SIST EN 15199-3:2008

2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 3: RohöleProduits pétroliers - Détermination de la répartition dans l'intervalle de distillation par chromatographie en phase gazeuse - Partie 3 : Pétrole brutPetroleum products - Determination of boiling range distribution by gas chromatography method - Part 3: Crude oil75.040Surova naftaCrude petroleumICS:Ta slovenski standard je istoveten z:EN 15199-3:2008SIST EN 15199-3:2008en01-julij-2008SIST EN 15199-3:2008SLOVENSKI
STANDARD



SIST EN 15199-3:2008



EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15199-3May 2008ICS 75.080 English VersionPetroleum products - Determination of boiling range distributionby gas chromatography method - Part 3: Crude oilProduits pétroliers - Détermination de la répartition dansl'intervalle de distillation par méthode de chromatographieen phase gazeuse - Partie 3: Pétrole brutMineralölerzeugnisse - GaschromatographischeBestimmung des Siedeverlaufes - Teil 3: RohöleThis European Standard was approved by CEN on 18 April 2008.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 CEN 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 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 are 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, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMITÉ EUROPÉEN DE NORMALISATIONEUROPÄISCHES KOMITEE FÜR NORMUNGManagement Centre: rue de Stassart, 36
B-1050 Brussels© 2008 CENAll rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15199-3:2008: ESIST EN 15199-3:2008



EN 15199-3:2008 (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.7 6 Apparatus.9 7 Sampling.11 8 Preparation of the apparatus.11 8.1 Gas chromatograph preparation.11 8.2 System performance check.11 9 Corrected sample and reference material preparation.11 10 Calibration.12 11 Procedure.13 12 Visual inspection of the chromatograms.14 13 Calculation.15 14 Expression of results.15 15 Precision.15 15.1 General.15 15.2 Repeatability.15 15.3 Reproducibility.15 16 Test report.16 Annex A (normative)
Calculation procedure.17 Annex B (informative)
Additional guidance for the calculation algorithm.20 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
SIST EN 15199-3:2008



EN 15199-3:2008 (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 status 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 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 distillates 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 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 of 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, 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 the United Kingdom. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 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 C100 or C120 can 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 standard 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 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 NOTE If the found recovery is less than 100 %, the final boiling point is reported as > 720 ºC or > 750 ºC at that recovery. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 5 3.3 area slice area resulting from the 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 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. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 6 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 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 use 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. Sample 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 components 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 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 calibration 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 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 boiling point distribution from C9 through C100 or 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 C1 up 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 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 (C1 to C9) are analyzed on the DHA system. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 7 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, with a purity no less than 99,999 % (V/V), and any oxygen present 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 with a purity of at least 98 % (m/m) from C5 to C10, C12, C14, C16, C18, C20, C24 and C28 to 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 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 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.
1)
These peak shapes are applicable only under cryogenic conditions. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 8 NOTE 3 For the DHA front end analysis, the calibration points are taken from the sample or a suitable calibration mixture. 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 (A.9.3).  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. Table 1 —Reference Material 5010 % OFF Average °C Allowable deviation ± °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 15199-3:2008



EN 15199-3:2008 (E) 9 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 point ranges that gives a baseline at the start, a baseline between the two peaks and an 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.
Key X retention time (min) Y response Figure 3 — Typical chromatogram of binary gravimetric blend distillate 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 the range mentioned in Table 2. 6.2 Column Use a metal column, 0,53 µm id 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. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 10 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. 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. Table 2 — Typical operating conditions for gas chromatograph
PTV Injector COC Injector Column length, m 5 5 Column internal diameter, mm 0,53 0,53 Column material Stainless steel Stainless steel Stationary phase Methyl silicone Methyl silicone Film thickness, µm 0,09 or 0,17 0,09 or 0,17 Initial column temperature, °C, Procedure A -20 -20 Initial column temperature, °C, Procedure B 40 40 Final column temperature, °C 430 430 Programme rate, °C/min 10 10 Hold time, min 5 5 Injector initial temperature, °C 100 ambient Injector final temperature, °C 430 no setpoint Programme rate, °C/min 15 15 Detector temperature, °C 430 430 Carrier gas He He Carrier gas flow rate, ml/min 19 19 Sample size, µl 1,0 1,0 Sample concentration, %(m/m) 2% a
2% a a see Clause 9
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 SIST EN 15199-3:2008



EN 15199-3:2008 (E) 11 7 Sampling 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. 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. NOTE Typical operating conditions are shown in Table 2. For Procedure B, where the front end is determined by a second analysis, the initial column temperature is higher than for Procedure A where a lower initial column temperature is recommended to optimise the resolution of the front end and to minimise co-elution of sample components with the solvent. 8.1.2 Deposits can form on the jet from combustion of decomposition products from the liquid stationary phase. These will affect the characteristics of the detector and should be removed. However, if poor results are still obtained, the jet should be replaced. 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 oil. 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 C. 9 Corrected 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 (6.5) and add 5 ml to 7 ml carbon disulfide. CAUTION — It is recommended that all work with carbon disulfide be 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: ()+=22111100σσmmmVm% (1) where
m1 is the mass of the test portion in grams; m2 is the mass of carbon disulfide, in grams; SIST EN 15199-3:2008



EN 15199-3:2008 (E) 12 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 Carry out the steps given in 10.2 to 10.4 each day before sample analysis. The first run of the day shall not be a blank, reference standard (5.9) or 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, 0,1 µl to 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 E. A typical chromatogram of the calibration mixture (5.8) is given in Figure 4 and a typical calibration curve is given in Figure 5.
Key X retention time Y signal Figure 4 — Typical chromatogram of calibration mixture SIST EN 15199-3:2008



EN 15199-3:2008 (E) 13 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.
Key X temperature (°C) Y retention time Figure 5 —
Typical calibration curve (retention time vs. temperature) 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 1 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. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 14
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 of the reference material. 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 (See Figure 6). NOTE 2 Users are encouraged to use in addition blank validation or rejection criteria proposed by simulated distillation software. 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 Annex C. 11.4 Continue the run until the time for the highest component used for calibration has been exceeded. 11.5 For Procedure B: Run the DHA front end analysis. NOTE A typical procedure for the DHA analysis is described in IP 344 [4]. 12 Visual inspection of the chromatograms Using the data system, expand the chromatogram of the reference material, 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 reference material baselines are merged. This is taken before the start of the sample and after the end of the solvent. SIST EN 15199-3:2008



EN 15199-3:2008 (E) 15  The end of the area of interest is taken at a point on the baseline where the blank and the reference material baselines are merged. This is taken after the end of the sample and at or before the end of run.  The start of the sample is determined as given in A.5.  The end of the sample is determined as given in A.6. 13 Calculation Use the calculation protocol given in Annex A for the production of results. For Procedure B: Merge these results with the data from the DHA front end analysis using Annex D. 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 99,5 % (m/m) point as the final boiling point; 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 [5] in a matrix of samples with properties in the range shown in Table 3. 15.2 Repeatability The difference between two test results, obtained by the same operator with the same apparatus under constant operating c
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