SIST EN 15984:2017

SLOVENSKI STANDARD
oSIST prEN 15984:2016
01-maj-2016
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Petroleum industry and products - Determination of composition of refinery heating gas
and calculation of carbon content and calorific value - Gas chromatography method
Mineralölindustrie und -produkte - Bestimmung der Zusammensetzung von Heizgas für
Raffinerien und Berechnung des Kohlenstoffgehaltes und des Heizwertes -
Gaschromtographisches Verfahren
Ta slovenski standard je istoveten z: prEN 15984
ICS:
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
75.160.30 Plinska goriva Gaseous fuels
oSIST prEN 15984:2016 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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oSIST prEN 15984:2016

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oSIST prEN 15984:2016


DRAFT
EUROPEAN STANDARD
prEN 15984
NORME EUROPÉENNE

EUROPÄISCHE NORM

April 2016
ICS 75.160.30 Will supersede EN 15984:2011
English Version

Petroleum industry and products - Determination of
composition of refinery heating gas and calculation of
carbon content and calorific value - Gas chromatography
method
 Mineralölindustrie und -produkte - Bestimmung der
Zusammensetzung von Heizgas für Raffinerien und
Berechnung des Kohlenstoffgehaltes und des
Heizwertes - Gaschromtographisches Verfahren
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee
CEN/TC 19.

If this draft becomes a European Standard, 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.

This draft European Standard was established by CEN 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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and
United Kingdom.

Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are
aware and to provide supporting documentation.

Warning : This document is not a European Standard. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a European Standard.


EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION

EUROPÄISCHES KOMITEE FÜR NORMUNG

CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels
© 2016 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 15984:2016 E
worldwide for CEN national Members.

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Contents Page
European foreword . 3
1 Scope . 4
2 Principle . 4
3 Reagents and materials . 4
4 Apparatus . 6
5 Gas chromatographic analysis. 6
5.1 Analysis systems . 6
5.2 System configuration . 6
5.3 Columns . 7
6 Calibration . 7
6.1 General . 7
6.2 Absolute response factors . 7
6.3 Relative response factors . 7
7 Calculation . 8
7.1 General . 8
7.2 Calculation of the non normalized mole fractions . 8
7.3 Validation of normalized composition (reference components) . 8
7.4 Calculation of carbon content . 9
7.5 Calculation of lower calorific value, on mass basis . 10
8 Expression of results . 10
9 Precision . 10
9.1 General . 10
9.2 Repeatability . 10
9.3 Reproducibility . 11
10 Test report . 11
Annex A (informative) Possible column combination . 12
Annex B (normative) Detector linearity check . 17
Annex C (informative) Calculation test data . 19
Annex D (normative) Data for calculation . 20
Bibliography . 21

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European foreword
This document (prEN 15984:2016) 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 document is currently submitted to the CEN Enquiry.
This document will supersede EN 15984:2011.
In this revision only the precision values have been updated to reflect the realistic values found in five
consecutive interlaboratory studies performed by the DIN/FAM over the years 2009 to 2014. These
pooled precision statements were calculated and approved by CEN/TC 19/WG 36.
This document is based on a DIN Standard [3] with the same scope.
3

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1 Scope
This draft European Standard defines a gas chromatographic analysis for the determination of the
composition of fuel gases, as used in refinery heating gas. These results are used to calculate the carbon
content and the lower calorific value.
With this gas chromatographic analysis, an overall of 23 refinery heating gas components are
determined in concentrations as typically found in refineries (see Table 1 for further details).
Water is not analyzed. The results represent dry gases.
NOTE 1 Depending on the equipment used, there is a possibility to determine higher hydrocarbons as well.
NOTE 2 For the purposes of this draft European Standard, the terms “% (V/V)” is used to represent the volume
fraction (φ).
IMPORTANT — 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.
2 Principle
This draft European Standard defines a procedure that is used to determine all components that are
present in a typical refinery heating gas, as indicated in Table 1.
NOTE The composition range in which each component can be analyzed does depend on the actual sample
composition as higher amounts of a certain component may affect the detection range of other components
eluting close by. The general ranges which apply to all the individual components are:
— hydrocarbons from 0,01 (mol/100 mol) up to 100 (mol/100 mol);
— non-condensable gases from 0,02 (mol/100 mol) up to 100 (mol/100 mol);
— for hydrogen sulfide a range between 0,1 (mol/100 mol) up to 10 (mol/100 mol) has been found applicable.
Three different analysis systems are necessary; they may be built in three separate gas
chromatographs, or be integrated into one.
Depending on the configuration, hydrocarbons with more than five carbon atoms are reported as a sum
parameter. The composition of the refinery heating gas is used to calculate the carbon content and the
calorific value. A typical procedure is described hereafter. A configuration is acceptable when the
determination gives the precision as described in Clause 9.
3 Reagents and materials
3.1 Gases.
3.1.1 Hydrogen, with a minimum purity of 99,995 % (V/V).
3.1.2 Helium, with a minimum purity of 99,995 % (V/V).
3.1.3 Nitrogen, with a minimum purity of 99,995 % (V/V).
3.1.4 Air, free of oil and water.
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3.1.5 Argon, as alternative for analysis system 2, with a minimum purity of 99,995 % (V/V).
3.2 Calibration sample.
A certified reference gas mixture in concentrations that allow the determination of the necessary
response factors (see 6.1) and retention times is required.
Table 1 — Refinery heating gas components
Number Description Chemical formula
1 Hydrogen H
2
2 Oxygen/Argon O /Ar
2
3 Nitrogen N
2
4 Carbon monoxide CO
5 Carbon dioxide CO
2
6 Hydrogen sulfide H2S
7 Methane CH
4
8 Ethane C H
2 6
9 Ethene C H
2 4
10 Ethyne (Acetylene) C H
2 2
11 Propane C H
3 8
12 Propene C H
3 6
13 Propyne (Methylacetylene) C H
3 4
14 Propadiene C H
3 4
15 iso-Butane C H
4 10
16 n-Butane C H
4 10
17 trans-2-Butene C H
4 8
18 1-Butene C H
4 8
19 2-Methyl-Propene C H
4 8
20 cis-2-Butene C H
4 8
21 1,3-Butadiene C H
4 6
22 iso-Pentane C H
5 12
23 n-Pentane C H
5 12
24 Other components with 5 or more Carbon atoms, excluding iso- and
n-Pentane (C )
5+

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4 Apparatus
4.1 Usual laboratory apparatus and glassware.
4.2 Gas chromatographic apparatus, consisting of at least three separation systems able to work
simultaneously in one gas chromatograph, with a Thermal Conductivity Detector (TCD) and Flame
Ionization Detector (FID) that should be available, and confirming to the requirements as given in
Clause 5.
5 Gas chromatographic analysis
5.1 Analysis systems
The gas chromatographic system consist of the following three parts:
1) Analysis system 1:
All components except hydrogen (see Table 1) are retained on a porous polymer and a molecular sieve
column and back flushed.
© ©
NOTE HayeSep and Molsieve are examples of such commercially available columns.
Hydrogen is determined on a TCD with nitrogen (3.1.3) as the carrier gas (see Figure A.4).
2) Analysis system 2:
The second analysis system separates non-condensable gases, carbon dioxide, and hydrocarbons with
two carbon atoms and hydrogen sulfide with helium (3.1.2) as the carrier gas and a TCD as a detector.
After a pre-separation on a porous polymer column (column 3) propane and higher hydrocarbons are
back flushed and vented. See Figure A.5 for details.
When the inert gases (O /Ar, N , CH and CO) are on the molecular sieve 13X column, this column is
2 2 4
isolated. Carbon dioxide, the C -hydrocarbons and hydrogen sulfide are eluted from the porous polymer
2
column (column 4) and are detected. The C -hydrocarbons from this fraction are not used for
2
quantification. After this the molecular sieve 13X column (column 6) is eluted and the components are
determined on the TCD. Methane is quantified on Analysis System 3.
3) Analysis system 3
The third analysis system separates and quantifies all hydrocarbons by an FID and hydrogen (3.1.1) or
helium (3.1.2) as the carrier gas. Two columns are used in series. From the methyl silicone column
(column 1), the components above a certain cut point e.g. n-pentane are back flushed and determined as
a summed peak. The hydrocarbons from the alumina oxide column, column 2, are then separated and
quantified. See Figure A.6 for details.
5.2 System configuration
The gas chromatographic system may consist of one or more gas chromatographs, with the possibility
for isothermal or temperature programmed runs or both depending on the selected system
configuration. A TCD and an FID shall be available.
A gas flow control system and gas sampling valves and switching valves are used.
Means for quantification shall be provided.
Optionally a vaporizer may be used.
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5.3 Columns
A combination of packed and capillary columns is possible.
It shall be ascertained that a quantitative separation of all the components that need to be determined
(see Table 1) is possible and that the summed total of C is quantitative. Adequate separation is
5+
required between the components on all three separation systems.
If cyclopropane can be determined, it shall be summed to propene.
An example for a typical configuration is given in Annex A.
6 Calibration
6.1 General
Depending on the production procedure of the reference gas mixture, it might be necessary to convert
the concentration units of the components in the calibration gas to (mol/mol) %.
Linearity of the detectors shall be checked according to Annex B.
If calibration is necessary, e.g. daily or for an analysis series, a reference gas mixture shall be analyzed.
For each analysis system (see 5.1) at least one component, the reference component, needs to be
calibrated. For example, for analysis system 1 hydrogen, for analysis system 2 nitrogen and for analysis
system 3 propane. With these three components, an external calibration is done. The absolute response
factor is calculated.
For all the other components, relative response factors will be used (see 6.3).
The relative response factor of the reference component will be set at 1,0.
As alternative all absolute response factors can be determined for all the components that need to be
analyzed in a
...