1、BRITISH STANDARDBS EN ISO 19739:2005Incorporating corrigenda December 2006 and April 2009 Natural gas Determination of sulfur compounds using gas chromatographyICS 75.060g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g4
2、0g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58National forewordThis British Standard is the UK implementation of EN ISO 19739:2005. It is identical with ISO 19739:2004, incorporating corrigendum April 2009. It supersedes BS ISO 19739:2004 which is withdrawn.The UK participati
3、on in its preparation was entrusted to Technical Committee PTI/15, Natural gas and gas analysis.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to include all the necessary provisions of a contract. Users are respons
4、ible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations.BS EN ISO 19739:2005This British Standard waspublished under the authorityof the Standards Policy andStrategy Committee on14 June 2004 BSI 2010Amendments/corrigenda issued since publicat
5、ionAmd. No. Date Comments 16788 29 December 2006 Renumbers BS ISO 19739:2004 as BS EN ISO 19739:200531 March 2010 Implementation of ISO corrigendum April 2009; Clause 6 amendedISBN 978 0 580 67742 7EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN ISO 19739November 2005ICS 75.060English VersionNatur
6、al gas - Determination of sulfur compounds using gaschromatography (ISO 19739:2004)Gaz naturel - Dtermination des composs soufrs parchromatographie en phase gazeuse (ISO 19739:2004)Erdgas - Bestimmung von Schwefelverbindungen mittelsGaschromatographie (ISO 19739:2004)This European Standard was appro
7、ved by CEN on 3 November 2005.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalst
8、andards may be obtained on application to the Central Secretariat or to any CEN member.This European Standard exists in three official versions (English, French, German). A version in any other language made by translationunder the responsibility of a CEN member into its own language and notified to
9、 the Central Secretariat has the same status as the officialversions.CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norw
10、ay, Poland, Portugal, Slovakia,Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2005 CEN All rights of exploitation in any form and by any m
11、eans reservedworldwide for CEN national Members.Ref. No. EN ISO 19739:2005: EForeword The text of ISO 19739:2004 has been prepared by Technical Committee ISO/TC 193 “Natural gas” of the International Organization for Standardization (ISO) and has been taken over as EN ISO 19739:2005 by CMC. This Eur
12、opean Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by May 2006, and conflicting national standards shall be withdrawn at the latest by May 2006. According to the CEN/CENELEC Internal Regulations, the national s
13、tandards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal
14、, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Endorsement notice The text of ISO 19739:2004 has been approved by CEN as EN ISO 19739:2005 without any modifications. BS EN ISO 19739:2005EN ISO 19739:2005 (E)Reference numberISO 19739:2004(E)INTERNATIONAL STANDARD ISO19739First e
15、dition2004-05-01Natural gas Determination of sulfur compounds using gas chromatography Gaz naturel Dtermination des composs soufrs par chromatographie en phase gazeuse BS EN ISO 19739:2005EN ISO 19739:2005 (E) ISO 4002 All irthgs erse.devr lnUeto sswrehise specified, on trap fo this lbupictaion maeb
16、 y cudorperro de tuilizi den yna form ro na ybm ynae,s lecetrinoc ro mceinahcla, incliduntohp gcoiypodna gn micrfoilm, wittuoh repmissii now nritign from ietI rehSa Ot tsserdda eh ebolw or ISOs memreb i ydobn the cnuotfo yr ttseuqer ehe.r ISO cirypothg fofice saCe tsopale 65 eneG 1121-HC 02 avleT. 4
17、 + 10 947 22 1 11 xaF0 947 22 14 + 9 74 E-mial coirypthgis.o groWe bwww.is.o groPulbisdehi n Switlrez dnaii iiiContents Page Foreword iv Introduction v 1 Scope 1 2 Normative references . 1 3 Terms and definitions. 1 4 Principle . 3 5 Apparatus. 3 6 Sampling 4 6.1 Safety precautions 4 6.2 Temperature
18、 control . 4 6.3 Construction materials. 5 6.4 Cleanness 5 6.5 Installation of the calibration gas cylinder. 5 6.6 Pressure control 5 6.7 Purging of reduction valve and transfer lines 5 6.8 Flow control. 6 6.9 Diffusion control . 6 6.10 Automation and sequences of sampling6 7 Calibration 6 8 Analysi
19、s 6 9 Performance characteristics required for sulfur analysis 7 10 Test report 8 Annex A (informative) Columns mostly used in sulfur analysis (with internal phase and dimensions) . 9 Annex B (informative) Types of detectors used in sulfur analysis . 10 Annex C (informative) GC method using capillar
20、y column and FPD 13 Annex D (informative) GC method using ED . 19 Annex E (informative) GC method using MSD. 25 Annex F (informative) GC method using AED . 28 Annex G (informative) GC methods using column switching and FPD 31 Annex H (informative) GC method using capillary column and SCD 43 Annex I
21、(informative) GC method using capillary column and PFPD . 50 Bibliography . 55 BS EN ISO 19739:2005EN ISO 19739:2005 (E)iv Foreword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International
22、 Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, a
23、lso take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are drafted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical commit
24、tees is to prepare International Standards. Draft International Standards adopted by the technical committees are circulated to the member bodies for voting. Publication as an International Standard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the pos
25、sibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. ISO 19739 was prepared by Technical Committee ISO/TC 193, Natural gas, Subcommittee SC 1, Analysis of natural gas. This first edit
26、ion of ISO 19739 cancels and replaces ISO 6326-2:1981 and ISO 6326-4:1994, of which it constitutes a technical revision. BS EN ISO 19739:2005EN ISO 19739:2005 (E)vIntroduction Sulfur compounds may occur naturally in natural gas and remain as traces after treatment, or they may have been injected del
27、iberately to allow subsequent olfactory detection for safety reasons. The standardization of several methods for the determination of sulfur compounds in natural gas is necessary in view of the diversity of these compounds (hydrogen sulfide, carbonyl sulfide, tetrahydrothiophene, etc.) and the requi
28、rements of the determinations (e.g. required uncertainty, measurement at the drilling head, clean-up plant or in transmission pipes). In order to enable its user to choose the most appropriate method for his/her particular needs and perform the measurements under the best conditions, this Internatio
29、nal Standard gives the requirements needed to perform a sulfur analysis. BS EN ISO 19739:2005EN ISO 19739:2005 (E)blank1Natural gas Determination of sulfur compounds using gas chromatography WARNING Some sulfur compounds can constitute a serious health hazard. 1 Scope This International Standard spe
30、cifies the determination of hydrogen sulfide, carbonyl sulfide, C1to C4thiols, sulfides and tetrahydrothiophene (THT) using gas chromatography (GC). Depending on the method chosen from those given in the annexes, the application ranges for the determination of sulfur compounds can vary, but whicheve
31、r of the methods is used, the requirements of this International Standard apply. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the r
32、eferenced document (including any amendments) applies. ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method ISO 6141, Gas analysis Requirements for certif
33、icates for calibration gases and gas mixtures ISO 6143, Gas analysis Comparison methods for determining and checking the composition of calibration gas mixtures ISO 6145-10, Gas analysis Preparation of calibration gas mixtures using dynamic volumetric methods Part 10: Permeation method ISO 10715:199
34、7, Natural gas Sampling guidelines ISO 14532:2001, Natural gas Vocabulary 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 alkane thiol alkyl mercaptan organic sulfur compound with the general formula R-SH (where R is the alkyl group), either
35、naturally present or added as an odorant to natural gas ISO 14532:2001, definition 2.5.3.3.1 EXAMPLE Methanethiol (MeSH), ethanethiol (EtSH), 2-methylpropane-2-thiol (tert-butylmercaptan TBM). BS EN ISO 19739:2005EN ISO 19739:2005 (E)2 3.2 alkyl disulfide organic sulfur compound with the general for
36、mula R-S-S-R (where R and R are alkyl groups) ISO 14532:2001, definition 3.5.3.3.3 3.3 alkyl sulfide thioether organic sulfur compound with the general formula R-S-R (where R and R are alkyl groups), either naturally present or added as an odorant to natural gas ISO 14532:2001, definition 3.5.3.3.2
37、EXAMPLE Dimethyl sulfide (DMS), diethyl sulfide (DES). 3.4 carbonyl sulfide COS sulfur compound found in natural gas, which contributes to the total sulfur content ISO 14532:2001, definition 3.5.3.3.4 3.5 chromatographic resolution column efficiency characteristic describing the degree of separation
38、 of two adjacent peaks in gas chromatography ISO 14532:2001, definition 2.5.3.4.6 NOTE The resolution is measured as twice the distance between the maximum of the named peaks divided by the sum of the intercepts on the baseline made by tangents drawn to the peaks at half the height. 3.6 cyclic sulfi
39、de thioether cyclic organic sulfur compound with one sulfur atom incorporated in a saturated hydrocarbon ring EXAMPLE Tetrahydrothiophene (thiophane or thiacyclopentane, THT), i.e. C4H8S, which is added as an odorant to natural gas. ISO 14532:2001, definition 2.5.3.3.6 3.7 hydrogen sulfide H2S colou
40、rless, toxic gas with an odour similar to rotten eggs ISO 14532:2001, definition 2.5.3.3.8 3.8 normal reference conditions reference conditions of pressure, temperature and humidity (state of saturation) equal to 101,325 kPa and 273,15 K for a dry, real gas ISO 14532:2001, definition 2.6.1.3 BS EN I
41、SO 19739:2005EN ISO 19739:2005 (E)33.9 standard reference conditions reference conditions of pressure, temperature and humidity (state of saturation) equal to 101,325 kPa and 288,15 K for a dry, real gas ISO 14532:2001, definition 2.6.1.4 3.10 total sulfur total amount of sulfur found in natural gas
42、 ISO 14532:2001, definition 2.5.3.3.17 NOTE The total amount of sulfur may be determined by an analytical method not differentiating between individual sulfur compounds. 3.11 working reference gas mixture WRM working standard gas mixture gas mixture whose component quantity levels have been validate
43、d by direct comparison with a secondary standard gas mixture (CRM) ISO 14532:2001, definition 2.5.3.5.2.3 3.12 secondary standard gas mixture gas mixture whose component quantity levels have been validated by direct comparison with a PSM ISO 14532:2001, definition 2.5.3.5.2.2 3.13 primary standard g
44、as mixture PSM gas mixture whose component quantity levels have been determined with the utmost accuracy and can be used as a reference gas for determining the component quantity levels of other gas mixtures ISO 14532:2001, definition 2.5.3.5.2.1 4 Principle All significant components or groups of c
45、omponents to be determined in a gaseous sample are physically separated by means of gas chromatography (GC) and measured by comparison with calibration or reference gases. The gas being used for calibration and the sample gas shall be analysed with the same measuring system under the same set of con
46、ditions 5 Apparatus 5.1 Gas chromatograph, containing injection device, oven, regulation system for temperature control and pressure, detector. 5.2 Chromatographic columns, with column tubing made of a material inert to sulfur compounds (see 6.4), and a stationary phase able to separate the sulfur c
47、ompounds to be analysed in order that the resolution between two adjacent peaks shall not be less than 1,5. NOTE 1 See Annex A for a list of chromatographic columns mostly used in sulfur analysis. NOTE 2 The absence of chromatographic separation between COS and H2S will lead to an error in total sul
48、fur amount calculation. BS EN ISO 19739:2005EN ISO 19739:2005 (E)4 5.3 Detectors for detecting sulfur compounds: sulfur-specific, multi-specific (respond to halogen, sulfur), and/or general detectors. See Annex B for descriptions of suitable detectors. NOTE 1 Separation problems on a column could be
49、 solved by using a sulfur-specific detector, as hydrocarbons will not be seen by it. NOTE 2 Matrix effects can occur in sulfur analysis with certain methods/detectors. NOTE 3 Sulfur response can be affected by quenching effects produced by hydrocarbons. NOTE 4 Many detectors use an excited state of a molecule or atom to detect sulfur. An atom or molecule with one electron shifted from its normal orbit to another (more energetic) is said to be excited. When it relaxes, returning to its normal state, the electron falls
