1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 15984:2011Petroleum industry and products Determination of composition of refinery heating gas and calculation of carbon content and calorific value Gas chromatography meth
2、odBS EN 15984:2011 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 15984:2011. The UK participation in its preparation was entrusted to T e c h n i c a l Committee PTI/15, Natural Gas and Gas Analysis.A list of organizations represented on this committee can be
3、obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. BSI 2011 ISBN 978 0 580 63809 1 ICS 75.160.30 Compliance with a British Standard cannot confer immunity from legal obligati
4、ons.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 May 2011.Amendments issued since publicationDate T e x t a f f e c t e dBS EN 15984:2011EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15984 April 2011 ICS 75.160 English Version Pe
5、troleum industry and products - Determination of composition of refinery heating gas and calculation of carbon content and calorific value - Gas chromatography method Industries et produits ptroliers - Dtermination de la composition des gaz combustibles de raffinerie, de leur pouvoir calorifique et
6、de leur teneur en carbone - Mthode par chromatographie en phase gazeuse Minerallindustrie und -produkte - Bestimmung der Zusammensetzung von Heizgas fr Raffinerien und Berechnung des Kohlenstoffgehaltes und des Heizwertes -Gaschromatographisches Verfahren This European Standard was approved by CEN o
7、n 9 March 2011. 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
8、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
9、 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, Luxe
10、mbourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rig
11、hts of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15984:2011: EBS EN 15984:2011EN 15984:2011 (E) 2 Contents Page Foreword 31 Scope 42 Principle 43 Reagents and materials 44 Apparatus .55 Gas chromatographic analysis 65.1 Analysis systems .65.2
12、System configuration 65.3 Columns 66 Calibration 76.1 General 76.2 Absolute response factors .76.3 Relative response factors .77 Calculation 87.1 General 87.2 Calculation of the non normalized mole fractions .87.3 Validation of normalized composition (reference components) 87.4 Calculation of carbon
13、 content 97.5 Calculation of lower calorific value, on mass basis 108 Expression of results . 109 Precision 109.1 General . 109.2 Repeatability 119.3 Reproducibility 1110 Test report . 11Annex A (informative) Possible column combination 12Annex B (normative) Detector linearity check 17Annex C (infor
14、mative) Calculation test data 19Annex D (normative) Data for calculation 20Bibliography . 21BS EN 15984:2011EN 15984:2011 (E) 3 Foreword This document (EN 15984:2011) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic
15、 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 October 2011, and conflicting national standards shall be withdrawn at the latest
16、by October 2011. 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. This document is based on a DIN Standard 3 with the same scope. Accor
17、ding to the CEN/CENELEC Internal Regulations, the national standards organizations 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, Ita
18、ly, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. BS EN 15984:2011EN 15984:2011 (E) 4 1 Scope This European Standard defines a gas chromatographic analysis for the determination of the comp
19、osition 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 (se
20、e 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 frac
21、tion (). 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 stan
22、dard 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
23、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 betw
24、een 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 s
25、um 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
26、. 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. 3.1.5 Argon, as alternative for analysis system 2, with a minimum purity of 99,995 % (V/V). BS
27、EN 15984:2011EN 15984:2011 (E) 5 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 Hydroge
28、n H22 Oxygen/Argon O2/Ar 3 Nitrogen N24 Carbon monoxide CO5 Carbon dioxide CO26 Hydrogen sulfide H2S 7 Methane CH48 Ethane C2H69 Ethene C2H410 Ethyne (Acetylene) C2H211 Propane C3H812 Propene C3H613 Propyne (Methylacetylene) C3H414 Propadiene C3H415 iso-Butane C4H1016 n-Butane C4H1017 trans-2-Butene
29、 C4H818 1-Butene C4H819 2-Methyl-Propene C4H820 cis-2-Butene C4H821 1,3-Butadiene C4H622 iso-Pentane C5H1223 n-Pentane C5H1224 Other components with 5 or more Carbon atoms, excluding iso- and n-Pentane (C5+) 4 Apparatus 4.1 Usual laboratory apparatus and glassware. 4.2 Gas chromatographic apparatus,
30、 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. BS EN 15984:2011EN 15984:2011 (E) 6
31、 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 HayeSepand Molsieveare exam
32、ples 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 he
33、lium (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, CH4and CO) are on the molecular sieve 13X column, this column
34、 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
35、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),
36、 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 o
37、ne 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 sha
38、ll be provided. NOTE Optionally a vaporizer may be used. 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 C5+is quantit
39、ative. 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. BS EN 15984:2011EN 15984:2011 (E) 7 6 Calibration 6.1 General Depending on the
40、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
41、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 these three components, an external
42、 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 com
43、ponents that need to be analyzed in a reference gas mixture. A check of this calibration can take place with a gas mixture with fewer components. 6.2 Absolute response factors The determination of absolute response factors is possible when a repeatable injection is possible under constant analysis c
44、onditions. The ratio between concentration and peak area is determined and the absolute response factor is calculated with the following equation: iiiAxRF =(1) where iRFis the absolute response factor of component i ; ix is the concentration of component i in (mol/100 mol) in the calibration gas; iA
45、 is the peak area of component i in the calibration gas. 6.3 Relative response factors For quantification relative response factors can be used too. In one analysis system, one component is used as a reference (reference component). The relative response factor is calculated with the following equat
46、ion: StiiRFRFRRF =(2) where iRRFis the relative response factor of component i ; BS EN 15984:2011EN 15984:2011 (E) 8 iRFis the absolute response factor of component i ; StRFis the absolute response factor of the reference component St. 7 Calculation 7.1 General For the calculation of parameters of g
47、as mixtures, as described in this standard, the molar composition of the gas mixture is necessary. NOTE A more accurate result may be obtained by analyzing the C5 olefins separately and not adding them to the sum of all heavier components. 7.2 Calculation of the non normalized mole fractions The con
48、centrations of the components, xi, sample, mentioned in Table 1 are calculated as mole fractions. The calculation of these follows Equation (3): StKStisampleisampleiRFRRFAx =,(3) where sampleiA,is the area of component i in the sample; StiRRF,is the relative response factor of component i relative t
49、o the reference component St ; StKRF is the absolute response factor of the reference component St in the reference gas mixture K . NOTE If only absolute response factors are used, then reference component St and component i are identical. Therefore, in Equation (3) RRF = 1 and each RF represents the individual component i . 7.3 Validation of normalized composition (reference components) The results can be normalized, when the sum of all the mole fractions of the components are not smaller than
