1、August 2009DEUTSCHE NORM English price group 22No part of this standard may be reproduced without prior permission ofDIN Deutsches Institut fr Normung e. V., Berlin. Beuth Verlag GmbH, 10772 Berlin, Germany,has the exclusive right of sale for German Standards (DIN-Normen).ICS 75.060!$YFX“1543553www.
2、din.deDDIN EN ISO 19739Natural gas Determination of sulfur compounds using gas chromatography(ISO 19739:2004) (includes Corrigendum AC:2009)English version of DIN EN ISO 19739:2009-08Erdgas Bestimmung von Schwefelverbindungen mittels Gaschromatographie (ISO 19739:2004)(enthlt Berichtigung AC:2009)En
3、glische Fassung DIN EN ISO 19739:2009-08SupersedesDIN EN ISO 19739:2006-03www.beuth.deDocument comprises 61 pagesDIN EN ISO 19739:2009-08 2 National foreword This standard has been prepared by Technical Committee ISO/TC 193 “Natural gas”, Subcommittee SC 1 “Analysis of natural gas” (Secretariat: NEN
4、, Netherlands). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Technical Committee NA 062-05-73 AA Gasanalyse und Gas-beschaffenheit. The DIN Standards corresponding to the International Standards referred to in
5、 this document are as follows: ISO 5725-2 DIN ISO 5725-2 ISO 6141 DIN EN ISO 6141 ISO 6143 DIN EN ISO 6143 ISO 10715 DIN EN ISO 10715 Amendments This standard differs from DIN EN ISO 19739:2006-03 as follows: a) An information has been included in clause 6 for samples to be removed to a remote locat
6、ion (AC:2009). b) An information on suitable sampling cylinders has been included (AC:2009). Previous editions DIN EN ISO 19739: 2006-03 National Annex NA (informative) Bibliography DIN EN ISO 6141, Gas analysis Requirements for certificates for calibration gases and gas mixtures DIN EN ISO 6143, Ga
7、s analysis Comparison methods for determining and checking the composition of calibration gas mixtures DIN EN ISO 10715, Natural gas Sampling guidelines DIN ISO 5725-2, Accuracy (trueness and precision) of measurement methods and results Part 2: Basic method for the determination of repeatability an
8、d reproducibility of a standard measurement method EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 19739 November 2005 +AC May 2009 ICS 75.060 English version Natural gas Determination of sulfur compounds using gas chromatography (ISO 19739:2004+Cor. 1:2009) Gaz naturel Dtermination des com
9、poss soufrs par chromatographie en phase gazeuse (ISO 19739:2004+Cor. 1:2009) Erdgas Bestimmung von Schwefelverbindungen mittels Gaschromatographie (ISO 19739:2004+Cor. 1:2009) EN ISO 19739:2005 was approved by CEN on 2005-11-03 and Corrigendum AC:2009 on 2009-05-27. CEN members are bound to comply
10、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 be obtained on application to the Management Cen
11、tre or to any CEN member. The European Standards exist 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 Management Centre has the same status as the official ve
12、rsions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia,
13、 Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2009 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN nationa
14、l Members. Ref. No. EN ISO 19739:2005+AC:2009 EContents Page Foreword3 Introduction .4 1 Scope 5 2 Normative references 5 3 Terms and definitions .5 4 Principle7 5 Apparatus .7 6 Sampling.8 6.1 Safety precautions.8 6.2 Temperature control8 6.3 Construction materials9 6.4 Cleanness.9 6.5 Installation
15、 of the calibration gas cylinder9 6.6 Pressure control 9 6.7 Purging of reduction valve and transfer lines 9 6.8 Flow control. 10 6.9 Diffusion control . 10 6.10 Automation and sequences of sampling . 10 7 Calibration . 10 8 Analysis . 10 9 Performance characteristics required for sulfur analysis 11
16、 10 Test report . 12 Annex A (informative) Columns mostly used in sulfur analysis (with internal phase and dimensions). 13 Annex B (informative) Types of detectors used in sulfur analysis . 14 Annex C (informative) GC method using capillary column and FPD 17 Annex D (informative) GC method using ED
17、. 23 Annex E (informative) GC method using MSD 29 Annex F (informative) GC method using AED. 32 Annex G (informative) GC methods using column switching and FPD 35 Annex H (informative) GC method using capillary column and SCD . 47 Annex I (informative) GC method using capillary column and PFPD . 54
18、Bibliography. 59 2 EN ISO 19739:2005+AC:2009 (E) DIN EN ISO 19739:2009-08 Foreword 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 Europe
19、an 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 stan
20、dards 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, S
21、lovakia, 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 modification. Endorsement notice The text of ISO 19739:2004/Cor. 1:2009 has been approved by CEN as a European Corrigendum without
22、 any modification. 3 EN ISO 19739:2005+AC:2009 (E) DIN EN ISO 19739:2009-08 Introduction Sulfur compounds may occur naturally in natural gas and remain as traces after treatment, or they may have been injected deliberately to allow subsequent olfactory detection for safety reasons. The standardizati
23、on 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 requirements of the determinations (e.g. required uncertainty, measurement at the drilling h
24、ead, 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 International Standard gives the requirements needed to perform a sulfur analysis. 4 EN ISO 19739
25、:2005+AC:2009 (E) DIN EN ISO 19739:2009-08 5WARNING Some sulfur compounds can constitute a serious health hazard. 1 Scope This International Standard specifies the determination of hydrogen sulfide, carbonyl sulfide, C1to C4thiols, sulfides and tetrahydrothiophene (THT) using gas chromatography (GC)
26、. Depending on the method chosen from those given in the annexes, the application ranges for the determination of sulfur compounds can vary, but whichever of the methods is used, the requirements of this International Standard apply. 2 Normative references The following referenced documents are indi
27、spensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 5725-2:1994, Accuracy (trueness and precision) of measurement methods and results Part 2
28、: Basic method for the determination of repeatability and reproducibility of a standard measurement method ISO 6141, Gas analysis Requirements for certificates for calibration gases and gas mixtures ISO 6143, Gas analysis Comparison methods for determining and checking the composition of calibration
29、 gas mixtures ISO 6145-10, Gas analysis Preparation of calibration gas mixtures using dynamic volumetric methods Part 10: Permeation method ISO 10715:1997, Natural gas Sampling guidelines ISO 14532:2001, Natural gas Vocabulary 3 Terms and definitions For the purposes of this document, the following
30、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 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-met
31、hylpropane-2-thiol (tert-butylmercaptan TBM). EN ISO 19739:2005+AC:2009 (E) DIN EN ISO 19739:2009-08 6 3.2 alkyl disulfide organic sulfur compound with the general formula 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 compoun
32、d 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 EXAMPLE Dimethyl sulfide (DMS), diethyl sulfide (DES). 3.4 carbonyl sulfide COS sulfur compound found in natural gas, which contribut
33、es 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 of two adjacent peaks in gas chromatography ISO 14532:2001, definition 2.5.3.4.6 NOTE The resolution is measured as twice the distan
34、ce 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 sulfide thioether cyclic organic sulfur compound with one sulfur atom incorporated in a saturated hydrocarbon ring EXAMPLE Tetrahydrothiop
35、hene (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 colourless, toxic gas with an odour similar to rotten eggs ISO 14532:2001, definition 2.5.3.3.8 3.8 normal reference conditions reference
36、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 EN ISO 19739:2005+AC:2009 (E) DIN EN ISO 19739:2009-08 73.9 standard reference conditions reference conditions of pressure, temperature and
37、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 ISO 14532:2001, definition 2.5.3.3.17 NOTE The total amount of sulfur may be determined by an analytical method not di
38、fferentiating between individual sulfur compounds. 3.11 working reference gas mixture WRM working standard gas mixture gas mixture whose component quantity levels have been validated by direct comparison with a secondary standard gas mixture (CRM) ISO 14532:2001, definition 2.5.3.5.2.3 3.12 secondar
39、y 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 gas mixture PSM gas mixture whose component quantity levels have been determined with the utmost accuracy and can be use
40、d 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 components to be determined in a gaseous sample are physically separated by means of gas chromatography (GC) and measure
41、d 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 conditions 5 Apparatus 5.1 Gas chromatograph, containing injection device, oven, regulation system for temperature control
42、 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 compounds to be analysed in order that the resolution between two adjacent peaks shall not be less than 1,5. NOTE 1 See
43、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 sulfur amount calculation. EN ISO 19739:2005+AC:2009 (E) DIN EN ISO 19739:2009-08 8 5.3 Detectors for detecting sulfur com
44、pounds: 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 solved by using a sulfur-specific detector, as hydrocarbons will not be seen by it. NOTE 2 Matrix effect
45、s 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
46、to another (more energetic) is said to be excited. When it relaxes, returning to its normal state, the electron falls back to its normal orbit emitting a photon. The energy of this photon is relative to the difference in energy between the orbits. The wavelength of the photon is specific for each ex
47、cited state. So, if photons of different wavelength are separated (by a filter, monochromator, diffraction prism, etc.), the amount of specific photons can be measured. 6 Sampling The sampling procedures are very important in the analysis of sulfur compounds. Sulfur compounds have a strong tendency
48、to adsorb on to, or to chemically react with, different materials of construction. Low contents of sulfur compounds in samples and calibration gas mixtures place demands on the sampling procedure to ensure that the sulfur compounds in correct quantity reach the analytical detector. Carry out represe
49、ntative sampling in such a way that the sample represents the bulk of the gas at the time of sampling. Sampling and sample transfer shall be in accordance with ISO 10715. Collecting a sample and removing it to a remote location should be done only when no other option is available. Even then, a stain tube should be run onsite to give some means of verifying the approximate level of sulfur compounds present prior to transporting the sample. How critical this is depends on the species of interest: ethyl mercaptan
