DIN EN ISO 20846-2012 Petroleum products - Determination of sulfur content of automotive fuels - Ultraviolet fluorescence method (ISO 20846 2011) German version EN ISO 20846 2011《石.pdf

1、January 2012 Translation by DIN-Sprachendienst.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).IC

2、S 75.160.20!$y,u“1860982www.din.deDDIN EN ISO 20846Petroleum products Determination of sulfur content of automotive fuels Ultraviolet fluorescence method (ISO 20846:2011)English translation of DIN EN ISO 20846:2012-01Minerallerzeugnisse Bestimmung des Schwefelgehaltes von Kraftstoffen fr Kraftfahrze

3、uge Ultraviolettfluoreszenz-Verfahren (ISO 20846:2011)Englische bersetzung von DIN EN ISO 20846:2012-01Produits ptroliers Dtermination de la teneur en soufre des carburants pour automobiles Mthode par fluorescence ultraviolette (ISO 20846:2011)Traduction anglaise de DIN EN ISO 20846:2012-01Supersede

4、sDIN EN ISO 20846:2004-07www.beuth.deDocument comprises pagesIn case of doubt, the German-language original shall be considered authoritative.1701.12 DIN EN ISO 20846:2012-01 2 A comma is used as the decimal marker. National foreword This standard has been prepared by Technical Committee CEN/TC 19 “

5、Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands) in collaboration with Technical Committee ISO/TC 28 “Petroleum products and lubricants” (Secretariat: ASTM, USA). The responsible German body involved in its prepa

6、ration was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee NA 062-06-42 AA Prfung von flssigen Kraft-stoffen und Heizlen of Section Minerall- und Brennstoffnormung. The DIN Standards corresponding to the International Standards referred to in this docume

7、nt are as follows: ISO 1042 DIN EN ISO 1042 ISO 3170 DIN EN ISO 3170 ISO 3171 DIN EN ISO 3171 ISO 3675 DIN EN ISO 3675 ISO 12185 DIN EN ISO 12185 Amendments This standard differs from DIN EN ISO 20846:2004-07 as follows: a) the determination of the sulfur content of motor gasolines containing up to

8、3,7 % (m/m) oxygen is now permitted; b) the scope has been extended to include B10 diesel fuel and E10 motor gasoline. Previous editions DIN EN ISO 20846: 2004-07 National Annex NA (informative) Bibliography DIN EN ISO 1042, Laboratory glassware One-mark volumetric flasks DIN EN ISO 3170, Petroleum

9、liquids Manual sampling DIN EN ISO 3171, Petroleum liquids Automatic pipeline sampling DIN EN ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer method DIN EN ISO 12185, Crude petroleum and petroleum products Determination of density Oscillating U-

10、tube method EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 20846 October 2011 ICS 75.160.30; 75.160.20 Supersedes EN ISO 20846:2004English Version Petroleum products - Determination of sulfur content of automotive fuels - Ultraviolet fluorescence method (ISO 20846:2011) Produits ptroliers

11、- Dtermination de la teneur en soufre des carburants pour automobiles - Mthode par fluorescence ultraviolette (ISO 20846:2011) Minerallerzeugnisse - Bestimmung des Schwefelgehaltes von Kraftstoffen fr Kraftfahrzeuge - Ultraviolettfluoreszenz-Verfahren (ISO 20846:2011) This European Standard was appr

12、oved by CEN on 30 September 2011. 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 natio

13、nal 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 langua

14、ge 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, Latvi

15、a, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussel

16、s 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 20846:2011: EContents Page Foreword 3 1 Scope 4 2 Normative references 4 3 Principle 4 4 Reagents and materials 5 5 Apparatus .6 6 Sampling .8 7 Apparatus preparation 8 8 A

17、pparatus calibration and verification 8 8.1 Multi-point calibration .8 8.2 One-point calibration 10 8.3 Verification 11 9 Procedure 11 10 Calculation . 12 10.1 Using multi-point calibration . 12 10.2 Using one-point calibration . 12 10.3 Calculation . 13 11 Expression of results . 13 12 Precision 13

18、 12.1 General . 13 12.2 Repeatability, r 13 12.3 Reproducibility, R 14 13 Test report . 14 Bibliography . 15 DIN EN ISO 20846:2012-01 EN ISO 20846:2011 (E) 2 Foreword This document (EN ISO 20846:2011) has been prepared by Technical Committee ISO/TC 28 “Petroleum products and lubricants” in collabora

19、tion 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

20、 by endorsement, at the latest by April 2012, and conflicting national standards shall be withdrawn at the latest by April 2012. 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

21、identifying any or all such patent rights. This document supersedes EN ISO 20846:2004. 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

22、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 the United Kingdom. Endorsement notice The text of ISO 20846:2011 h

23、as been approved by CEN as a EN ISO 20846:2011 without any modification. DIN EN ISO 20846:2012-01 EN ISO 20846:2011 (E) 3 WARNING The use of this International Standard may involve hazardous materials, operations and equipment. This International Standard does not purport to address all of the safet

24、y problems associated with its use. It is the responsibility of the user of this International Standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use.1 ScopeThis International Standard specifies an ultraviolet (UV) fluores

25、cence test method for the determination of the sulfur content of motor gasolines containing up to 3,7 % (m/m) oxygen including those blended with ethanol up to about 10 % (V/V), and of diesel fuels, including those containing up to about 10 % (V/V) fatty acid methylester (FAME), having sulfur conten

26、ts in the range 3 mg/kg to 500 mg/kg. Other products can be analysed and other sulfur contents can be determined according to this test method, however, no precision data for products other than automotive fuels and for results outside the specified range have been established for this International

27、 Standard. Halogens interfere with this detection technique at concentrations above approximately 3 500 mg/kg.NOTE 1 Some process catalysts used in petroleum and chemical refining can be poisoned when trace amounts of sulfur-bearing materials are contained in the feedstocks.NOTE 2 This test method c

28、an be used to determine sulfur in process feeds and can also be used to control sulfur in effluents.NOTE 3 For the purposes of this International Standard, the terms “% (m/m)” and “% (V/V)” are used to represent the mass fraction and the volume fraction of a material respectively.NOTE 4 Sulfate spec

29、ies in ethanol do not have the same conversion factor of organic sulfur in ethanol. Nevertheless, sulfates have a conversion factor close to that of organic sulfur.NOTE 5 It is preferable to check the nitrogen interference and to take it into account, especially when sulfur content is measured on di

30、esel blended with cetane improver containing nitrogen. For example, alkyl nitrate, as 2-ethyl hexyl nitrate (EHN), added as cetane improver to diesel fuel shows an enhancing effect on sulfur content that can range from 0 to 1,7 mg/kg when 2 000 mg/kg EHN is added to diesel fuel containing 10 mg/kg s

31、ulfur.2 Normative referencesThe 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.ISO 1042, Laboratory g

32、lassware One-mark volumetric flasksISO 3170, Petroleum liquids Manual samplingISO 3171, Petroleum liquids Automatic pipeline samplingISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer methodISO 12185, Crude petroleum and petroleum products Determin

33、ation of density Oscillating U-tube method3 PrincipleA hydrocarbon sample is injected into a UV fluorescence detector. The sample enters a high temperature combustion tube (1 000 C to 1 100 C), where the sulfur is oxidized to sulfur dioxide (SO2) in an oxygen-rich atmosphere. Water produced during t

34、he sample combustion is removed and the sample combustion gases areDIN EN ISO 20846:2012-01 EN ISO 20846:2011 (E) 4 exposed to UV light. The SO2absorbs the energy from the UV light and is converted to excited sulfur dioxide (SO2*). The fluorescence emitted from the excited SO2* as it returns to a st

35、able state SO2is detected by a photomultiplier tube and the resulting signal is a measure of the sulfur contained in the sample.4 Reagents and materials4.1 Inert gas, argon or helium, high purity grade with a minimum purity of 99,998 % (V/V).4.2 Oxygen, high purity grade with a minimum purity of 99,

36、75 % (V/V).CAUTION Vigorously accelerates combustion.4.3 Solvent4.3.1 GeneralUse either that specified in 4.3.2 or 4.3.3, or a solvent similar to that occurring in the sample under analysis. Correction for sulfur contribution from solvents used in standard preparation and sample dilution is required

37、. Alternatively, use of a solvent with non-detectable sulfur contamination relative to the unknown sample makes the blank correction unnecessary.4.3.2 Toluene, reagent grade.4.3.3 Isooctane, reagent grade.CAUTION Flammable solvents.4.4 Sulfur compounds4.4.1 GeneralCompounds with a minimum purity of

38、99 % (m/m). Examples are given in 4.4.2 to 4.4.4. Where the purity of these compounds is less than 99 % (m/m), the concentrations and nature of all impurities shall be established.NOTE A correction for chemical impurity can be applied when the sulfur content is known with accuracy.Certified referenc

39、e materials (CRM) from accredited suppliers are suitable alternatives to the compounds listed in 4.4.2 to 4.4.4.4.4.2 Dibenzothiophene (DBT), of molecular mass 184,26, with a nominal sulfur content of 17,399 % (m/m).4.4.3 Dibutyl sulfide (DBS), of molecular mass 146,29, with a nominal sulfur content

40、 of 21,915 % (m/m).4.4.4 Thionaphthene (Benzothiophene) (TNA), of molecular mass 134,20, with a nominal sulfur content of 23,890 % (m/m).4.5 Sulfur stock solutionPrepare a stock solution of approximately 1 000 mg/l sulfur content by accurately weighing the appropriate quantity of sulfur compound (4.

41、4) in a volumetric flask (5.9). Ensure complete dissolution with solvent (4.3). Calculate the exact sulfur concentration of the stock solution to the nearest 1 mg/l. This stock solution is used for the preparation of calibration standards. As an alternative procedure, a sulfur stock solution of appr

42、oximately 1 000 mg/kg can be prepared by accurately weighing the appropriate quantity of sulfur compound (4.4) in a volumetric flask (5.9) and reweighing the volumetric flask once it has been filled to the mark with the solvent (4.3). Take precautions to ensure that evaporation of the solvent and/or

43、 sulfur compounds is not causing weighing errors.DIN EN ISO 20846:2012-01 EN ISO 20846:2011 (E) 5 The appropriate mass of sulfur compound described in 4.4.2 to 4.4.4 to add to the 100 ml flask is 0,574 8 g (DBT), 0,456 3 g (DBS) and 0,418 6 g (TNA).NOTE The shelf life of the stock solution is approx

44、imately three months when stored at low temperature, typically in a refrigerator.4.6 Calibration standardsPrepare the calibration standards by dilution of the stock solution (4.5) with the selected solvent (4.3).Calculate the exact sulfur content of each calibration standard.Calibration standards wi

45、th a known sulfur concentration, in milligrams per litre, (or content, in milligrams per kilogram) can be obtained with a volume/volume dilution (or mass/mass dilution, respectively) of the stock solution at 1 000 mg/l (or 1 000 mg/kg respectively). Other practices are possible, but those mentioned

46、above avoid any density correction.New calibration standards should be prepared on a regular basis, depending upon the frequency of use and age. When stored at low temperature, typically in a refrigerator, the calibration standards with a sulfur content above 30 mg/kg (or mg/l) have a shelf life of

47、at least one month. Below this sulfur content (30 mg/kg), the shelf life should be reduced.4.7 Quality control samplesQuality control samples are stable samples representative of the materials being analysed, which have a sulfur content that is known by this test method over a substantial period of

48、time. Alternatively, there are standard materials with a certified value commercially available. Prior to use, ensure that the material is within its shelf life.4.8 Quartz woolFollow the manufacturers recommendations.5 ApparatusFigure 1 illustrates the basic pieces of the UVF.5.1 Furnace, comprising an electric device, capable of maintaining a temperature sufficient to pyrolyse all of the sample and oxidize all sulfur to sulfur dioxide (SO2).It can be set either in a horizontal or vertical position.5.2