1、September 2008DEUTSCHE NORM English price group 14No part of this standard 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!$Qf?“1466728w
2、ww.din.deDDIN EN 15199-3Petroleum products Determination of boiling range distribution by gas chromatographymethod Part 3: Crude oilEnglish version of DIN EN 15199-3:2008-09Minerallerzeugnisse Gaschromatographische Bestimmung des Siedeverlaufes Teil 3: RohleEnglische Fassung DIN EN 15199-3:2008-09ww
3、w.beuth.deDocument comprises 30 pagesDIN EN 15199-3:2008-09 2 National foreword This standard 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, Netherlands). The responsible
4、German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Technical Committee NA 062-06-81 AA Gasfrmige und flssige Kraft- und Brennstoffe, Schmierstoffe und verwandte Produkte mit minerallstmmiger, synthetischer oder biologischer Herkunf
5、t of the Fachausschuss Minerall- und Brennstoffnormung (FAM). DIN EN 15199 consists of the following parts, under the general title Petroleum products Determination of boiling range distribution by gas chromatography method: Part 1: Middle distillates and lubricating base oils Part 2: Heavy distilla
6、tes and residual fuels Part 3: Crude oil EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15199-3May 2008ICS 75.080English VersionPetroleum products - Determination of boiling range distributionby gas chromatography method - Part 3: Crude oilProduits ptroliers - Dtermination de la rpartition dansli
7、ntervalle de distillation par mthode de chromatographieen phase gazeuse - Partie 3: Ptrole brutMinerallerzeugnisse - GaschromatographischeBestimmung des Siedeverlaufes - Teil 3: RohleThis European Standard was approved by CEN on 18 April 2008.CEN members are bound to comply with the CEN/CENELEC Inte
8、rnal 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 CEN Management Centre or to any CEN membe
9、r.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 CEN Management Centre has the same status as theofficial versions.CEN members ar
10、e the national standards bodies of Austria, Belgium, Bulgaria, 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, Switzerl
11、and and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2008 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 1519
12、9-3:2008: EEN 15199-3:2008 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Terms and definitions .4 4 Principle6 5 Reagents and materials 7 6 Apparatus .9 7 Sampling.11 8 Preparation of the apparatus11 8.1 Gas chromatograph preparation11 8.2 System performance check 11 9 Corrected
13、 sample and reference material preparation11 10 Calibration 12 11 Procedure .13 12 Visual inspection of the chromatograms 14 13 Calculation15 14 Expression of results 15 15 Precision.15 15.1 General15 15.2 Repeatability.15 15.3 Reproducibility.15 16 Test report 16 Annex A (normative) Calculation pro
14、cedure17 Annex B (informative) Additional guidance for the calculation algorithm20 Annex C (normative) System performance check .24 Annex D (informative) Calculation method for amount recovered 26 Annex E (informative) Boiling points of normal alkanes.27 Bibliography 28 DIN EN 15199-3:2008-09 EN 151
15、99-3:2008 (E) 3 Foreword This document (EN 15199-3:2008) 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 st
16、atus of a national standard, either by publication of an identical text or by endorsement, at the latest by November 2008, and conflicting national standards shall be withdrawn at the latest by November 2008. Attention is drawn to the possibility that some of the elements of this document may be the
17、 subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. EN 15199 consists of the following parts, under the general title Petroleum products Determination of boiling range distribution by gas chromatography method: Part 1: Middle dis
18、tillates and lubricating base oils Part 2: Heavy distillates and residual fuels Part 3: Crude oil A fourth part on light fractions is under study. This part of the standard describes the determination of boiling range distribution of materials with initial boiling points (IBP) below 100 C and final
19、boiling points (FBP) above 750 C. For testing materials with initial boiling points (IBP) above 100 C and final boiling point (FBP) below 750 C, part 1 of the standard may be used. For testing materials with initial boiling points (IBP) above 100 C and final boiling point (FBP) above 750 C, part 2 o
20、f the standard may be used. This part of the standard is harmonized with IP 545 1 and ASTM D 7169 2. 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, Cyprus, C
21、zech 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. DIN EN 15199-3:2008-09 EN 15199-3:2008 (E)
22、 4 1 Scope This European Standard describes a method for the determination of the boiling range distribution of petroleum products by capillary gas chromatography using flame ionisation detection. The standard is applicable to crude oils. The boiling range distribution and recovery to C100or C120 ca
23、n be determined. Two procedures are described: single and dual analysis mode. The basis of each is the calculation procedure as described in Annex A. NOTE 1 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 stan
24、dard to establish appropriate safety and health practices and determine the applicability of regulatory limitations. NOTE 2 For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction and the volume fraction. WARNING Use of this
25、European Standard may involve hazardous materials, operations and equipment. This European 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 determ
26、ine 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
27、(including any amendments) applies. 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. NOTE Explanation of
28、some of the terms is given in Figure 1. 3.1 initial boiling point IBP temperature corresponding to the retention time at which a net area count equal to 0,5 % of the total sample area under the chromatogram is obtained 3.2 final boiling point FBP temperature corresponding to the retention time at wh
29、ich a net area count equal to 99,5 % of the total sample area under the chromatogram is obtained NOTE If the found recovery is less than 100 %, the final boiling point is reported as 720 C or 750 C at that recovery. DIN EN 15199-3:2008-09 EN 15199-3:2008 (E) 5 3.3 area slice area resulting from the
30、integration of the chromatographic detector signal within a specified retention time interval NOTE In area slice mode peak detection parameters are bypassed and the detector signal integral is recorded as area slices of consecutive, fixed duration time interval. key 1 start of elution 2 initial boil
31、ing point (IBP) 3 final boiling point (FBP) 4 end of elution Figure 1 Typical chromatogram 3.4 corrected area slice area slice corrected for baseline offset by subtraction of the exactly corresponding area slice in a previously recorded blank (non-sample) analysis 3.5 cumulative corrected area accum
32、ulated sum of corrected area slices from the beginning of the analysis through a given retention time, ignoring any non-sample area for example of solvent 3.6 slice rate time interval used to integrate the continuous (analogue) chromatographic detector response during an analysis NOTE The slice rate
33、 is expressed in Hz (for example integrations per second or slices per second). 3.7 slice time analysis time associated with each area slice throughout the chromatographic analysis NOTE The slice time is the time at the end of each contiguous area slice. DIN EN 15199-3:2008-09 EN 15199-3:2008 (E) 6
34、3.8 total sample area cumulative corrected area, from the initial area point to the final area point, where the chromatographic signal has returned to baseline after complete sample elution 3.9 net area cumulative area counts for the sample minus the cumulative area count for the blank 3.10 recovery
35、 ratio of the cumulative area count of the sample to that of the reference material (external standard) corrected for dilution and material weights combined with the percentage of light ends, if applicable 4 Principle The boiling range distribution determination by distillation is simulated by the u
36、se of gas chromatography. A non-polar open tubular (capillary) gas chromatographic column is used to elute the hydrocarbon components of the sample in order of increasing boiling point. A sample aliquot is diluted with a viscosity reducing solvent and introduced into the chromatographic system. Samp
37、le vaporization is provided by separately heating the point of injection or in conjunction with column oven heating. The column oven temperature is raised at a specified linear rate to affect separation of the hydrocarbon components in order of increasing boiling point. The elution of sample compone
38、nts is quantitatively determined using a flame ionization detector. The detector signal is recorded as area slices for consecutive retention time intervals during the analysis. Retention times of known normal paraffin hydrocarbons, spanning the scope of the test method, are determined and correlated
39、 to their boiling point temperatures. The normalized cumulative corrected sample areas for each consecutive recorded time interval are used to calculate the boiling range distribution. The boiling point temperature at each reported percent off increment is calculated from the retention time calibrat
40、ion following Annex A and the recovery at 720 C (C100) or 750 C (C120) is determined. NOTE Further guidance on the algorithm used is given in Annex B. Two procedures are described in this standard: Procedure A, Single analysis mode: The boiling range can be determined by a single analysis, but with
41、a modified (quench corrected) detector response for those components that co-elute with the sample diluent. A quench compensation calculation procedure is described in C.5 Procedure B, Dual analysis mode: This is an extension to the Procedure A method, where Procedure A is used to determine the boil
42、ing point distribution from C9through C100or C120. The extension to an analysis of the front end of the sample (including the quenched co-elution region) is achieved by a second analysis. This so-called Detailed Hydrocarbon Analysis (DHA) is used to determine the boiling point distribution from C1up
43、 to C9. The results from Procedure A and DHA analysis are merged using the calculation procedure described in Annex D. Procedure B does not use the compensation calculation procedure given in C.5. Procedure A (Single Analysis Mode): Cryogenic Initial Column Temperature (see Table 2) is preferred to
44、improve resolution of low boiling components. Procedure B (Dual Analysis Mode): Ambient Initial Column Temperature is used on the analyzer as the low boiling components (C1to C9) are analyzed on the DHA system. DIN EN 15199-3:2008-09 EN 15199-3:2008 (E) 7 5 Reagents and materials Unless otherwise st
45、ated, only chemicals of recognized analytical quality shall be used. 5.1 Liquid stationary phase, a methyl silicone stationary phase for the column. 5.2 Carrier gases, helium, nitrogen or hydrogen, with a purity no less than 99,999 % (V/V), and any oxygen present removed by a chemical resin filter.
46、WARNING Follow the safety instructions from the filter supplier. 5.3 Hydrogen, grade suitable for flame ionisation detectors. 5.4 Compressed air, regulated for flame ionisation detectors. 5.5 Alkanes, normal alkanes with a purity of at least 98 % (m/m) from C5to C10, C12, C14, C16, C18, C20, C24and
47、C28to be used with Polywax (see 5.6). NOTE The calibration mixture from ISO 3924 3 is also suitable. 5.6 Polywax 655 or 1000 5.7 Carbon disulfide, with a purity of no less than 99,7 % (V/V). WARNING Extremely flammable and toxic by inhalation. NOTE To confirm the suitability of the carbon disulfide
48、as a solvent, it is recommended to check elution profiles (see Figure 2). Figure 2 Example of a good (A) and a bad (B) carbon disulfide solvent peak shape1)5.8 Calibration mixture The mixture shall contain at least one normal alkane with a boiling point lower than the IBP of the sample, and at least
49、 one normal alkane with a boiling point close to the temperature at which the recovery is measured. Dissolve 0,1 g of Polywax (5.6) in 7 ml carbon disulfide (5.7), warming gently if necessary. Prepare an equal volume mixture of alkanes (5.5) and add 10 l to the Polywax solution. NOTE 1 Commercially available alkane standards are suitable for column performance checks. NOTE 2 The calibration mix is used to determine the column resolution, skewness of the C20peak, and retention time versus boiling point calibration c
