SIST EN 15199-2:2006

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 2: Schweröle und RückstandsöleProduits pétroliers - Détermination de la répartition dans l'intervalle de distillation par méthode de chromatographie en phase gazeuse - Partie 2: Fiouls lourds et fiouls résiduelsPetroleum products - Determination of boiling range distribution by gas chromatography method - Part 2: Heavy distillates and residual fuels75.160.01Goriva na splošnoFuels in general75.080Naftni proizvodi na splošnoPetroleum products in generalICS:Ta slovenski standard je istoveten z:EN 15199-2:2006SIST EN 15199-2:2006en01-december-2006SIST EN 15199-2:2006SLOVENSKI
STANDARD



SIST EN 15199-2:2006



EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15199-2October 2006ICS 75.080 English VersionPetroleum products - Determination of boiling range distributionby gas chromatography method - Part 2: Heavy distillates andresidual fuelsProduits pétroliers - Détermination de la répartition dansl'intervalle de distillation par méthode chromatographie enphase gazeuse - Partie 2: Distillats severes et residualsMineralölerzeugnisse - GaschromatographischeBestimmung des Siedeverlaufes - Teil 2: Schweröle undRückstandsöleThis 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 and 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 responsibility 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, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania,Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2006 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15199-2:2006: ESIST EN 15199-2:2006



EN 15199-2:2006 (E) 2 Contents Page Foreword.3 1 Scope.4 2 Normative references.4 3 Terms and definitions.4 4 Principle.6 5 Reagents and materials.6 6 Apparatus.9 7 Sampling procedure.10 8 Preparation of the apparatus.10 8.1 Gas chromatograph preparation.10 8.2 System performance check.10 9 Sample and reference material preparation.10 10 Calibration.11 11 Procedure.13 12 Visual inspection of the chromatograms.13 13 Calculation.14 14 Expression of results.14 15 Precision.14 15.1 General.14 15.2 Repeatability.14 15.3 Reproducibility.14 16 Test report.15 Annex A (normative)
Calculation procedure.16 Annex B (normative)
System performance check.19 Annex C (informative)
Boiling points of normal alkanes.21 Annex D (informative)
Additional guidance for the calculation algorithm.22 Bibliography.26
SIST EN 15199-2:2006



EN 15199-2:2006 (E) 3 Foreword This document (EN 15199-2:2006) 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 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 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 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 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) 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 development 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, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
SIST EN 15199-2:2006



EN 15199-2:2006 (E) 4 1 Scope 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 temperature, 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 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 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 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 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. 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 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 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 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 SIST EN 15199-2:2006



EN 15199-2:2006 (E) 5 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 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 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 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 associated with each area slice throughout the 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 SIST EN 15199-2:2006



EN 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 (external 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 at 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 conditions. 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 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 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, regulated for flame ionisation detectors. 5.5 Alkanes, normal alkanes of at least 98 % (m/m) purity from C5 to C10, C12, C14, C16, C18, C20, C24 and C28 to 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, with 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). SIST EN 15199-2:2006



EN 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 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 µl 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 C20 peak, 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 (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 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 Cyclohexane. (C6H12)—(99+ % pure) may be used in place of CS2 for 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 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. SIST EN 15199-2:2006



EN 15199-2:2006 (E) 8
Key: A response B retention time (min) Figure 3 — Typical chromatogram of binary gravimetric blend distillate Table 1 — Reference Material 5010 % recovered Reference temperature°C 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
SIST EN 15199-2:2006



EN 15199-2:2006 (E) 9 6 Apparatus 6.1 Gas chromatograph, with the following performance characteristics. 6.1.1 Flame ionisation detector, connected to the column so as to avoid any cold spots. The detector shall be capable of operating at a temperature at least equivalent to the maximum column temperature employed in the method. NOTE The capillary column should sit just below the flame tip and it is recommended that the orifice of the jet should be 0,6 mm minimum to prevent frequent blocking with silicones. 6.1.2 Column temperature programmer, capable of linear programmed temperature operation over a range of 10 °C above ambient to 450 °C. 6.1.3 Sample inlet system, consisting of a programmable temperature vaporizer (PTV) or cold on-column (COC) injection port. The maximum temperature of the injection device shall be equal to, or higher than, the final oven temperature. The minimum temperature shall be low enough to prevent sample or solvent flashback, but high enough to allow sample focusing at the front of the column. Table 2 contains the typical operating conditions. 6.2 Column Use a metal column with 0,53 mm internal diameter and coated with methyl silicone (5.1). Commercially available columns with film thickness (df) = 0,09 µm (for analysis up to C120) and (df) = 0,17 µm (for analysis up to C100) have been found to be satisfactory. NOTE 1 It is recommended that the column resolution, R, is at least 2 and not more than 4 (see B.2). Use some form of column bleed compensation to obtain a stable baseline. NOTE 2 This may be carried out by subtraction of a column bleed profile previously obtained using exactly the same conditions as used for the sample analysis, by injecting the same volume, using solvent for the blank run and sample dilution from one batch taken at the same time, to avoid differences due to contamination. Table 2 — Typical operating conditions for gas chromatograph Column length, m 5 Column internal diameter, mm 0,53 Column material Ultimetal Stationary phase Methyl silicone Film thickness, µm 0,09 or 0,17 Initial column temperature, °C 35 Final column temperature, °C 430 Program rate, °C/min 10 Injector initial temperature, °C 100 Injector final temperature, °C 430 Program rate, °C/min 15 Hold time, min 5 Detector temperature, °C 450 Carrier gas He Carrier gas flow rate, ml/min 19 Sample size, µl 1,0 Sample concentration, % (m/m) 2 Injector PTV or COC SIST EN 15199-2:2006



EN 15199-2:2006 (E) 10 6.3 Carrier gas control The chromatograph shall be able to deliver a constant carrier gas flow over the whole temperature range of the analysis. 6.4 Micro-syringe, of appropriate volume, e.g. 10 µl, for introduction of 1 µl of the calibration mixture and test portions. NOTE 1 The micro-syringe may be operated either manually or automatically. NOTE 2 Plunger in needle syringes are not recommended due to excessive carry over of heavy ends to the following analysis. 6.5 Volumetric flask, 10 ml capacity. 6.6 Refrigerator NOTE It is recommended that the refrigerator be of an explosion-protected design. 6.7 Analytical balance, able to weigh with a precision of 0,1 mg. 7 Sampling procedure Samples shall be taken as described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the requirements of national standards or regulations for the sampling of petroleum products. Store samples in either glass or metal containers. Plastic containers for sample storage shall not be used as prolonged contact with the sample can cause contamination of the sample due to possible leaching of the plasticizer. 8 Preparation of the apparatus 8.1 Gas chromatograph preparation 8.1.1 Set up and operate the gas chromatograph in accordance with the manufacturer’s instructions. Typical operating conditions are shown in Table 2. 8.1.2 Deposits may form on the jet from combustion of decomposition products from the liquid stationary phase. These will affect the characteristics of the detector and shall be removed. NOTE The following parameters are affected by deposits on the jet: increase in inlet pressure; FID difficult to light; increase in the CS2 response and an off specification reference material. To clean the jet, it is recommended that it is put in an ultrasonic cleaner with a suitable solvent, and a cleaning wire used. 8.2 System performance check Check the system performance at the intervals given and by the procedures specified in Annex B. 9 Sample and reference material preparation 9.1 Mix the sample by shaking, warming prior to shaking where necessary. 9.2 Weigh approximately 0,1 g to 0,3 g of the sample to the nearest 0,1 mg, into a clean 10 ml volumetric flask (0.5) and add 5 ml to 7 ml carbon disulfide. SIST EN 15199-2:2006



EN 15199-2:2006 (E) 11 CAUTION — It is recommended that all work with carbon disulfide is carried out in an explosion protected fume cupboard. Shake the mixture to completely dissolve the test portion and then add carbon disulfide to the mark. Immediately transfer the solution to auto test portion vials, seal, and store in a refrigerator until ready for use. If the density of the sample is known, the test portion may be prepared on a mass/mass basis, and the following correction applied: ()+=22111100%σσmmmVm (1) where m1 is the mass of the test portion, in grams; m2 is the mass of carbon disulfide, in grams; 11 is the density of the test portion at 20 °C, in kilograms per litre; 12 is the density of carbon disulfide at 20 °C, in kilograms per litre (= 1,26). NOTE The density is quoted at 20 °C as a temperature approximately ambient in most laboratories. If the laboratory temperature is outside 20 °C ± 5 °C, appropriate adjustments should be made. 10 Calibration 10.1 Proceed in accordance with 10.2 to 10.4 each day before sample analysis. The first run of the day shall not be a blank, a reference standard (5.9) or a test portion, but it may be the calibration mixture (5.8). 10.2 Run the calibration mixture (5.8) using the specified procedure described in Clause 11. NOTE Take care to ensure the test portion volume chosen does not allow any peak to exceed the linear range of the detector, or overload the column. A skew of > 3 indicates the sample is too concentrated and a skew of < 1 indicates an old column or dirty liner. As a guide, 1 µl of the calibration mixture (5.8) has been found to be suitable for columns with film thickness less than 0,17 µm. 10.3 Record the retention time of each component and plot the retention time versus the atmospheric boiling point for each component to obtain the calibration curve. NOTE The atmospheric boiling points of the alkanes are given in Annex C. A typical chromatogram of the calibration mixture (5.8) is given in Figure 4 and a typical calibration curve is given in Figure 5. 10.4 Run the reference material (5.9) using the specified procedure in Clause 11. Calculate the boiling range distribution of the reference material by the procedures specified in Annex A and compare this with the consensus values for the reference material used. If the results are not within the specified range, it is advised to carefully follow the manufacturer's instructions regarding chromatographic problem solving and related diagnostics. SIST EN 15199-2:2006



EN 15199-2:2006 (E) 12
Key: A response B retention time Figure 4 — Typical chromatogram of calibration mixture
Key A retention time B temperature °C Figure 5 — Typical calibration curve SIST EN 15199-2:2006



EN 15199-2:2006 (E) 13 11 Procedure 11.1 Run a solvent (blank) baseline analysis before the first sample analysis, and then after every five samples. Subtract blank baselines from subsequent analyses (see Figure 6). NOTE It is good practice to follow each test portion with a carbon disulfide blank to prevent carryover of heavy non-volatile material into the next analysis.
good baseline bad baseline bad baseline
merging parallel crossing
(high FBP) (low FBP) Figure 6 — Baselines The identification of a constant baseline at the end of the run is critical to the analysis. Constant attention shall be given to all factors that influence baseline stability, e.g. column substrate bleed, septum bleed, detector temperature control, constancy of carrier gas flow, leaks and instrument drift. The baseline at the end of each analysis shall merge with the baseline of the blank run associated with it. Both signals shall merge to confirm integrity; if they do not, the analysis shall be repeated. 11.2 Cool the column to the starting temperature, and inject the selected sample volume. 11.3 Immediately start programming the column temperature upward at a rate that produces the separation specified in B.2. 11.4 Continue the run until the time for the highest component used for calibration has been exceeded. 12 Visual inspection of the chromatograms Using the data system, expand the chromatogram of the secondary working standard or test portion, by 5 times. Merge the blank baseline and observe the following points: The start of the area of interest is taken at a point on the baseline where the blank and the test portion baselines are merged. This is taken before the start of the test portion and after the end of the solvent. The end of the area of interest of the test portion is taken at the retention time equivalent to the required temperature at which the recovery is determined. The end of the area of interest of the secondary working standard is taken at a point on the baseline where the blank and standard baselines are merged. This is taken before the end of the temperature programme. The start of the test portion is determined as given in A.5. SIST EN 15199-2:2006



EN 15199-2:2006 (E) 14 The end of the test portion is determined as given in A.6. 13 Calculation Use the calculation protocol given in Annex A for the production of results. 14 Expression of results Report the tabulated results as follows: a) report all temperatures to the nearest 1 °C; b) report all percentages to the nearest 1 % (m/m); c) report the 0,5 % (m/m) point as the initial boiling point, and the recovery at selected final elution temperature (720 ºC or 750 ºC); d) report intermediate percentages as required, at intervals of not less than 1 % (m/m). 15 Precision 15.1 General The precision was determined by statistical examination of inter-laboratory test results using EN ISO 4259 [4]. 15.2 Repeatability The difference between two test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values given in Table 3 only in one case in twenty. 15.3 Reproducibility The difference between two single and independent test results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values given in Table 3 only in one case in twenty. SIST EN 15199-2:2006



EN 15199-2:2006 (E) 15 Table 3 — Precision values % (m/m) recovered Repeatability (r) °C Reproducibility (R) °C IBP 2,1 8,7 5 0,9 3,8 10 0,7 3,3 20 0,8 3,6 30 0,8 4,1 40 1,2 5,2 50 1,4 6,7 60 2,0 6,7 70 2,9 6,4 80 4,0 6,7 90 5,9 9,5 95 8,1 13 Fractions % C Repeatability (r) % Reproducibility (R) % 300 < 0,1 0,6 350 < 0,1 0,6 400 0,1 0,7 450 0,2 0,7 500 0,3 0,8 550 0,4 1,2 600 0,6 1,7 650 0,8 2,0 700 1,0 2,0 750 No data available No data available 16 Test report The test report shall specify: a) a reference to this European Standard, i.e. EN 15199-2; b) the type and complete identification of the material tested; c) the result of the test (see Clause 14); d) any deviation, by agreement or otherwise, from the standard procedures specified; e) date of the test. SIST EN 15199-2:2006



EN 15199-2:2006 (E) 16 Annex A (normative)
Calculation procedure A.1 Application The algorithm given in this Annex only applies for a slice width of 0,1 s to 0,2 s (10 Hz to 5 Hz). The chromatogram for the reference material (5.9), the sample, and the baseline shall be zeroed. The baseline chromatogram is subtracted from the Reference Material 5010 (5.9.2) and from the sample chromatogram in order to obtain the net area. An extended procedure is given as informative guidance in Annex D. A.2 Starting conditions The following data are required for the commencement of calculations: i) sample data array (N data points); ii) reference material data array (N data points); iii) blank data array (N data points); iv) processed data file from calibration run with retention times of normal alkanes; v) boiling points of normal alkanes used in calibration run; vi) start sample time; vii) end sample time. The data collection of the test portion or reference shall be identical to the used data points in the blank. A.3 Zer
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