EN 12916-2016 en Petroleum products - Determination of aromatic hydrocarbon types in middle distillates - High performance liquid chromatography method with refractive index detect.pdf

1、BSI Standards PublicationBS EN 12916:2016Petroleum products Determination of aromatichydrocarbon types in middledistillates High performanceliquid chromatography methodwith refractive index detectionBS EN 12916:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of E

2、N 12916:2016.It supersedes BS EN 12916:2006 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/15, Natural Gas and Gas Analysis.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not p

3、urport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2016.Published by BSI Standards Limited 2016ISBN 978 0 580 87277 8ICS 75.080Compliance with a British Standard cannot confer immunity fromlegal obligations

4、.This British Standard was published under the authority of theStandards Policy and Strategy Committee on 29 February 2016.Amendments/corrigenda issued since publicationDate T e x t a f f e c t e dBS EN 12916:2016EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 12916 February 2016 ICS 75.080 Sup

5、ersedes EN 12916:2006English Version Petroleum products - Determination of aromatic hydrocarbon types in middle distillates - High performance liquid chromatography method with refractive index detection Produits ptroliers - Dtermination des familles dhydrocarbures dans les distillats moyens - Mthod

6、e par chromatographie liquide haute performance avec dtection par rfractomtrie diffrentielle Minerallerzeugnisse - Bestimmung von aromatischen Kohlenwasserstoffgruppen in Mitteldestillaten - Hochleistungsflssigkeitschromatographie-Verfahren mit Brechzahl-Detektion This European Standard was approved

7、 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 s

8、tandards 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 an

9、d 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, Hunga

10、ry, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELE

11、C Management Centre: Avenue Marnix 17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 12916:2016 EBS EN 12916:2016EN 12916:2016 2 Contents Page European foreword . 3 1 Scope 4 2 Normative references 4 3 Terms

12、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 Pol

13、ycyclic 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 BS EN 12916:2016EN 12916:2016 3 European foreword

14、 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 standar

15、d, 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

16、 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

17、% (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 elut

18、ed. 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,

19、 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. BS EN 12916:2016EN 12916:2016 4 1 Scope This European Standard specifies a test met

20、hod 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

21、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 interfer

22、e, 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/

23、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

24、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 usi

25、ng 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 Sta

26、ndard 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 applica

27、tion 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. F

28、or 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 v

29、olumetric flasks (ISO 1042) EN ISO 3170, Petroleum liquids - Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids - Automatic pipeline sampling (ISO 3171) BS EN 12916:2016EN 12916:2016 5 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 no

30、n-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

31、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

32、 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 hydrocarbo

33、ns 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 cycli

34、c 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 di

35、benzothiophenes, 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 BS EN 12916:2016EN 12916:

36、2016 6 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 hy

37、drocarbons. 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

38、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

39、 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 a

40、llow 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;

41、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 mo

42、bile 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 o

43、f 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-Phenyldod

44、ecane, 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) mini

45、mum 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) BS EN 12916:2016EN 12916:2016 7 5.11 9-Methylanthracene, of 95 % (m/m) minimum purity (CAS RN 779-02-2) 5.12 Chrysene, of 95 % (m/m) minim

46、um 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, w

47、ith 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 l of sample solution with a repeatability better than 1 %. Equal and constant volumes of the calibration and

48、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 inject

49、ion 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 l (typically in the range 3 l to 20 l) may be used provided they meet the requirements for injection repeatability, refractive index sensitivity and linearity (see 9.4), and column resolut