SIST EN 15984:2017
(Main)Petroleum industry and products - Determination of composition of refinery heating gas and calculation of carbon content and calorific value - Gas chromatography method
Petroleum industry and products - Determination of composition of refinery heating gas and calculation of carbon content and calorific value - Gas chromatography method
This European Standard specifies 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 analysed. 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 European Standard, the terms “% (V/V)” is used to represent the volume
fraction (φ).
WARNING — The use of this standard 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 users of this standard to take appropriate measures to ensure the safety and health of
personnel prior to application of the document, and fulfil statutory and regulatory requirements for this
purpose.
Mineralölindustrie und -produkte - Bestimmung der Zusammensetzung von Heizgas für Raffinerien und Berechnung des Kohlenstoffgehaltes und des Heizwertes - Gaschromatographisches Verfahren
Der Entwurf dieser Europäischen Norm beschreibt eine gaschromatographische Analyse für die Bestimmung der Zusammensetzung von Brenngasen, wie sie in Raffinerien als Heizgase verwendet werden. Die Ergebnisse werden zur Berechnung des Kohlenstoffgehaltes und des unteren Heizwertes verwendet.
Mit dieser gaschromatographischen Analyse werden insgesamt 23 Bestandteile von Heizgasen in Konzentrationen bestimmt, wie sie typischerweise in Raffinerien anfallen (siehe Tabelle 1 für weitere Informationen).
Wasser wird nicht analysiert. Die Ergebnisse beziehen sich auf trockene Gase.
ANMERKUNG 1 Je nach verwendeter Ausrüstung besteht die Möglichkeit, auch höhere Kohlenwasserstoffe zu bestimmen.
ANMERKUNG 2 Für die Zwecke dieses Europäischen Norm wird zur Angabe des Volumenanteils (φ) einer Substanz der Ausdruck "% (V/V)" verwendet.
WICHTIG - Diese Norm gibt nicht vor, alle mit ihrer Anwendung verbundenen Sicherheitsprobleme anzusprechen. Der Anwender dieser Internationalen Norm ist dafür verantwortlich, vorher angemessene Maßnahmen in Hinblick auf Sicherheit und Gesundheit zu ergreifen und die Anwendbarkeit einschränkender Vorschriften zu ermitteln.
Industries et produits pétroliers - Détermination de la composition des gaz combustibles de raffinerie, de leur pouvoir calorifique et de leur teneur en carbone - Méthode par chromatographie en phase gazeuse
La présente Norme européenne définit une méthode d’analyse chromatographique gazeuse pour la détermination de la composition des gaz combustibles de raffineries. Les résultats obtenus permettent de calculer leur teneur en carbone ainsi que leur pouvoir calorifique inférieur.
Cette analyse chromatographique des gaz permet de déterminer 23 composants des gaz combustibles de raffineries au total, à des concentrations habituellement trouvées dans les raffineries (voir le Tableau 1 pour de plus amples détails).
L’eau n’est pas analysée. Les résultats représentent les gaz à l’état sec.
NOTE 1 Selon l’équipement utilisé, il est aussi possible de déterminer les hydrocarbures supérieurs.
NOTE 2 Pour les besoins de la présente Norme européenne, les termes “% (V/V)” sont utilisés pour représenter la fraction volumique (φ).
IMPORTANT — La présente norme n'est pas censée aborder tous les problèmes de sécurité concernés par son usage. Il est de la responsabilité de l'utilisateur d'établir des règles de sécurité et d'hygiène appropriées et de déterminer l'applicabilité des restrictions réglementaires.
Naftna industrija in proizvodi - Določevanje sestave rafinerijskega plina za ogrevanje in izračunavanje vsebnosti ogljika in kalorične vrednosti - Plinska kromatografska metoda
Ta evropski standard določa analizo s plinsko kromatografijo za določanje sestave gorivnih plinov, kot se uporabljajo pri rafinerijskem plinu za ogrevanje. Rezultati se uporabljajo za izračun deleža ogljika in nižje kalorične vrednosti.
S to analizo s plinsko kromatografijo je skupaj določenih 23 komponent rafinerijskega plina za ogrevanje
v koncentracijah, ki so običajne za rafinerije (za dodatne podrobnosti glej preglednico 1).
Voda ni analizirana. Rezultati predstavljajo suhe pline.
OPOMBA 1 Glede na uporabljeno opremo obstaja tudi možnost določitve višjih ogljikovodikov.
OPOMBA 2 Za namene tega evropskega standarda se termin »% (V/V)« uporablja za prostorninski delež (φ).
OPOZORILO – Pri uporabi tega standarda so lahko prisotni nevarni materiali, postopki in oprema. Ta dokument ne obravnava vseh varnostnih težav, ki se nanašajo na njegovo uporabo. Za sprejetje ustreznih ukrepov za zagotavljanje varnosti in zdravja osebja pred uporabo standarda ter izpolnjevanje zakonskih in regulativnih zahtev za ta namen so odgovorni uporabniki tega standarda.
General Information
Relations
Standards Content (Sample)
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Mineralölindustrie und -produkte - Bestimmung der Zusammensetzung von Heizgas für Raffinerien und Berechnung des Kohlenstoffgehaltes und des Heizwertes - Gaschromatographisches VerfahrenIndustries et produits pétroliers - Détermination de la composition des gaz combustibles de raffinerie, de leur pouvoir calorifique et de leur teneur en carbone - Méthode par chromatographie en phase gazeusePetroleum industry and products - Determination of composition of refinery heating gas and calculation of carbon content and calorific value - Gas chromatography method75.160.30Plinska gorivaGaseous fuels71.040.50Fizikalnokemijske analitske metodePhysicochemical methods of analysisICS:Ta slovenski standard je istoveten z:EN 15984:2017SIST EN 15984:2017en,fr,de01-oktober-2017SIST EN 15984:2017SLOVENSKI
STANDARDSIST EN 15984:20111DGRPHãþD
SIST EN 15984:2017
EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 15984
August
t r s y ICS
y wä s x rä u r Supersedes EN
s w { z vã t r s sEnglish Version
Petroleum industry and products æ Determination of composition of refinery heating gas and calculation of carbon content and calorific value æ Gas chromatography method Industries et produits pétroliers æ Détermination de la composition des gaz combustibles de raffinerieá de leur pouvoir calorifique et de leur teneur en carbone æ Méthode par chromatographie en phase gazeuse
Mineralölindustrie und æprodukte æ Bestimmung der Zusammensetzung von Heizgas für Raffinerien und Berechnung des Kohlenstoffgehaltes und des Heizwertes æ Gaschromatographisches Verfahren This European Standard was approved by CEN on
s { June
t r s yä
egulations which stipulate the conditions for giving this European Standard the status of a national standard without any alterationä Upætoædate lists and bibliographical references concerning such national standards may be obtained on application to the CENæCENELEC Management Centre or to any CEN memberä
translation under the responsibility of a CEN member into its own language and notified to the CENæCENELEC Management Centre has the same status as the official versionsä
CEN members are the national standards bodies of Austriaá Belgiumá Bulgariaá Croatiaá Cyprusá Czech Republicá Denmarká Estoniaá Finlandá Former Yugoslav Republic of Macedoniaá Franceá Germanyá Greeceá Hungaryá Icelandá Irelandá Italyá Latviaá Lithuaniaá Luxembourgá Maltaá Netherlandsá Norwayá Polandá Portugalá Romaniaá Serbiaá Slovakiaá Sloveniaá Spainá Swedená Switzerlandá Turkey and United Kingdomä
EUROPEAN COMMITTEE FOR STANDARDIZATION COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre:
Avenue Marnix 17,
B-1000 Brussels
9
t r s y CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Membersä Refä Noä EN
s w { z vã t r s y ESIST EN 15984:2017
EN 15984:2017 (E) 2
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 . 18 Annex C (informative)
Calculation test data . 20 Annex D (normative)
Data for calculation . 21 Bibliography . 22
SIST EN 15984:2017
EN 15984:2017 (E) 3 European foreword This document (EN 15984:2017) 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 February 2018, and conflicting national standards shall be withdrawn at the latest by February 2018. 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 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. 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, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. SIST EN 15984:2017
EN 15984:2017 (E) 4
1 Scope This European Standard specifies 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 analysed. 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 European Standard, the terms “% (V/V)” is used to represent the volume fraction (). WARNING — The use of this standard 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 users of this standard to take appropriate measures to ensure the safety and health of personnel prior to application of the document, and fulfil statutory and regulatory requirements for this purpose. 2 Principle This 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. The composition range in which each component can be analysed 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. SIST EN 15984:2017
EN 15984:2017 (E) 5 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 H2 2 Oxygen/Argon O2/Ar 3 Nitrogen N2 4 Carbon monoxide CO 5 Carbon dioxide CO2 6 Hydrogen sulfide H2S 7 Methane CH4 8 Ethane C2H6 9 Ethene C2H4 10 Ethyne /Acetylene C2H2 11 Propane C3H8 12 Propene C3H6 13 Prop-1-yne
(Propyne, Methylacetylene) C3H4 14 Allene (Propadiene) C3H4 15 Methylpropane (iso-Butane) C4H10 16 n-Butane C4H10 17 But-2-ene Trans
(trans-2-Butene) C4H8 18 But-1-ene (1-Butene) C4H8 19 2-methylprop-1-ene
(2-Methyl-Propene) C4H8 20 Cis But-2-ene (cis-2-Butene) C4H8 21 Buta-1,3-diene
(1,3-Butadiene) C4H6 22 2-Methylbutane (iso-Pentane) C5H12 23 n-Pentane C5H12 24 Other components with 5 or more Carbon atoms, excluding 2-Methylbutaneand
Pentane (C5+) SIST EN 15984:2017
EN 15984:2017 (E) 6
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 consists 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. 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 (O2/Ar, N2, CH4 and CO) are on the molecular sieve 13X column, this column is isolated. Carbon dioxide, the C2-hydrocarbons and hydrogen sulfide are eluted from the porous polymer column (column 4) and are detected. The C2-hydrocarbons from this fraction are not used for 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. SIST EN 15984:2017
EN 15984:2017 (E) 7 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 are to be determined (see Table 1) is possible and that the summed total of C5+ is quantitative. Adequate separation is 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 analysed. 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 the
...
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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oSIST prEN 15984:2016
prEN 15984:2016 (E)
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
2
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prEN 15984:2016 (E)
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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oSIST prEN 15984:2016
prEN 15984:2016 (E)
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.
4
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prEN 15984:2016 (E)
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+
5
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prEN 15984:2016 (E)
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.
6
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oSIST prEN 15984:2016
prEN 15984:2016 (E)
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
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