BS EN ISO 6326-1-2009 Natural gas - Determination of sulfur compounds - General introduction《天然气 硫化合物的测定 一般介绍》.pdf

1、BS EN ISO 6326-1:2009 ICS 75.060 NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAW BRITISH STANDARD Natural gas Determination of sulfur compounds Part 1: General introduction (ISO 6326-1:2007) Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled

2、Copy, (c) BSIThis British Standard was published under the authority of the Standards Policy and Strategy Committee on 28 February 2010 BSI 2010 ISBN 978 0 580 67933 9 Amendments/corrigenda issued since publication Date Comments BS EN ISO 6326-1:2009 National foreword This British Standard is the UK

3、 implementation of EN ISO 6326-1:2009. It is identical to ISO 6326-1:2007. It supersedes BS 3156-11.4.1:1994 which is withdrawn.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 ca

4、n be obtained on request to its secretary. The flame photometric detector is available from most manufacturers of 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 operate

5、d under completely dif- ferent conditions in order to measure carbonyl sulfide to those used for all other sulfur compounds. 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

6、cannot confer immunity from legal obligations. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 6326-1 July 2009 ICS 75.060 English Version Natural gas - Determination of sulfur compounds - Par

7、t 1: General introduction (ISO 6326-1:2007) Gaz naturel - Dtermination des composs soufrs - Partie 1: Introduction gnrale (ISO 6326-1:2007) Erdgas - Bestimmung von Schwefelverbindungen - Teil 1: Allgemeine Einleitung (ISO 6326-1:2007) This European Standard was approved by CEN on 20 June 2009. CEN m

8、embers 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 be obtained on applic

9、ation 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 translation under the responsibility of a CEN member into its own language and notified to the CEN Management Centre ha

10、s the same status as the official 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, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Po

11、rtugal, 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 2009 CEN All rights of exploitation in any form and by any mea

12、ns reserved worldwide for CEN national Members. Ref. No. EN ISO 6326-1:2009: E Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 EN ISO 6326-1:2009 (E) 3 Foreword The text of ISO 6326-1:2007 has been prepared by Technical Committ

13、ee ISO/TC 193 “Natural gas” of the International 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,

14、 and conflicting national standards shall be withdrawn 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.

15、According to the CEN/CENELEC Internal Regulations, 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,

16、Latvia, Lithuania, Luxembourg, Malta, Netherlands, 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. Licensed Copy: Wang Bin

17、, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 ISO 6326-1:2007(E) ISO 2007 All rights reserved iii Contents 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 det

18、ermination 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 determination of individual sulfur compounds or groups of sulfur compounds 5 5.1 Gas chromatography method (ISO 19739). 5 5.2 Potentiometric method (ISO 6326

19、-3). 5 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 ISO 6326-1:2007(E) iv ISO 2007 All rights reservedForeword ISO (the International Organization for Standardization) is a worldwide federation of national standards bodies (

20、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 represented on that committee. International organizations, go

21、vernmental 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 drafted in accordance with the rules given in the ISO/IE

22、C 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 Standard requires approval by at least 75 % of the memb

23、er 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 prepared by Technical Committee ISO/TC 193, Natural gas, Sub

24、committee 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 Determination of sulfur compounds using gas chromatog

25、raphy, 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 Determination of sulfur compounds: Part 1: General intro

26、duction Part 3: Determination of hydrogen sulfide, mercaptan sulfur and carbonyl sulfide sulfur by potentiometry Part 5: Lingener combustion method Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 ISO 6326-1:2007(E) ISO 2007 All

27、 rights reserved v Introduction Sulfur compounds 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 com

28、pounds in natural gas is necessary in view of the 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

29、 order to enable the user to choose the method most 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 choic

30、e of the method. The other parts of ISO 6326 and ISO 19739 describe in detail the various standardized methods. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 0

31、1:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 INTERNATIONAL STANDARD ISO 6326-1:2007(E) ISO 2007 All rights reserved 1 Natural gas Determination of sulfur compounds Part 1: General introduction WARNING The majority of sulfur compounds are extremely toxic and thus present a serious health haz

32、ard 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 range of concentrations for which the method is suit

33、able 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 sulfur, b) sulfur contained in specific groups (e.g.

34、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 combustion method: for total sulfur determination

35、(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 sulfur compounds are available but are not considered he

36、re. 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 sulfides and disulfides. Licensed Copy: Wang Bin, ISO

37、/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 ISO 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/m 3Reference Total sulfur Wickbold combu

38、stion method 1 to 20 000 ISO 4260 Lingener combustion method 0,5 to 1 000 ISO 6326-5 Potentiometry W 1 ISO 6326-3 Hydrogen sulfide (H 2 S) 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) Potentiometr

39、y W 1 ISO 6326-3 Tetrahydrothiophene (THT) Gas chromatography 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 chromato

40、graphy 0,1 to 100 ISO 19739 aFor the determination of 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 g

41、as. 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 referenced document (including any amendments) applies. ISO 4260, Petroleum pr

42、oducts and hydrocarbons Determination of sulfur content 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 compou

43、nds Part 5: Lingener combustion method ISO 10715, Natural 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 ar

44、e very important in the analysis of sulfur compounds. 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

45、ensure that the sulfur compounds in correct quantity reach the analytical device. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 08/06/2010 01:42, Uncontrolled Copy, (c) BSIBS EN ISO 6326-1:2009 ISO 6326-1:2007(E) ISO 2007 All rights reserved 3 Carry out representative sampling in such a way

46、 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 should be long enough to obtain replicate stable analytical results within the acceptable standard deviation of the analyser. The purge time needed

47、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 of the gas can be carried out in two different ways: at atmospheric pressure in a silanized glass vessel, equipped with polytetrafluoroethylene (PT

48、FE) plugs or a sampling bag made of material inert to sulfur compounds, such as polyvinylfluoride (PVF) or PTFE, which has been flushed with dilute hydrochloric acid, subsequently flushed with distilled water and dried; after the glass vessel is filled with the gas under study, it should be shielded

49、 from daylight; under pressure in a stainless steel or aluminium cylinder, if the sulfur content exceeds 50 mg/m 3 . 3.2 Safety precautions Safety precautions 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 and advice for the use, sampling and handling of