
Produits pétroliers - Détermination des familles d'hydrocarbures dans les distillats moyens - Méthode par chromatographie liquide à haute performance avec détection par réfractométrie différentielle
Naftni proizvodi - Določevanje aromatskih ogljikovodikov v srednjih destilatih - Metoda tekočinske kromatografije visoke ločljivosti z detekcijo lomnega količnika
Ta evropski standard opredeljuje preskusno metodo za določanje vsebnosti monoaromatskih, diaromatskih in tri+-aromatskih ogljikovodikov v dizelskih gorivih, ki lahko vsebujejo do 30-odstotne (V/V) metilne estre maščobnih kislin (FAME) in naftne destilate z območjem vrelišča od 150 °C do 400 °C. Vsebnost policikličnih aromatskih ogljikovodikov je izračunana na podlagi vsote diaromatskih in tri+-aromatskih ogljikovodikov, skupna vsebnost aromatskih spojin pa je izračunana na podlagi vsote posameznih
vrst aromatskih ogljikovodikov.
Spojine z vsebnostjo žvepla, dušika in kisika lahko povzročajo motnje pri določanju; monoalkeni
ne povzročajo motenj, vendar jih konjugirani dialkeni in polialkeni lahko povzročajo, če so prisotni.
Izjava o natančnosti preskusne metode je bila določena za dizelska goriva s komponentami za mešanje z metilnimi estri maščobnih kislin in brez njih,
ki imajo 6-odstotno (m/m) do 30-odstotno (m/m) vsebnost monoaromatskih spojin, 1-odstotno (m/m) do 10-odstotno (m/m) vsebnost diaromatskih spojin, 0-odstotno (m/m) do
2-odstotno (m/m) vsebnost tri+-aromatskih spojin, 1-odstotno (m/m) do 12-odstotno (m/m) vsebnost policikličnih aromatskih spojin in 7-odstotno (m/m) do 42-odstotno (m/m) skupno vsebnost aromatskih spojin.
OPOMBA 1: V tem evropskem standardu sta uporabljeni oznaki % (m/m) in % (V/V), ki predstavljata masni delež oziroma prostornino materiala.
OPOMBA 2: Po dogovoru so vrste aromatskih ogljikovodikov opredeljene na podlagi njihovih elucijskih lastnosti določene kolone tekočinske kromatografije v primerjavi z modelnimi aromatskimi spojinami. Njihova kvantifikacija se izvede z uporabo zunanjega umerjanja z enojno aromatsko spojino za posamezno vrsto aromatskih ogljikovodikov, ki je lahko reprezentativna za aromatske spojine iz vzorca ali pa tudi ne. Druge tehnike in preskusne metode lahko drugače razvrstijo in kvantificirajo posamezne vrste aromatskih ogljikovodikov.
OPOZORILO: Pri uporabi tega standarda so lahko prisotni nevarni materiali, postopki in oprema. Ta standard ne obravnava vseh varnostnih težav, ki se nanašajo na njegovo uporabo. Za sprejetje ustreznih ukrepov za zagotavljanje varnosti in zdravja osebja pred uporabo standarda ter izpolnjevanje zakonskih in regulativnih zahtev za ta namen so odgovorni uporabniki tega standarda.
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
SIST EN 12916:2016
01-april-2016
1DGRPHãþD
SIST EN 12916:2006
1DIWQLSURL]YRGL'RORþHYDQMHDURPDWVNLKRJOMLNRYRGLNRYYVUHGQMLKGHVWLODWLK
0HWRGDWHNRþLQVNHNURPDWRJUDILMHYLVRNHORþOMLYRVWL]GHWHNFLMRORPQHJDNROLþQLND
Petroleum products - Determination of aromatic hydrocarbon types in middle distillates -
High performance liquid chromatography method with refractive index detection
Mineralölerzeugnisse - Bestimmung der Kohlenwasserstoffgruppe in Mitteldestillaten -
Hochleistungsflüssigkeitschromatografisches Verfahren (HPLC) mit Brechzahl-Detektion
Produits pétroliers - Détermination des familles d'hydrocarbures dans les distillats
moyens - Méthode par chromatographie liquide à haute performance avec détection par
réfractométrie différentielle
Ta slovenski standard je istoveten z: EN 12916:2016
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.080 Naftni proizvodi na splošno Petroleum products in
general
SIST EN 12916:2016 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST EN 12916:2016
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SIST EN 12916:2016
EN 12916
EUROPEAN STANDARD
NORME EUROPÉENNE
February 2016
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN 12916:2006
English Version
Petroleum products - Determination of aromatic
hydrocarbon types in middle distillates - High
performance liquid chromatography method with
refractive index detection
Produits pétroliers - Détermination des familles Mineralölerzeugnisse - Bestimmung von aromatischen
d'hydrocarbures dans les distillats moyens - Méthode Kohlenwasserstoffgruppen in Mitteldestillaten -
par chromatographie liquide à haute performance avec Hochleistungsflüssigkeitschromatographie-Verfahren
détection par réfractométrie différentielle mit Brechzahl-Detektion
This European Standard was approved by CEN on 13 December 2015.
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, Former Yugoslav Republic of Macedonia, 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
CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2016 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 12916:2016 E
worldwide for CEN national Members.
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SIST EN 12916:2016
EN 12916:2016
Contents Page
European foreword . 3
1 Scope . 4
2 Normative references . 4
3 Terms and definitions . 5
4 Principle . 6
5 Reagents and materials . 6
6 Apparatus . 7
7 Sampling . 8
8 Apparatus preparation . 8
9 Calibration . 11
10 Procedure. 12
11 Calculation . 14
11.1 Retention times . 14
11.2 Column resolution . 14
11.3 Cut times . 14
11.4 Aromatic hydrocarbons type content . 15
11.5 Polycyclic and total aromatic hydrocarbons content . 15
12 Expression of results . 15
13 Precision . 15
13.1 General . 15
13.2 Repeatability . 15
13.3 Reproducibility . 16
14 Test report . 16
Annex A (informative) Column selection and use . 17
Bibliography . 18
2
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SIST EN 12916:2016
EN 12916:2016
European foreword
This document (EN 12916:2016) 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 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 August 2016, and conflicting national standards shall
be withdrawn at the latest by August 2016.
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.
This document supersedes EN 12916:2006.
The third version of the method has been updated to extend the scope of the method beyond the
common diesel products to middle distillates with FAME contents up to 30 % (V/V) on the basis of the
results of a study performed on B5, B10, and B30 samples. As the procedure remains unchanged, the
precision statement from the previous version is still valid.
Additionally the method allows the use of a backflush to clean the column once the tri+-aromatics have
been eluted.
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, Former Yugoslav Republic of Macedonia,
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.
3
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SIST EN 12916:2016
EN 12916:2016
1 Scope
This European Standard specifies a test method for the determination of the content of mono-aromatic,
di-aromatic and tri+-aromatic hydrocarbons in diesel fuels that may contain fatty acid methyl esters
(FAME) up to 30 % (V/V) and petroleum distillates in the boiling range from 150 °C to 400 °C. The
polycyclic aromatic hydrocarbons content is calculated from the sum of di-aromatic and tri+-aromatic
hydrocarbons and the total content of aromatic compounds is calculated from the sum of the individual
aromatic hydrocarbon types.
Compounds containing sulfur, nitrogen and oxygen can interfere in the determination; mono-alkenes do
not interfere, but conjugated di-alkenes and poly-alkenes, if present, may do so.
The precision statement of the test method has been established for diesel fuels with and without FAME
blending components, with a mono-aromatic content in the range from 6 % (m/m) to 30 % (m/m), a di-
aromatic content from 1 % (m/m) to 10 % (m/m), a tri+-aromatic content from 0 % (m/m) to
2 % (m/m), a polycyclic aromatic content from 1 % (m/m) to 12 % (m/m), and a total aromatic content
from 7 % (m/m) to 42 % (m/m).
NOTE 1 For the purpose of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent
the mass fraction and the volume fraction of a material respectively.
NOTE 2 By convention, the aromatic hydrocarbon types are defined on the basis of their elution characteristics
from the specified liquid chromatography column relative to model aromatic compounds. Their quantification is
performed using an external calibration with a single aromatic compound for each of them, which may or may not
be representative of the aromatics present in the sample. Alternative techniques and test methods may classify
and quantify individual aromatic hydrocarbon types differently.
WARNING — The use of this Standard can involve hazardous materials, operations and
equipment. This Standard does not purport to address all of the safety problems associated with
its use. It is the responsibility of users of this standard to take appropriate measures to ensure
the safety and health of personnel prior to application of the standard, and fulfil statutory and
regulatory requirements for this purpose.
2 Normative references
The following documents, in whole or in part, are normatively referenced in this document and are
indispensable for its application. For dated references, only the edition cited applies. For undated
references, the latest edition of the referenced document (including any amendments) applies.
EN 14214, Liquid petroleum products — Fatty acid methyl esters (FAME) for use in diesel engines and
heating applications — Requirements and test methods
EN ISO 1042, Laboratory glassware - One-mark volumetric flasks (ISO 1042)
EN ISO 3170, Petroleum liquids - Manual sampling (ISO 3170)
EN ISO 3171, Petroleum liquids - Automatic pipeline sampling (ISO 3171)
4
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EN 12916:2016
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
non-aromatic hydrocarbon
compound having a shorter retention time on the specified polar column than the majority of mono-
aromatic hydrocarbons
3.2
mono-aromatic hydrocarbon
MAH
compound having a longer retention time on the specified polar column than the majority of non-
aromatic hydrocarbons, but a shorter retention time than the majority of di-aromatic hydrocarbons
3.3
di-aromatic hydrocarbon
DAH
compound having a longer retention time on the specified polar column than the majority of mono-
aromatic hydrocarbons, but a shorter retention time than the majority of tri+-aromatic hydrocarbons
3.4
tri+-aromatic hydrocarbon
T+AH
compound having a longer retention time on the specified polar column than the majority of di-
aromatic hydrocarbons, but a shorter retention time than chrysene
3.5
polycyclic aromatic hydrocarbon
POLY-AH
sum of the di-aromatic hydrocarbons and tri+-aromatic hydrocarbons
3.6
total aromatic hydrocarbon
sum of the mono-aromatic hydrocarbons, di-aromatic hydrocarbons and tri+-aromatic hydrocarbons
Note 1 to entry: Published and unpublished data indicate that the major constituents for each hydrocarbon type
may include:
a) non-aromatic hydrocarbons: acyclic and cyclic alkanes (paraffins and naphthenes), mono-alkenes (if
present),
b) MAHs: benzenes, tetralins, indanes and higher naphthenobenzenes (e.g. octahydrophenanthrenes),
thiophenes, styrenes, conjugated polyalkenes,
c) DAHs: naphthalenes, biphenyls, indenes, fluorenes, acenaphthenes, benzothiophenes and dibenzothiophenes,
d) T+AHs: phenanthrenes, pyrenes, fluoranthenes, chrysenes, triphenylenes, benzanthracenes.
3.7
fatty acid methyl ester
FAME
mixture of fatty acid methyl esters derived from vegetable oil or animal fats and complying to the
specification defined in EN 14214
5
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SIST EN 12916:2016
EN 12916:2016
4 Principle
A known mass of sample is diluted with heptane and a fixed volume of this solution injected into a high
performance liquid chromatograph fitted with a polar column. This column has little affinity for non-
aromatic hydrocarbons, while exhibiting a strong selectivity for aromatic hydrocarbons. As a result of
this selectivity, the aromatic hydrocarbons are separated from the non-aromatic hydrocarbons and into
distinct bands according to their ring structure, i.e. MAH, DAH and T+AH compounds.
The column is connected to a refractive index detector which detects the components as they elute from
the column. The electronic signal from the detector is continually monitored by a data processor. The
amplitudes of the signals from the aromatics in the sample are compared with those obtained from
calibration standards in order to calculate the mass fraction of MAHs, DAHs and T+AHs in the sample.
The sum of the DAHs and T+AHs mass fractions is reported as the mass fraction of POLY-AH, and the
sum of the MAHs, DAHs and T+AHs mass fractions is reported as the mass fraction of total aromatic
hydrocarbons.
After the aromatics have eluted from the column it may be backflushed to allow any remaining
components such as FAME to elute in a backflush peak. This will allow for a better cleaning of the
column but care should be taken as it can affect the lifetime of the column.
5 Reagents and materials
5.1 General
The highest purity reagents and materials available should be used; those required to be of high
performance liquid chromatography (HPLC) grade are commercially available from major suppliers.
5.2 Cyclohexane, of 99 % (m/m) minimum purity (CAS registry number 110-82-7)
NOTE Cyclohexane can contain benzene as an impurity.
5.3 Heptane, HPLC analytical grade, as the mobile phase (CAS RN 142-82-5)
Batch to batch variation of the solvent water content, viscosity, refractive index, and purity can cause
unpredictable column behaviour. Drying (for example, by standing over activated molecular sieve type
5A) and filtering the mobile phase may help reducing the effect of trace impurities present in the
solvent.
It is recommended practice to de-gas the mobile phase before use; this can be done conveniently online
or off-line by helium sparging, vacuum degassing or ultrasonic agitation. A failure to de-gas the mobile
phase can lead to negative peaks.
5.4 1-Phenyldodecane, of 98 % (m/m) minimum purity (CAS RN 123-01-3)
5.5 1,2-Dimethylbenzene (o-xylene), of 98 % (m/m) minimum purity (CAS RN 95-47-6)
5.6 Hexamethylbenzene, of 98 % (m/m) minimum purity (CAS RN 87-85-4)
5.7 Naphthalene, of 98 % (m/m) minimum purity (CAS RN 91-20-3)
5.8 Fluorene, of 98 % (m/m) minimum purity (CAS RN 86-73-7)
5.9 Phenanthrene, of 98 % (m/m) minimum purity (CAS RN 85-01-8)
5.10 Dibenzothiophene, of 95 % (m/m) minimum purity (CAS RN 132-65-0)
6
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EN 12916:2016
5.11 9-Methylanthracene, of 95 % (m/m) minimum purity (CAS RN 779-02-2)
5.12 Chrysene, of 95 % (m/m) minimum purity (CAS RN 218-01-9)
5.13 FAME, compliant to EN 14214
WARNING — Protective gloves should be worn when handling aromatic compounds.
6 Apparatus
6.1 Liquid chromatograph, consisting of a high performance instrument capable of pumping the
mobile phase at flow rates from 0,5 ml/min to 1,5 ml/min, with a precision better than 0,5 % and a
pulsation of < 1 % full scale deflection under the test conditions described in Clause 8.
6.2 Sample injection system, capable of nominally injecting 10 μl of sample solution with a
repeatability better than 1 %.
Equal and constant volumes of the calibration and sample solutions are injected into the
chromatograph. Both manual and automatic sample injection systems, using either complete or partial
filling of the sample loop, can meet these repeatability requirements when used correctly. When using
the partial filling mode, it is recommended that the injection volume is less than half the total loop
volume. For complete filling of the loop, best results are obtained by overfilling the loop at least six
times.
The repeatability of the injection system may be checked by comparing peak areas from at least four
injections of the system calibration standard (see 8.3).
Sample and calibration injection volumes different from 10 μl (typically in the range 3 μl to 20 μl) may
be used provided they meet the requirements for injection repeatability, refractive index sensitivity and
linearity (see 9.4), and column resolution (see 8.9).
6.3 Sample filter, if required (see 10.1), consisting of a microfilter of porosity 0,45 μm or less,
chemically inert towards hydrocarbon solvents, for the removal of particulate matter from the sample
solutions.
NOTE polytetrafluorethyleen (PTFE) filters have been found to be suitable.
6.4 Column system, consisting of a stainless steel HPLC column(s) packed with a commercial 3 μm,
5 μm or 10 μm amino-bonded (or amino/cyano-bonded) silica stationary phase meeting the resolution
requirements given in 8.6, 8.7, 8.9 and 8.11 . See Annex A for guidance on the selection and use of
suitable co
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