1、BRITISH STANDARDBS EN 15199-2:2006 BS 2000-507: 2006Petroleum products Determination of boiling range distribution by gas chromatography method Part 2: Heavy distillates and residual fuelsThe European Standard EN 15199-2:2006 has the status of a British StandardICS 75.080g49g50g3g38g50g51g60g44g49g4
2、2g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58Licensed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIBS EN 15199-2:2006This British Standa
3、rd was published under the authority of the Standards Policy and Strategy Committee on 31 January 2007 BSI and Energy Institute 2007ISBN 978 0 580 50181 4National forewordThis British Standard was published by BSI. It is the UK implementation of EN 15199-2:2006.The UK participation in its preparatio
4、n was entrusted to Technical Committee PTI/13, Petroleum testing and terminology.A list of organizations represented on PTI/13 can be obtained on request to its secretary.Energy Institute, under the brand of IP, publishes and sells all Parts of BS 2000, and all BS EN petroleum test methods that woul
5、d be Part of BS 2000, both in its annual publication “Standard methods for analysis and testing of petroleum and related products and British Standard 2000 Parts” and individually.Further information is available from: Energy Institute, 61 New Cavendish Street, London W1G 7AR. Tel: 020 7467 7100. Fa
6、x: 020 7255 1472.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations.Amendments issued since publicationAmd. No. Date CommentsLicens
7、ed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15199-2October 2006ICS 75.080English VersionPetroleum products - Determination of boiling range distributionby gas chromatography method - Part 2: Heavy distillates
8、andresidual fuelsProduits ptroliers - Dtermination de la rpartition danslintervalle de distillation par mthode chromatographie enphase gazeuse - Partie 2: Distillats severes et residualsMinerallerzeugnisse - GaschromatographischeBestimmung des Siedeverlaufes - Teil 2: Schwerle undRckstandsleThis Eur
9、opean Standard was approved by CEN on 28 August 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 con
10、cerning 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 l
11、anguage 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, M
12、alta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of explo
13、itation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15199-2:2006: ELicensed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-2:2006 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Terms and definitio
14、ns .4 4 Principle6 5 Reagents and materials 6 6 Apparatus .9 7 Sampling procedure 10 8 Preparation of the apparatus10 8.1 Gas chromatograph preparation10 8.2 System performance check 10 9 Sample and reference material preparation10 10 Calibration 11 11 Procedure .13 12 Visual inspection of the chrom
15、atograms 13 13 Calculation14 14 Expression of results 14 15 Precision.14 15.1 General14 15.2 Repeatability.14 15.3 Reproducibility.14 16 Test report 15 Annex A (normative) Calculation procedure16 Annex B (normative) System performance check .19 Annex C (informative) Boiling points of normal alkanes
16、21 Annex D (informative) Additional guidance for the calculation algorithm22 Bibliography 26 Licensed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-2:2006 (E) 3 Foreword This document (EN 15199-2:2006) has been prepared by Technical Committee CEN/TC 19 “G
17、aseous 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 Ap
18、ril 2007, and conflicting national standards shall be withdrawn at the latest by April 2007. 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
19、oils Part 2: Heavy distillates and residual fuels Part 3: Crude oil This part of the standard describes the determination of boiling range distribution of materials with initial boiling points (IBP) above 100 C and final boiling points (FBP) above 750 C. For testing materials with initial boiling po
20、ints (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) below 100 C and final boiling points (FBP) above 750 C, such as crude oils, Part 3 is applicable. This part of the standard is a joint develop
21、ment between the EI 1, ASTM 2 and CEN. 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, Hunga
22、ry, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Licensed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-2:2006 (E) 4 1 Sco
23、pe This European Standard specifies 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 materials having a vapour pressure low enough to permit sampling at ambient tempe
24、rature, and which have a boiling range of at least 100 C. The standard is applicable to materials with initial boiling points (IBP) above 100 C and final boiling points (FBP) above 750 C, for example, heavy distillate fuels and residuals. The method is not applicable to bituminous samples. The test
25、method is not applicable for the analysis of petroleum or petroleum products containing low molecular weight components (for example naphthas, reformates, gasolines, diesel). Components containing hetero atoms (for example alcohols, ethers, acids, or esters) or residue are not to be analyzed by this
26、 test method. NOTE 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 The use of this European Standard may involve hazardous materials, operations and equipment. This European Standard d
27、oes 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 re
28、ferenced 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 ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN
29、 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 some of the terms is given in Figure 1. 3.1 initial boiling point IBP temperature corresponding to the re
30、tention 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 which a net area count equal to 99,5 % of the total sample area under the chromatogram is obtained 3.3 area
31、 slice area resulting from the integration of the chromatographic detector signal within a specified retention time interval Licensed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-2:2006 (E) 5 NOTE In area slice mode peak detection parameters are bypassed
32、 and the detector signal integral is recorded as area slices of consecutive, fixed duration time interval. Key: 1 start of elution 2 initial boiling 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 offse
33、t by subtraction of the exactly corresponding area slice in a previously recorded blank (non-sample) analysis 3.5 cumulative corrected area accumulated 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
34、3.6 slice rate time interval used to integrate the continuous (analogue) chromatographic detector response during an analysis NOTE The slice rate 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
35、 chromatographic analysis NOTE The slice time is the time at the end of each contiguous area slice. 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 Licensed C
36、opy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-2:2006 (E) 6 3.9 net area cumulative area counts for the sample minus the cumulative area count for the blank 3.10 recovery ratio of the cumulative area count of the sample to that of the reference material (ex
37、ternal standard) corrected for dilution and material weights combined with the percentage of light ends, if applicable 4 Principle A test portion is introduced into a gas chromatographic column, which separates hydrocarbons in the order of increasing boiling point. The column temperature is raised a
38、t a linear reproducible rate and the area under the chromatogram is recorded throughout the analysis. Boiling points are assigned to the time-axis from a calibration curve, which is obtained by running a mixture of known normal alkanes covering the test portion boiling range, under the same conditio
39、ns. From these data, the boiling range distribution is obtained. The recovery at a specified temperature is determined by comparing the area under the chromatogram with that of a reference standard which has been completely eluted. The temperature at which the recovery was measured is recorded. NOTE
40、 If the found recovery is less than 100 %, the final boiling point is reported as 720 C or 750 C at that recovery. 5 Reagents and materials Unless otherwise stated, only chemicals of recognized analytical quality shall be used. 5.1 Liquid stationary phase, a methyl silicone stationary phase for the
41、column. 5.2 Carrier gases, helium, nitrogen or hydrogen, of at least 99,999 % (V/V) purity. Any oxygen present is removed by a chemical resin filter. Warning Follow the safety instructions from the filter supplier. 5.3 Hydrogen, grade suitable for flame ionisation detectors. 5.4 Compressed air, regu
42、lated for flame ionisation detectors. 5.5 Alkanes, normal alkanes of at least 98 % (m/m) purity from C5to C10, C12, C14, C16, C18, C20, C24and C28to be used with Polywax 655 or 1000 (5.6). NOTE The calibration mixture from ISO 3924 3 is also suitable. 5.6 Polywax 655 or 1000 5.7 Carbon disulfide, wi
43、th a minimum purity of 99,7 % (V/V). WARNING Extremely flammable and toxic. NOTE To confirm the suitability of the carbon disulfide as a solvent, it is recommended to check elution profiles (see Figure 2). Licensed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN
44、15199-2:2006 (E) 7 Key: / good X bad Figure 2 Solvent peak shape 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 one normal alkane with a boiling point close to the temperature at which the recovery is m
45、easured. 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 calibrati
46、on mix is used to determine the column resolution, skewness of the C20peak, and retention time versus boiling point calibration curve. 5.9 Reference materials (RM) 5.9.1 A reference material has two functions: External Standard: to determine the recovery of samples by comparing the total sample area
47、 (3.8) of the reference material with the total sample area of the unknown sample. Boiling Point Distribution Standard: to check the proper functioning of the system by comparing the results with a known boiling point distribution on a routine basis. Typical example is given in (5.9.2). 5.9.2 Refere
48、nce Material 5010, a reference sample that has been analyzed by laboratories participating in the test method cooperative study. Consensus values for the boiling range distribution of this sample are given in Table 1. 5.9.3 Cyclohexane. (C6H12)(99+ % pure) may be used in place of CS2for the preparat
49、ion of the calibration mixture. 5.9.4 Binary gravimetric blend, a binary distillate mixture with boiling points ranges that gives a baseline at the start, a baseline between the two peaks and an end time that is as close to the end of the chromatogram as possible (see Figure 3 and B.3). This mixture is used to check the relative response of the two distillates and to check the baselines at the start, middle and end of the chromatogram. Licensed Copy: Wang Bin, na, Wed Apr 11 05:50:04 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15
