SIST EN 15199-1:2006
(Main)Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils
Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils
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 a boiling range of at least 100 °C. The standard is applicable to 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 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.
Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 1: Mitteldestillate und Grundöle
Diese Europäische Norm legt ein Verfahren zur Bestimmung des Siedeverlaufes in Mineralölerzeugnissen mit Hilfe der Kapillar-Gaschromatographie mit einem Flammenionisationsdetektor (FID) fest. Die Norm ist anwendbar auf Mineralölerzeugnisse mit einem für die Probenahme bei Umgebungstemperatur ausreichend niedrigen Dampfdruck und mit einem Siedebereich von mindestens 100 °C. Die Norm ist anwendbar auf Destillate mit einem Siedebeginn (IBP, Initial Boiling Point) oberhalb von 100 °C und mit einem Siedeende (FBP, Final Boiling Point) unterhalb von 750 °C, wie z. B. Mitteldestillate und Grundöle.
Das Prüfverfahren ist nicht einsetzbar für die Analyse von Mineralölerzeugnissen mit niedermolekularen Anteilen (z. B. Naphtha, Reformat, Ottokraftstoff, Dieselkraftstoff). Ebenso können Komponenten, die Heteroatome enthalten (z. B. Alkohole, Ether, Säuren oder Ester), mit diesem Prüfverfahren nicht untersucht werden.
ANMERKUNG Für den Anwendungsbereich dieser Norm werden die Bezeichnungen % (m/m) und % (V/V) für die Kennzeichnung des Massenanteils in Prozent und des Volumenanteils in Prozent verwendet.
WARNUNG Die Anwendung dieser Europäischen Norm kann den Einsatz gefährlicher Stoffe, Arbeitsgänge und Geräte mit sich bringen. Diese Europäische Norm gibt nicht vor, alle mit ihrer Anwendung verbundenen Sicherheitsprobleme anzusprechen. Der Anwender dieser Norm ist dafür verantwortlich, vorher angemessene Maßnahmen in Hinblick auf Sicherheit und Gesundheit zu ergreifen und die Anwendbarkeit einschränkender Vorschriften zu ermitteln.
Produits pétroliers - Détermination de la répartition dans l'intervalle de distillation par méthode de chromatographie en phase gazeuse - Partie 1: Distillats moyens et huiles lubrifiantes
La présente Norme européenne spécifie une méthode de détermination de la répartition dans l’intervalle de distillation des produits pétroliers par chromatographie en phase gazeuse capillaire avec une détection par ionisation de flamme. Cette Norme s’applique aux produits dont la pression de vapeur est suffisamment faible pour permettre l’échantillonnage a la température ambiante et dont l’intervalle de distillation est d’au moins 100 °C. La Norme s’applique aux distillats dont le point d’ébullition initial (PEI) est supérieur a 100 °C et le point d’ébullition final (PEF) est inférieur a 750 °C, par exemple, les distillats moyens et les huiles lubrifiantes.
La méthode d’essai ne s’applique pas pour l’analyse de pétrole ou de produits pétroliers ayant des composants de faible masse moléculaire (par exemple naphtas, réformats, carburants essence et carburant diesel). Les composants contenant des hétero-atomes (par exemple alcools, éthers, acides ou esters) ou les résidus ne peuvent pas etre analysés suivant cette méthode.
NOTE Pour les besoins de cette Norme européenne, les termes % (m/m) et % (V/V) sont utilisés pour représenter respectivement la fraction massique et la fraction volumique.
AVERTISSEMENT L’utilisation de la présente Norme européenne implique l’utilisation de produits, d’opérations et d’équipements a caractere dangereux. La présente Norme européenne n’a pas la prétention d’aborder tous les problemes de sécurité concernés par son usage. Il est de la responsabilité de l’utilisateur de consulter et d’établir des regles de sécurité et d’hygiene appropriées et de déterminer l’applicabilité des restrictions réglementaires avant utilisation.
Naftni proizvodi - Določanje porazdelitve območja vrelišč z metodo plinske kromatografije - 1. del: Srednji destilati in mazalna olja
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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 1: Mitteldestillate und GrundöleProduits pétroliers - Détermination de la répartition dans l'intervalle de distillation par méthode de chromatographie en phase gazeuse - Partie 1: Distillats moyens et huiles lubrifiantesPetroleum products - Determination of boiling range distribution by gas chromatography method - Part 1: Middle distillates and lubricating base oils75.100MazivaLubricants, industrial oils and related productsICS:Ta slovenski standard je istoveten z:EN 15199-1:2006SIST EN 15199-1:2006en01-december-2006SIST EN 15199-1:2006SLOVENSKI
STANDARD
SIST EN 15199-1:2006
EUROPEAN STANDARDNORME EUROPÉENNEEUROPÄISCHE NORMEN 15199-1October 2006ICS 75.080 English VersionPetroleum products - Determination of boiling range distributionby gas chromatography method - Part 1: Middle distillates andlubricating base oilsProduits pétroliers - Détermination de la répartition dansl'intervalle de distillation par méthode par chromatographieen phase gazeuse - Partie 1: Distillats moyens et huileslubrifiantesMineralölerzeugnisse - GaschromatographischeBestimmung des Siedeverlaufes - Teil 1: Mitteldestillateund GrundöleThis 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 15199-1:2006: ESIST EN 15199-1:2006
EN 15199-1:2006 (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.10 8 Preparation of the apparatus.11 8.1 Gas chromatograph preparation.11 8.2 System performance check.11 9 Sample preparation.11 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.15 15.3 Reproducibility.15 16 Test report.15 Annex A (normative)
Calculation procedure.16 Annex B (normative)
System performance check.20 Annex C (informative)
Boiling points of normal alkanes.22 Bibliography.23
SIST EN 15199-1:2006
EN 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, 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) below 750 °C. 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. 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 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 15199-1:2006
EN 15199-1:2006 (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 a boiling range of at least 100 °C. The standard is applicable to 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 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 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. SIST EN 15199-1:2006
EN 15199-1:2006 (E) 5 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.
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 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 SIST EN 15199-1:2006
EN 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 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 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 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 (5.6). NOTE The calibration 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 2).
SIST EN 15199-1:2006
EN 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 at 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 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. 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 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 15199-1:2006
EN 15199-1:2006 (E) 8 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 15199-1:2006
EN 15199-1:2006 (E) 9
Key: A response B retention time (min) 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 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. SIST EN 15199-1:2006
EN 15199-1:2006 (E) 10 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
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 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. SIST EN 15199-1:2006
EN 15199-1:2006 (E) 11 8 Preparation of the apparatus 8.1 Gas chromatograph preparation 8.1.1 Set up and operate the gas c
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