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

1、June 2016 English price group 11No part of this translation may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 75.080!%VpO“2517744www.din.deDIN EN

2、 12916Petroleum products Determination of aromatic hydrocarbon types in middle distillates High performance liquid chromatography method with refractive index detection;English version EN 12916:2016,English translation of DIN EN 12916:2016-06Minerallerzeugnisse Bestimmung von aromatischen Kohlenwass

3、erstoffgruppen in Mitteldestillaten Hochleistungsflssigkeitschromatographie-Verfahren mit Brechzahl-Detektion;Englische Fassung EN 12916:2016,Englische bersetzung von DIN EN 12916:2016-06Produits ptroliers Dtermination des familles dhydrocarbures dans les distillats moyens Mthode par chromatographie

4、 liquide haute performance avec dtection par rfractomtrie diffrentielle;Version anglaise EN 12916:2016,Traduction anglaise de DIN EN 12916:2016-06SupersedesDIN EN 12916:2006-08www.beuth.deDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritat

5、ive.Document comprises 20 pages 05.16 2A comma is used as the decimal marker. National 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” (Secretariat: NEN

6、, Netherlands). The responsible German body involved in its preparation was DIN-Normenausschuss Materialprfung (DIN Standards Committee Materials Testing), Working Committee NA 062-06-14 AA Chromatographische Analyse of the Fachausschuss Minerall- und Brennstoffnormung (FAM). It should be noted that

7、 this standard includes a national footnote to Clause 1 to explain that the interference with the determination was detected in commercially available fuels. Amendments This standard differs from DIN EN 12916:2006-08 as follows: a) the scope has been extended to include diesel fuels containing up to

8、 30 % (V/V) fatty acid methyl esters (FAME); b) the method now allows the use of a backflush to clean the column. Previous editions DIN EN 12916: 2001-08, 2001-11, 2006-08 DINEN 12916:2016-06This should be verified in special cases.EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 12916 February

9、2016 ICS 75.080 Supersedes 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 distil

10、lats moyens - Mthode par chromatographie liquide haute performance avec dtection par rfractomtrie diffrentielle Minerallerzeugnisse - Bestimmung von aromatischen Kohlenwasserstoffgruppen in Mitteldestillaten - Hochleistungsflssigkeitschromatographie-Verfahren mit Brechzahl-Detektion This European St

11、andard 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 concern

12、ing 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

13、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, Ger

14、many, Greece, Hungary, 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

15、 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 worldwide for CEN national Members. Ref. No. EN 12916:2016 EEN 12916:2016 2 Contents Page European foreword . 3 1 Scope 4 2 Normative references 4 3 Ter

16、ms 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

17、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 DINEN 12916:2016-06 EN 12916:2016 3 European f

18、oreword 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

19、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 righ

20、ts. 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

21、 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 be

22、en 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,

23、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. DINEN 12916:2016-06 EN 12916:20164 1 Scope This European Standard specifies

24、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 c

25、ontent 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 no

26、t 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 fr

27、om 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 repr

28、esent 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 per

29、formed 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 o

30、f 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

31、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

32、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 -

33、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) DINEN 12916:2016-06 N1) National footnote: See National foreword. N1)EN 12916:2016 5 3 Terms and definitions For the purposes of t

34、his 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 pola

35、r 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 ret

36、ention 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 s

37、um 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 ty

38、pe 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, biphe

39、nyls, 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

40、the specification defined in EN 14214 DINEN 12916:2016-06EN 12916:2016 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 h

41、ydrocarbons, 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 connect

42、ed 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 standar

43、ds 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 th

44、e 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 Th

45、e 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 ben

46、zene 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

47、 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 d

48、e-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

49、) 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) DINEN 12916:2016-06 EN 12916:20167 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