BS EN 15984-2017 Petroleum industry and products Determination of composition of refinery heating gas and calculation of carbon content and calorific value Gas chromatography metho.pdf

1、Petroleum industry and products - Determination of composition of refinery heating gas and calculation of carbon content and calorific value - Gas chromatography methodBS EN 15984:2017BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06EUROPEAN STANDARD NORME EUROPENNE E

2、UROPISCHE NORM EN 15984 August 2017 ICS 75.160.30 Supersedes EN 15984:2011English Version Petroleum 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 - Dtermi

3、nation de la composition des gaz combustibles de raffinerie, de leur pouvoir calorifique et 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 d

4、es Heizwertes - Gaschromatographisches Verfahren This European Standard was approved by CEN on 19 June 2017. 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 altera

5、tion. 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

6、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

7、, 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 United Kingdom. EUROPEAN COMMITTEE FOR

8、 STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15984:2017 ENational forewordThis

9、British Standard is the UK implementation of EN 15984:2017. It supersedes BS EN 15984:2011, which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee PTI/13, Petroleum Testing and Terminology.A list of organizations represented on this committee can be obtained

10、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. The British Standards Institution 2017 Published by BSI Standards Limited 2017ISBN 978 0 580 93208 3ICS 75.160; 75.160.30Compliance

11、with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 30 September 2017.Amendments/corrigenda issued since publicationDate Text affectedBRITISH STANDARDBS EN 15984:2017EUROPEAN S

12、TANDARD NORME EUROPENNE EUROPISCHE NORM EN 15984 August 2017 ICS 75.160.30 Supersedes EN 15984:2011English Version Petroleum industry and products - Determination of composition of refinery heating gas and calculation of carbon content and calorific value - Gas chromatography method Industries et pr

13、oduits ptroliers - Dtermination de la composition des gaz combustibles de raffinerie, de leur pouvoir calorifique et de leur teneur en carbone - Mthode par chromatographie en phase gazeuse Minerallindustrie und -produkte - Bestimmung der Zusammensetzung von Heizgas fr Raffinerien und Berechnung des

14、Kohlenstoffgehaltes und des Heizwertes - Gaschromatographisches Verfahren This European Standard was approved by CEN on 19 June 2017. 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 st

15、andard 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

16、 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 R

17、epublic, 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 United Kingdo

18、m. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15984:201

19、7 EBS EN 15984:2017EN 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

20、 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 Exp

21、ression 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

22、 calculation . 21 Bibliography . 22 BS EN 15984:2017EN 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 whi

23、ch 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 po

24、ssibility 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 val

25、ues 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 Regulat

26、ions, 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, Ital

27、y, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 15984:2017EN 15984:2017 (E) 4 1 Scope This European Standard specifies a gas chromatographic analysis for the determin

28、ation 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

29、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 represen

30、t 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 ensur

31、e 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 indicat

32、ed 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:

33、 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 b

34、uilt 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

35、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, wit

36、h a minimum purity of 99,995 % (V/V). 3.1.4 Air, free of oil and water. BS EN 15984:2017EN 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 determina

37、tion 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 H22 Oxygen/Argon O2/Ar 3 Nitrogen N24 Carbon monoxide CO 5 Carbon dioxide CO26 Hydrogen sulfide H2S 7 Methane CH48 Ethane C2H69 Eth

38、ene C2H410 Ethyne /Acetylene C2H211 Propane C3H812 Propene C3H613 Prop-1-yne (Propyne, Methylacetylene) C3H414 Allene (Propadiene) C3H415 Methylpropane (iso-Butane) C4H1016 n-Butane C4H1017 But-2-ene Trans (trans-2-Butene) C4H818 But-1-ene (1-Butene) C4H819 2-methylprop-1-ene (2-Methyl-Propene) C4H8

39、20 Cis But-2-ene (cis-2-Butene) C4H821 Buta-1,3-diene (1,3-Butadiene) C4H622 2-Methylbutane (iso-Pentane) C5H1223 n-Pentane C5H1224 Other components with 5 or more Carbon atoms, excluding 2-Methylbutaneand Pentane (C5+) BS EN 15984:2017EN 15984:2017 (E) 6 4 Apparatus 4.1 Usual laboratory apparatus a

40、nd 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

41、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 determi

42、ned 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

43、 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 is isolated. Carbon dioxide, the C2-hydrocarbons and hydrogen

44、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

45、 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 ba

46、ck 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 isother

47、mal 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. BS EN 15984

48、:2017EN 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 req

49、uired 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