SIST EN 12916:2006
(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 5 % (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 may interfere in the determination; mono-alkenes do not interfere, but conjugated di-alkenes and polyalkenes, 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 may involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated wit
Mineralölerzeugnisse - Bestimmung von aromatischen Kohlenwasserstoffgruppen in Mitteldestillaten - HPLC-Verfahren mit Brechzahl-Detektor
Diese Europäische Norm legt ein Verfahren zur Bestimmung des Gehaltes an mono-aromatischen, di-aromatischen und tri+-aromatischen Kohlenwasserstoffen in Dieselkraftstoffen, mit bis zu 5 % (V/V) Fettsäuremethylester (FAME) und in Mineralöldestillaten, deren Siedepunkt im Bereich zwischen 150 °C und 400 °C liegt, fest. Der Gehalt an polycyclischen aromatischen Kohlenwasserstoffen wird als Summe der Gehalte an di-aromatischen und tri+-aromatischen Kohlenwasserstoffen berechnet. Der Gesamtgehalt an aromatischen Kohlenwasserstoffen errechnet sich aus der Summe der einzelnen Kohlenwasserstoffgruppen.
Verbindungen, die Schwefel, Stickstoff oder Sauerstoff enthalten, können die Bestimmung stören; Mono-Alkene interferieren nicht, di-Alkene und Poly-Alkene können stören, wenn sie vorhanden sind.
Die Präzision dieses Verfahrens wurde für Dieselkraftstoffe (mit und ohne zugeblendete Fettsäure-Methylester, FAME) ermittelt, welche 6 % (m/m) bis 30 % (m/m) mono-aromatische Kohlenwasserstoffe, 1 % (m/m) bis 10 % (m/m) di-aromatische Kohlenwasserstoffe, 0 % (m/m) bis 2 % (m/m) tri+-aromatische Kohlenwasserstoffe, 1 % (m/m) bis 12 % (m/m) polycyclische aromatische Kohlenwasserstoffe, und einen Gesamtgehalt an aromatischen Kohlenwasserstoffen von 7 % (m/m) bis 42 % (m/m) enthalten.
ANMERKUNG 1 Für den Zweck dieser Europäischen Norm wird % (m/m) als Ausdruck für den Massenanteil in % und % (V /V) als Ausdruck für den Volumenanteil in % verwendet.
ANMERKUNG 2 Diese Norm definiert die aromatischen Kohlenwasserstofftypen durch Konvention, basierend auf ihrer Elutionscharakteristik von der festgelegten Chromatographiesäule relativ zu aromatischen Modellverbindungen. Die Quantifizierung für jede aromatische Verbindungsklasse erfolgt durch externe Kalibrierung mit einzelnen aromatischen Verbindungen für jede Verbindungsklasse, die für die Verbindungen in der Probe unter Umständen nicht repräsentativ sind. Andere Bestimmungsverfahren können die verschiedenen aromatischen Kohlenwasse
Produits pétroliers - Détermination des familles d'hydrocarbures aromatiques dans les distillats moyens - Méthode par chromatographie liquide a haute performance avec détection par réfractométrie différentielle
La présente Norme européenne prescrit une méthode pour déterminer la teneur en hydrocarbures mono aromatiques, diaromatiques, et tri+-aromatiques des carburants diesel, qui peuvent contenir des esters méthyliques d’acides gras (EMAG) jusqu’a 5 % (V/V), et distillats pétroliers d'intervalle d'ébullition de 150 °C a 400 °C. La teneur en hydrocarbures aromatiques polycycliques est calculée a partir de la somme des diaromatiques, et tri+-aromatiques, et la teneur globale en composés aromatiques est calculée a partir de la somme des teneurs des différentes familles de composés aromatiques.
Les composés soufrés, azotés et oxygénés peuvent interférer dans la mesure. Les mono-oléfines n'interferent pas, au contraire des dioléfines conjuguées et des polyoléfines qui peuvent interférer, si elles sont présentes.
Les données de fidélité de la méthode ont été établies pour des carburants diesels contenant ou ne contenant pas d’EMAG, avec une teneur en mono-aromatiques située dans la gamme 6 % (m/m) a 30 % (m/m), une teneur en diaromatiques dans la gamme 1 % (m/m) a 10 % (m/m), une teneur en tri+-aromatiques dans la gamme 0 % (m/m) a 2 % (m/m), une teneur en hydrocarbures aromatiques polycycliques dans la gamme 1 % (m/m) a 12 % (m/m), et une teneur en aromatiques totaux dans la gamme 7 % (m/m) a 42 % (m/m).
NOTE 1 Pour les besoins de la présente Norme européenne, les expressions « % (m/m) » et « % (V/V) » sont utilisées pour désigner respectivement les fractions massiques et les fractions volumiques d’un produit.
NOTE 2 Par convention, la présente Norme définit les familles d’hydrocarbures aromatiques a partir de leurs caractéristiques d’élution dans la colonne de chromatographie liquide prescrite, et par comparaison aux temps d'élution des composés aromatiques servant de modele.
Naftni proizvodi – Določevanje aromatskih ogljikovodikov v srednjih destilatih – Metoda tekočinske kromatografije visoke ločljivosti z detekcijo lomnega količnika
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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Petroleum products - Determination of aromatic hydrocarbon types in middle distillates - High performance liquid chromatography method with refractive index detectionProduits pétroliers - Détermination des familles d'hydrocarbures aromatiques dans les distillats moyens - Méthode par chromatographie liquide a haute performance avec détection par réfractométrie différentielleMineralölerzeugnisse - Bestimmung von aromatischen Kohlenwasserstoffgruppen in Mitteldestillaten - HPLC-Verfahren mit Brechzahl-DetektorTa slovenski standard je istoveten z:EN 12916:2006SIST EN 12916:2006en75.080ICS:SIST EN 12916:20001DGRPHãþDSLOVENSKI
STANDARDSIST EN 12916:200601-september-2006
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 12916May 2006ICS 75.080Supersedes EN 12916:2000
English VersionPetroleum products - Determination of aromatic hydrocarbontypes in middle distillates - High performance liquidchromatography method with refractive index detectionProduits pétroliers - Détermination des famillesd'hydrocarbures aromatiques dans les distillats moyens -Méthode par chromatographie liquide à haute performanceavec détection par réfractométrie différentielleMineralölerzeugnisse - Bestimmung von aromatischenKohlenwasserstoffgruppen in Mitteldestillaten - HPLC-Verfahren mit Brechzahl-DetektorThis European Standard was approved by CEN on 20 April 2006.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, 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 STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2006 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 12916:2006: E
EN 12916:2006 (E) 2 Contents Page Foreword.3 1 Scope.4 2 Normative references.4 3 Terms and definitions.4 4 Principle.5 5 Reagents and materials.6 6 Apparatus.6 7 Sampling.7 8 Apparatus preparation.7 9 Calibration.9 10 Procedure.11 11 Calculation.12 12 Expression of results.13 13 Precision.14 14 Test report.14 Annex A (informative)
Column selection and use.15 Bibliography.16
EN 12916:2006 (E) 3 Foreword This document (EN 12916:2006) 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 November 2006, and conflicting national standards shall be withdrawn at the latest by November 2006. This document supersedes EN 12916:2000. The method has been updated and improved in the sense that: a method without back-flush is prescribed resulting in simplicity of the instrument; the integration of aromatic hydrocarbon types has been better defined (definition of cut times); fluorene is used as calibrant for the determination of aromatic hydrocarbons content instead of 1-methylnaphthalene in order to minimize the bias on the di-aromatic hydrocarbons content between the former method and this version; diesel fuels containing FAME up to 5 % (V/V) are included in the scope of the method and the interferences between FAME and tri+-aromatic hydrocarbons do not exist any more; The precision of the method has been re-calculated using data from a new inter-laboratory test programme. The precision statement for % (m/m) PAHs, as defined by EN 590: 2004 [1], is now included. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, 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.
EN 12916:2006 (E) 4 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 5 % (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 may interfere in the determination; mono-alkenes do not interfere, but conjugated di-alkenes and polyalkenes, 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 may 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 the user of this standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use. 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. EN 14214, Automotive fuels – Fatty acid methyl esters (FAME) for diesel engines – Requirements and test methods EN ISO 1042, Laboratory glassware – One-mark volumetric flasks (ISO 1042:1998) EN ISO 3170, Petroleum liquids – Manual sampling (ISO 3170:2004) EN ISO 3171, Petroleum liquids – Automatic pipeline sampling (ISO 3171:1988) 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
EN 12916:2006 (E) 5 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 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 as specified in EN 14214 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, whilst 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.
EN 12916:2006 (E) 6 5 Reagents and materials NOTE 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. 5.1 Cyclohexane, of 99 % (m/m) minimum purity NOTE Cyclohexane may contain benzene as an impurity. 5.2 Heptane, HPLC analytical grade, as the mobile phase NOTE 1 Batch to batch variation of the solvent water content, viscosity, refractive index, and purity may 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. NOTE 2 It is recommended practice to de-gas the mobile phase before use; this can be done conveniently on-line or off-line by helium sparging, vacuum degassing or ultrasonic agitation. A failure to de-gas the mobile phase may lead to negative peaks. 5.3 1-Phenyldodecane, of 98 % (m/m) minimum purity 5.4 1,2-Dimethylbenzene (o-xylene), of 98 % (m/m) minimum purity 5.5 Hexamethylbenzene, of 98 % (m/m) minimum purity 5.6 Naphthalene, of 98 % (m/m) minimum purity 5.7 Fluorene, of 98 % (m/m) minimum purity 5.8 Phenanthrene, of 98 % (m/m) minimum purity 5.9 Dibenzothiophene, of 95 % (m/m) minimum purity 5.10 9-Methylanthracene, of 95 % (m/m) minimum purity 5.11 Chrysene, of 95 % (m/m) minimum purity 5.12 FAME (see 3.7) 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 %. NOTE 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).
EN 12916:2006 (E) 7 NOTE 2 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 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 and 8.9 . See Annex A for guidance on the selection and use of suitable column systems. 6.5 Temperature control, consisting of either a heating block, or an air-circulating HPLC column oven or an alternative form of temperature control, such as a temperature-controlled laboratory, capable of maintaining a constant temperature in the range 20 °C ± 1 °C to 40 °C ± 1 °C. NOTE The refractive index detector is sensitive to both sudden and gradual changes in the temperature of the eluent. All necessary precautions should be taken to establish constant temperature conditions throughout the liquid chromatograph system. The temperature should be optimised depending on the stationary phase. 6.6 Ref
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