SIST EN 15199-1:2021

SLOVENSKI STANDARD
01-marec-2021
Nadomešča:
SIST EN 15199-1:2006
Naftni proizvodi - Določanje porazdelitve območja vrelišč z metodo plinske
kromatografije - 1. del: Srednji destilati in mazalna olja
Petroleum products - Determination of boiling range distribution by gas chromatography
method - Part 1: Middle distillates and lubricating base oils
Mineralölerzeugnisse - Gaschromatographische Bestimmung des Siedeverlaufes - Teil 1:
Mitteldestillate und Grundöle
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
Ta slovenski standard je istoveten z: EN 15199-1:2020
ICS:
75.080 Naftni proizvodi na splošno Petroleum products in
general
75.100 Maziva Lubricants, industrial oils and
related products
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EN 15199-1
EUROPEAN STANDARD
NORME EUROPÉENNE
December 2020
EUROPÄISCHE NORM
ICS 75.080 Supersedes EN 15199-1:2006
English Version
Petroleum products - Determination of boiling range
distribution by gas chromatography method - Part 1:
Middle distillates and lubricating base oils
Produits pétroliers - Détermination de la répartition Mineralölerzeugnisse - Gaschromatographische
dans l'intervalle de distillation par méthode de Bestimmung des Siedeverlaufes - Teil 1:
chromatographie en phase gazeuse - Partie 1 : Distillats Mitteldestillate und Grundöle
moyens et huiles lubrifiantes
This European Standard was approved by CEN on 23 November 2020.

CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this
European Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references
concerning such national standards may be obtained on application to the CEN-CENELEC 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
translation under the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management
Centre has the same status as the official versions.

CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway,
Poland, Portugal, Republic of North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2020 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 15199-1:2020 E
worldwide for CEN national Members.

Contents Page
European 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 . 11
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 . 14
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 . 16
Annex A (normative) Calculation procedure . 17
Annex B (normative) System performance check . 22
Annex C (normative) Boiling points of n-alkanes . 24
Bibliography . 26

European foreword
This document (EN 15199-1:2020) 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 June 2021, and conflicting national standards shall be
withdrawn at the latest by June 2021.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
This document supersedes EN 15199-1:2006.
The main changes in this edition are:
—  the precision is extended for the recovery points between 10 % and 50 %;
—  the text has been updated editorially in order to give better guidance to operators executing the
test.
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;
— Part 4: Light fractions of crude oil.
This document specifies 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 can
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 can be used. Part 4 describes the determination of boiling
range distribution of hydrocarbons up to n-nonane in crude oil.
This document is based on IP Test Method IP 480 [4] and ASTM Test Method ASTM D6352 [3].
According to the CEN-CENELEC Internal Regulations, the national standards organisations of the
following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria,
Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland,
Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Republic of
North Macedonia, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the
United Kingdom.
1 Scope
This document specifies a method for the determination of the boiling range distribution of petroleum
products by capillary gas chromatography using flame ionization 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 naphtha’s, reformates, gasolines) or middle distillates like
Diesel and Jet fuel.
Petroleum or petroleum products containing blending components which contain heteroatoms (for
example alcohols, ethers, acids, or esters) or residue are not to be analysed by this test method.
NOTE For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to represent
respectively the mass fraction and the volume fraction.
WARNING — The use of this document can involve hazardous materials, operations and equipment.
This document 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 documents are referred to in the text in such a way that some or all of their content
constitutes requirements 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)
EN ISO 3171, Petroleum liquids — Automatic pipeline sampling (ISO 3171)
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
— ISO Online browsing platform: available at https://www.iso.org/obp
— IEC Electropedia: available at http://www.electropedia.org/
3.1
initial boiling point
IBP
temperature corresponding to the retention time at which a net area counts equal to 0,5 % of the total
sample area (3.6) under the chromatogram is obtained (see Figure 1)
3.2
final boiling point
FBP
temperature corresponding to the retention time at which a net area (3.7) counts equal to 99,5 % of the
total sample area (3.6) under the chromatogram is obtained (see Figure 1)
3.3
area slice
area resulting from the integration of the chromatographic detector signal within a specified retention
time interval
Note 1 to entry: 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.
3.4
corrected area slice
area slice (3.3) 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 (3.4) from the beginning of the analysis through a given
retention time, ignoring any non-sample area for example of solvent
3.6
total sample area
cumulative corrected area (3.5), from the initial area point to the final area point, where the
chromatographic signal has returned to baseline after complete sample elution

Key
1 start of elution 4 end of elution
2 IBP (3.1) X retention time (minutes)
3 FBP (3.2) Y Response (pA)
Figure 1 — Typical chromatogram
3.7
net area
cumulative area counts for the sample minus the cumulative area count for the blank
3.8
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 n-alkanes, covering the
sample boiling range, under the same conditions. From these data, the boiling range distribution is
obtained.
Several SIMDIS methods are standardized test methods and each one is dedicated to a certain boiling
point range or product.
EN ISO 3924 [1] is limited to products having an initial boiling point greater than 55 °C, a final boiling
point lower than 538 °C and having a vapour pressure sufficiently low to permit sampling at ambient
temperature.
EN 15199-2 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.
EN 15199-3 is applicable to crude oils. The boiling range distribution and recovery (3.8) up to C or
C can be determined.
5 Reagents and materials
Unless otherwise stated, only chemicals of recognized analytical quality shall be used.
5.1 Carrier gas, helium, 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.
5.2   Hydrogen, grade suitable for flame ionization detectors.
5.3   Compressed air, suitable for flame ionization detectors.
5.4  Alkanes, n-alkanes of at least 98 % (m/m) purity from C to C , C , C , C , C , C , C and
5 10 12 14 16 18 20 24
C .
NOTE The calibration mixture from EN ISO 3924 [1] is also suitable.
5.5   Polywax 655® or 1000®
5.6   Carbon disulfide, (CS ) purity 99,7 % (V/V) minimum.
WARNING — Extremely flammable and toxic by inhalation.
CAUTION — It is recommended that all work with CS is carried out in an explosion protected fume
cupboard.
Cyclohexane (C H )—(>99 % pure) can be used in place of CS for the preparation of the calibration
6 12 2
mixture. However, the precision of this method is based on calibration mixtures, reference material and
samples prepared with CS only.
5.7   Calibration mixture
Dissolve 0,1 g of Polywax (5.5) in 7 ml CS (5.6), warming gently if necessary. Prepare an equal volume
mixture of alkanes (5.4) 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 C peak, and
retention time versus boiling point calibration curve.
5.8   Reference materials
5.8.1  A reference material has two functions:
— External Standard: to determine the recovery of samples by comparing the total sample area (3.6)
of the reference material with the total sample area (3.5) 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
(5.8.2).
5.8.2 Reference Material 5010, a reference sample that has been analysed by laboratories
participating in the test method cooperative study. Consensus values for the boiling range distribution
of this sample are given in Table 1.
5.8.3 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 2 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.

Table 1 — Reference Material 5010
Accepted
% Allowable difference
Reference
Recovery 95,5 % Confidence Interval
value
°C °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
Key
Y response (pA)
X retention time (minutes)
Figure 2 — Typical chromatogram of binary gravimetric blend distillate
6 Apparatus
6.1   Gas chromatograph, with the following performance characteristics.
6.1.1   Flame ionization detector, connected to the column 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.
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
6.2.1 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.
6.2.2 Use a metal column, 0,53 µm internal diameter coated with methyl silicone. Commercially
available columns with film thickness (d ) = 0,09 µm (for analysis up to C ) and (d ) = 0,17 µm (for
f 120 f
analysis up to C ) have been found to be satisfactory.
It is recommended that the column resolution, R, is at least 2 and not more than 4 (see B.2).
6.2.3  Use some form of column bleed compensation to obtain a stable baseline. This can 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
Unit Specification
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
Detector hydrogen flow (5.2) ml/min 35
Detector air flow (5.3) ml/min 350
Carrier gas — Helium
a
Carrier gas flow rate ml/min 19
Sample size µl 1,0
Sample concentration % (m/m) 2
Injector — PTV or COC
a
A carrier gas flow rate up to 25 ml/min can be used to ensure all material elutes before the
end of the temperature program.

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. 5 µl, for introduction of 1 µl of the calibration mixture
and test portions. 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, shall be of an explosion-protected design.
6.7   Analytical balance, capable of weighing to the nearest 0,1 mg.
7 Sampling
Samples shall be taken as specified in EN ISO 3170 or EN ISO 3171 (see the requirements of national
standards or regulations for the sampling of petroleum produc
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