1、BS EN ISO 6326-1:2009ICS 75.060NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDNatural gas Determination of sulfur compoundsPart 1: General introduction (ISO 6326-1:2007)This British Standard was published under the authority of the Standards Policy and Strategy
2、 Committee on 28 February 2010 BSI 2010ISBN 978 0 580 67933 9Amendments/corrigenda issued since publicationDate CommentsBS EN ISO 6326-1:2009National forewordThis British Standard is the UK implementation of EN ISO 6326-1:2009. It is identical to ISO 6326-1:2007. It supersedes BS 3156-11.4.1:1994 wh
3、ich is withdrawn.The UK participation in its preparation was entrusted to Technical Committee PTI/15, Natural Gas and Gas Analysis.A list of organizations represented on this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.The flame photometric detector is available from most manufacturers of
4、chromatographs, both laboratory and process units, and is applicable to any sulfur compounds. By contrast, the electrochemical detector is available from a single supplier and is operated under completely dif-ferent conditions in order to measure carbonyl sulfide to those used for all other sulfur c
5、ompounds.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.Compliance with a British Standard cannot confer immunity from legal obligations.EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN ISO 6326-1July 2009IC
6、S 75.060English VersionNatural gas - Determination of sulfur compounds - Part 1:General introduction (ISO 6326-1:2007)Gaz naturel - Dtermination des composs soufrs - Partie1: Introduction gnrale (ISO 6326-1:2007)Erdgas - Bestimmung von Schwefelverbindungen - Teil 1:Allgemeine Einleitung (ISO 6326-1:
7、2007)This European Standard was approved by CEN on 20 June 2009.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 ref
8、erences concerning such nationalstandards may be obtained on application to the CEN 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 translationunder the responsibility of a CEN member i
9、nto its own language and notified to the CEN Management Centre has the same status as theofficial versions.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,
10、 Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: Avenue Marnix 17, B-1000 Brussels 2009
11、CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN ISO 6326-1:2009: EBS EN ISO 6326-1:2009EN ISO 6326-1:2009 (E) 3 Foreword The text of ISO 6326-1:2007 has been prepared by Technical Committee ISO/TC 193 “Natural gas” of the Internation
12、al Organization for Standardization (ISO) and has been taken over as EN ISO 6326-1:2009. 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 January 2010, and conflicting national standards shall be w
13、ithdrawn at the latest by January 2010. 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. According to the CEN/CENELEC Internal Regulati
14、ons, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherla
15、nds, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 6326-1:2007 has been approved by CEN as EN ISO 6326-1:2009 without any modification. BS EN ISO 6326-1:2009ISO 6326-1:2007(E) ISO 2007 All rights reserved
16、iiiContents Page Foreword iv Introduction v 1 Scope . 1 2 Normative references . 2 3 Sampling 2 3.1 General. 2 3.2 Safety precautions 3 4 Methods for determination of total sulfur content 3 4.1 Wickbold combustion method (ISO 4260) 3 4.2 Lingener combustion method (ISO 6326-5) . 4 5 Methods for dete
17、rmination of individual sulfur compounds or groups of sulfur compounds 5 5.1 Gas chromatography method (ISO 19739). 5 5.2 Potentiometric method (ISO 6326-3). 5 BS EN ISO 6326-1:2009ISO 6326-1:2007(E) iv ISO 2007 All rights reservedForeword ISO (the International Organization for Standardization) is
18、a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International 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 represent
19、ed on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standardization. International Standards are dra
20、fted in accordance with the rules given in the ISO/IEC Directives, Part 2. The main task of technical committees 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 St
21、andard requires approval by at least 75 % of the member bodies casting a vote. Attention is drawn to the possibility 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 6326-1 was prepare
22、d by Technical Committee ISO/TC 193, Natural gas, Subcommittee SC 1, Analysis of natural gas. This second edition cancels and replaces the first edition (ISO 6326-1:1989), which has been technically revised due to the replacement of ISO 6326-2:1981 and ISO 6326-4:1994 by ISO 19739:2004, Natural gas
23、Determination of sulfur compounds using gas chromatography, which gives the requirements needed to perform a sulfur analysis by gas chromatography. This second edition also provides a general introduction to ISO 19739. ISO 6326 consists of the following parts, under the general title Natural gas Det
24、ermination of sulfur compounds: Part 1: General introduction Part 3: Determination of hydrogen sulfide, mercaptan sulfur and carbonyl sulfide sulfur by potentiometry Part 5: Lingener combustion method BS EN ISO 6326-1:2009ISO 6326-1:2007(E) ISO 2007 All rights reserved vIntroduction Sulfur compounds
25、 can 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 standardization of several methods for the determination of sulfur compounds in natural gas is necessary in view of th
26、e diversity of these compounds hydrogen sulfide, carbonyl sulfide, tetrahydrothiophene (THT), etc. and the requirements of the determinations (required uncertainty, measurement at the well head, at clean-up plant or in the transmission pipes, etc.). In order to enable the user to choose the method m
27、ost appropriate to his needs and to perform the measurements under the best conditions, ISO 6326 has been prepared in several parts. This part of ISO 6326 gives a rapid comparison of standardized methods and therefore provides information for the choice of the method. The other parts of ISO 6326 and
28、 ISO 19739 describe in detail the various standardized methods. BS EN ISO 6326-1:2009BS EN ISO 6326-1:2009INTERNATIONAL STANDARD ISO 6326-1:2007(E) ISO 2007 All rights reserved 1Natural gas Determination of sulfur compounds Part 1: General introduction WARNING The majority of sulfur compounds are ex
29、tremely toxic and thus present a serious health hazard if handled without precautions. 1 Scope This part of ISO 6326 gives a brief description of standardized methods that can be used for the determination of sulfur compounds in natural gas. The principle of each method is described generally, the r
30、ange of concentrations for which the method is suitable is indicated, and the analytical range and precision of each method is given. It should enable the user to select judiciously the proper method for the application being considered. Sulfur analysis is performed in order to determine a) total su
31、lfur, b) sulfur contained in specific groups (e.g. thiol sulfur), c) individual sulfur compounds, and d) specific groups of sulfur compounds. The standardized methods available in the field of sulfur analysis are the Wickbold combustion method: for total sulfur determination (ISO 4260), the Lingener
32、 combustion method: for total sulfur determination (ISO 6326-5), gas chromatography: for determination of individual sulfur compounds (ISO 19739), and potentiometry: for determination of hydrogen sulfide, carbonyl sulfide and thiol compounds (ISO 6326-3). Other methods for the determination of sulfu
33、r compounds are available but are not considered here. Table 1 gives an overview of the standardized methods which can be used for the determination of total sulfur, hydrogen sulfide, carbonyl sulfide, tetrahydrothiophene, thiol sulfur, individual thiols, individual thiophenes, individual organic su
34、lfides and disulfides. BS EN ISO 6326-1:2009ISO 6326-1:2007(E) 2 ISO 2007 All rights reservedTable 1 Methods for the determination of sulfur compounds in natural gas Concentration range aDetermination Method mg/m3Reference Total sulfur Wickbold combustion method 1 to 20 000 ISO 4260 Lingener combust
35、ion method 0,5 to 1 000 ISO 6326-5 Potentiometry W 1 ISO 6326-3 Hydrogen sulfide (H2S) Gas chromatography 0,1 to 100 (or 0,5 to 600 depending on the detector used) ISO 19739 Gas chromatography 0,1 to 30 ISO 19739 Carbonyl sulfide (COS) Potentiometry W 1 ISO 6326-3 Tetrahydrothiophene (THT) Gas chrom
36、atography 0,1 to 100 ISO 19739 Thiol sulfur Potentiometry W 1 ISO 6326-3 Individual thiols Gas chromatography 0,1 to 100 ISO 19739 Individual thiophenes Gas chromatography 0,1 to 100 ISO 19739 Individual organic sulfides and disulfides Gas chromatography 0,1 to 100 ISO 19739 aFor the determination o
37、f total sulfur, the sulfur content is expressed as milligrams of sulfur per cubic metre of gas. For the determination of sulfur compounds, the mass concentration of sulfur compounds is expressed as milligrams of sulfur compound per cubic metre of gas. 2 Normative references The following referenced
38、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 referenced document (including any amendments) applies. ISO 4260, Petroleum products and hydrocarbons Determination of sulfur cont
39、ent Wickbold combustion method ISO 6326-3, Natural gas Determination of sulfur compounds Part 3: Determination of hydrogen sulfide, mercaptan sulfur and carbonyl sulfide sulfur by potentiometry ISO 6326-5, Natural gas Determination of sulfur compounds Part 5: Lingener combustion method ISO 10715, Na
40、tural gas Sampling guidelines ISO 16664, Gas analysis Handling of calibration gases and gas mixtures Guidelines ISO 19739:2004, Natural gas Determination of sulfur compounds using gas chromatography 3 Sampling 3.1 General The sampling procedures are very important in the analysis of sulfur compounds
41、. Sulfur compounds have a strong tendency to adsorb on to, or to chemically react with, different materials of construction. Low contents of sulfur compounds in samples and calibration gas mixtures put demands on the sampling procedure in order to ensure that the sulfur compounds in correct quantity
42、 reach the analytical device. BS EN ISO 6326-1:2009ISO 6326-1:2007(E) ISO 2007 All rights reserved 3Carry out representative 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. Purge time s
43、hould be long enough to obtain replicate stable analytical results within the acceptable standard deviation of the analyser. The purge time needed depends on the type and concentration of the sulfur compound, materials in contact with the gas, and the gas flow rate through the sample loop. Sampling
44、of the gas can be carried out in two different ways: at atmospheric pressure in a silanized glass vessel, equipped with polytetrafluoroethylene (PTFE) plugs or a sampling bag made of material inert to sulfur compounds, such as polyvinylfluoride (PVF) or PTFE, which has been flushed with dilute hydro
45、chloric acid, subsequently flushed with distilled water and dried; after the glass vessel is filled with the gas under study, it should be shielded from daylight; under pressure in a stainless steel or aluminium cylinder, if the sulfur content exceeds 50 mg/m3. 3.2 Safety precautions Safety precauti
46、ons required in handling gas cylinders with pressurized flammable gas mixtures are described in ISO 10715. If a pressure regulator is to be connected to the cylinder, always use a regulator whose materials of construction are recommended by the producer of the calibration gas. For other precautions
47、and advice for the use, sampling and handling of gas mixtures containing sulfur compounds, see Clause 3 of ISO 19739:2004 and ISO 16664. 4 Methods for determination of total sulfur content To carry out the analyses, reference should be made to the specific methods which are described in detail in IS
48、O 4260, ISO 19739, ISO 6326-3 and ISO 6326-5. 4.1 Wickbold combustion method (ISO 4260) 4.1.1 Scope This method is applicable to products having sulfur content on the order of 1 mg/m3, and is particularly suitable for gases with total sulfur content in the range 1 mg/m3to 20 000 mg/m3and for distill
49、ates with total sulfur content of less than 300 mg/m3. 4.1.2 Principle The natural gas is supplied to the burner of a hydrogen-oxygen flame, where the sulfur compounds undergo combustion with a considerable excess of oxygen. The resulting sulfur oxides are converted into sulfuric acid by absorption in hydrogen peroxide solution. Depending on the sulfur content of the sample, the sulfate ions in the absorption solution are determined by colorimetric, nephelometric, turbidimetric or conductometric titra
