1、BRITISH STANDARDBS EN 15199-1:2006 BS 2000-480: 2006Petroleum products Determination of boiling range distribution by gas chromatography method Part 1: Middle distillates and lubricating base oilsThe European Standard EN 15199-1:2006 has the status of a British StandardICS 75.080g49g50g3g38g50g51g60
2、g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58Licensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIBS EN 15199-1:2006This Britis
3、h Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2007 BSI and Energy Institute 2007ISBN 978 0 580 50180 7National forewordThis British Standard was published by BSI. It is the UK implementation of EN 15199-1:2006.The UK participation in its pr
4、eparation 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 t
5、hat would 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
6、7100. Fax: 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 Commen
7、tsLicensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15199-1October 2006ICS 75.080English VersionPetroleum products - Determination of boiling range distributionby gas chromatography method - Part 1: Middle dis
8、tillates andlubricating base oilsProduits ptroliers - Dtermination de la rpartition danslintervalle de distillation par mthode par chromatographieen phase gazeuse - Partie 1: Distillats moyens et huileslubrifiantesMinerallerzeugnisse - GaschromatographischeBestimmung des Siedeverlaufes - Teil 1: Mit
9、teldestillateund GrundleThis European 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 an
10、d bibliographical references concerning 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 responsibilit
11、y of a CEN member into its own language 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,
12、Latvia, Lithuania, Luxembourg, Malta, 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 Bruss
13、els 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15199-1:2006: ELicensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-1:2006 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative re
14、ferences 4 3 Terms and definitions .4 4 Principle6 5 Reagents and materials 6 6 Apparatus .9 7 Sampling.10 8 Preparation of the apparatus11 8.1 Gas chromatograph preparation11 8.2 System performance check 11 9 Sample preparation .11 10 Calibration 11 11 Procedure .13 12 Visual inspection of the chro
15、matograms 13 13 Calculation14 14 Expression of results 14 15 Precision.14 15.1 General14 15.2 Repeatability.15 15.3 Reproducibility.15 16 Test report 15 Annex A (normative) Calculation procedure16 Annex B (normative) System performance check .20 Annex C (informative) Boiling points of normal alkanes
16、 22 Bibliography 23 Licensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-1:2006 (E) 3 Foreword This document (EN 15199-1:2006) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, sy
17、nthetic 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 April 2007, and conflicting national standards shall be withdrawn at the la
18、test 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 oils Part 2: Heavy distillates and residual fuels Part 3: Crude oil This p
19、art 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) below 750 C. 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. 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 may be used. This part of the standard is a joint development between the EI 1, ASTM 2 and CEN. According to the CEN/CENELEC Internal
21、 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, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlan
22、ds, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Licensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-1:2006 (E) 4 1 Scope This European Standard specifies a method for the determination of the bo
23、iling 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 temperature and a boiling range of at least 100 C. The standard is applicable to
24、distillates with initial boiling points (IBP) above 100 C and final boiling points (FBP) below 750 C, for example, middle distillates and lubricating base stocks. The test method is not applicable for the analysis of petroleum or petroleum products containing low molecular weight components (for exa
25、mple naphthas, reformates, gasolines, diesel). Components containing hetero atoms (for example alcohols, ethers, acids, or esters) or residue are not to be analyzed by this test method. NOTE For the purposes of this European Standard, the terms “% (m/m)” and “% (V/V)” are used to represent respectiv
26、ely the mass fraction and the volume fraction. WARNING The use of this 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 stan
27、dard to establish appropriate safety and health practices and to determine 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.
28、 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 ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171:1988) 3 Terms and definitions For the purposes of this docume
29、nt, 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 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 boil
30、ing 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 slice area resulting from the integration of the chromatographic detector signal within a specified retention time interval NOT
31、E 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. Licensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-1:2006 (E) 5 3.4 corrected area sl
32、ice 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 accumulated sum of corrected area slices from the beginning of the analysis through a given retention time, ignoring
33、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 is expressed in Hz (for example integrations per second or slices per second). 3.7 slice time analysis time ass
34、ociated with each area slice throughout the chromatographic analysis NOTE The slice time is the time at the end of each contiguous area slice. Key: 1 start of elution 2 initial boiling point (IBP) 3 final boiling point (FBP) 4 end of elution Figure 1 Typical chromatogram 3.8 total sample area cumula
35、tive 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 Licensed Copy: Wang Bin, na, Wed Apr 11 0
36、5:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-1:2006 (E) 6 3.10 recovery 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 Princip
37、le 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 at a linear reproducible rate and the area under the chromatogram is recorded throughout the analysis. Boiling points are assigne
38、d to the time-axis from a calibration curve obtained by running a mixture of known normal alkanes, covering the sample boiling range, under the same conditions. From these data, the boiling range distribution is obtained. 5 Reagents and materials Unless otherwise stated, only chemicals of recognized
39、 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, of at least 99,999 % (V/V) purity. Any oxygen present is removed by a chemical resin filter. WARNING Follow the safety instructions from
40、 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 of at least 98 % (m/m) purity from C5to C10, C12, C14, C16, C18, C20, C24and C28to be used with Polywax (5.6). NOTE The calibrat
41、ion mixture from ISO 3924 3 is also suitable. 5.6 Polywax 655 or 1000 5.7 Carbon disulfide, purity 99,7 % (V/V) minimum. WARNING Extremely flammable and toxic by inhalation. NOTE To confirm the suitability of the carbon disulfide as a solvent, it is recommended to check elution profiles (see Figure
42、2). Licensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-1:2006 (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 a
43、t least one normal alkane with a boiling point higher than the FBP of the sample. 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 s
44、tandards 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 curve. 5.9 Reference materials (RM) 5.9.1 A reference material has two functions: External Standard
45、: to determine the recovery of samples by comparing the total sample area (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 distribut
46、ion on a routine basis. A typical example is given in (5.9.2). 5.9.2 Reference 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 C
47、yclohexane. (C6H12)(99+ % pure) may be used in place of CS2for the preparation 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 t
48、he 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 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (
49、c) BSIEN 15199-1:2006 (E) 8 Table 1 Reference Material 5010 % recovered Reference temperatureC Maximum allowable range 95,5 % CI C IBP 428 9 5 477 3 10 493 3 15 502 3 20 510 3 25 518 4 30 524 4 35 531 4 40 537 4 45 543 4 50 548 5 55 554 4 60 560 4 65 566 4 70 572 4 75 578 5 80 585 4 85 593 4 90 602 4 95 616 4 FBP 655 18 Licensed Copy: Wang Bin, na, Wed Apr 11 05:47:56 GMT+00:00 2007, Uncontrolled Copy, (c) BSIEN 15199-1:2006 (E) 9 Key: A response B retention time (min) Figure 3 Typical chromatogram of binary gravimetric blend
