1、August 2011 Translation by DIN-Sprachendienst.English price group 12No part of this translation 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
2、 13.040.40!$sl/“1807312www.din.deDDIN EN ISO 25139Stationary source emissions Manual method for the determination of the methane concentrationusing gas chromatography (ISO 25139:2011)English translation of DIN EN ISO 25139:2011-08Emissionen aus stationren Quellen Manuelles Verfahren zur Bestimmung d
3、er Methan-Konzentration mit Gaschromatographie(ISO 25139:2011)Englische bersetzung von DIN EN ISO 25139:2011-08missions de sources fixes Mthode manuelle pour la dtermination de la concentration en mthane parchromatographie en phase gazeuse (ISO 25139:2011)Traduction anglaise de DIN EN ISO 25139:2011
4、-08www.beuth.deDocument comprises pagesIn case of doubt, the German-language original shall be considered authoritative.24This standard has been included in the VDI/DIN Handbook on air quality, Volume 5. 07.11 DIN EN ISO 25139:2011-08 A comma is used as the decimal marker. National foreword This sta
5、ndard has been prepared by Technical Committee ISO/TC 146 “Air quality”, Subcommittee SC 1 “Stationary source emissions” in collaboration with Technical Committee CEN/TC 264 “Air quality” (the secretariats are held by DIN, Germany). The responsible German body involved in its preparation was the Kom
6、mission Reinhaltung der Luft (KRdL) im VDI und DIN Normenausschuss (Commission on Air Pollution Prevention of VDI and DIN Standards Committee), Section IV Umweltmesstechnik. The DIN Standards corresponding to the International Standards referred to in this document are as follows: ISO 5725-2 DIN ISO
7、 5725-2 ISO 9169 DIN EN ISO 9169 ISO 20988 DIN EN ISO 20988 ISO 25140 DIN EN ISO 25140 ISO/IEC Guide 98-3 DIN V ENV 13005 National Annex NA (informative) Bibliography DIN V ENV 13005, Guide to the expression of uncertainty in measurement DIN EN ISO 9169, Air quality Definition and determination of p
8、erformance characteristics of an automatic measuring system DIN EN ISO 20988, Air quality Guidelines for estimating measurement uncertainty DIN EN ISO 25140, Stationary source emissions Automatic method for the determination of the methane concentration using flame ionisation detection (FID) DIN ISO
9、 5725-2, 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 2 EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 25139 April 2011 ICS 13.040.40 English Version Sta
10、tionary source emissions Manual method for the determination of the methane concentration using gas chromatography (ISO 25139:2011) missions de sources fixes Mthode manuelle pour la dtermination de la concentration en mthane par chromatographie en phase gazeuse (ISO 25139:2011) Emissionen aus statio
11、nren Quellen Manuelles Verfahren zur Bestimmung der Methan-Konzentration mit Gaschromatographie (ISO 25139:2011)This European Standard was approved by CEN on 14 April 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this Europe
12、anStandard 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 CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official versions (
13、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-CENELEC Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgi
14、um, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMIT
15、TEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 25139:2011: EContents Page Foreword
16、 3Introduction . 4 1 Scope 5 2 Normative references 53 Terms and definitions . 5 4 Symbols and abbreviated terms 6 5 Principle . 7 6 Equipment 8 6.1 Sampling system . 8 6.2 Analytical apparatus . 10 7 Measurement procedure . 10 7.1 General . 10 7.2 Sampling 10 7.3 Analytical determination . 12 7.4 I
17、nterferents . 12 8 Calculation of the results . 12 9 Quality assurance and quality control procedures . 14 9.1 General . 14 9.2 Criteria and frequency of checks . 14 9.3 Performing the checks 15 9.4 Check of the measurement system . 16 10 Performance characteristics 16 11 Test report 16 Annex A (nor
18、mative) Operational gases 17 Annex B (normative) Quality assurance and quality control procedures 18 Annex C (informative) Typical performance characteristics 20 Bibliography 22 EN ISO 25139:2011 (E) DIN EN ISO 25139:2011-08 2Foreword This document (EN ISO 25139:2011) has been prepared by Technical
19、Committee ISO/TC 146 “Air quality“ in collaboration with Technical Committee CEN/TC 264 “Air quality” the secretariat of which is held by DIN. 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 Octob
20、er 2011, and conflicting national standards shall be withdrawn at the latest by October 2011. 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
21、rights. 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, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland,
22、 Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 25139:2011 has been approved by CEN as a EN ISO 25139:2011 without any modification. EN ISO
23、 25139:2011 (E) DIN EN ISO 25139:2011-08 3Introduction Methane (CH4) is a gas of relevance to the climate (“greenhouse gas”) and contributes directly to the atmospheric greenhouse effect. The emissions of methane originate from natural sources and those due to human activity. Significant sources are
24、, for example, cattle breeding, cultivation of rice, extraction and transport of natural gas, and landfills. Other important sources contributing to emissions of methane are, for example, composting plants, the use of biogas and natural gas, and biomass firings. This International Standard specifies
25、 a method of measurement for the determination of methane emissions from stationary sources. EN ISO 25139:2011 (E) DIN EN ISO 25139:2011-08 41 Scope This International Standard specifies a manual method for the determination of the concentration of methane emissions from stationary sources. This Int
26、ernational Standard specifies an independent method of measurement, which is validated for mass concentrations up to 1 500 mg/m3. NOTE 1 An independent method of measurement is used for such purposes as calibration or validation of permanently installed measuring systems. NOTE 2 An “independent meth
27、od of measurement” is termed “standard reference method (SRM)” in EN 141815. 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 refer
28、enced document (including any amendments) applies. ISO 9169, Air quality Definition and determination of performance characteristics of an automatic measuring system EN 15267-3, Air quality Certification of automated measuring systems Part 3: Performance criteria and test procedures for automated me
29、asuring systems for monitoring emissions from stationary sources 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 reference gas air quality gas of known, reliable and stable composition NOTE In the context of this International Standard, a ref
30、erence gas is used to calibrate the gas chromatograph. 3.2 interferent interfering substance air quality substance present in the air mass under investigation, other than the measurand, that affects the response ISO 9169:2006, 2.1.12 EN ISO 25139:2011 (E) DIN EN ISO 25139:2011-08 53.3 mass concentra
31、tion stationary source emissions concentration of a substance in an emitted waste gas expressed as mass per volume NOTE Mass concentration is often expressed in milligrams per cubic metre. ISO 25140:20103, 3.14 3.4 uncertainty (of measurement) parameter, associated with the result of a measurement,
32、that characterizes the dispersion of the values that could reasonably be attributed to the measurand ISO/IEC Guide 98-3:20084, 2.2.3 3.5 standard uncertainty uncertainty of the result of a measurement expressed as a standard deviation ISO/IEC Guide 98-3:20084, 2.3.1 4 Symbols and abbreviated terms A
33、MS automatic measuring system FID flame ionization detector FKM fluoro rubber GC gas chromatograph PE polyethylene PET poly(ethylene terephthalate) PLOT porous layer open tubular PTFE polytetrafluoroethylene QA/QC quality assurance and quality control A peak area ejresidual at mass concentration lev
34、el jfGCGC calibration factor k slope of the calibration line L limit of detection 2HO,vm mass of water vapour 4CHM molecular mass of methane (16 g/mol) EN ISO 25139:2011 (E) DIN EN ISO 25139:2011-08 62HOM molecular mass of water (18 g/mol) n number of measurements srrepeatability standard deviation
35、SGCGC signal SGC,calGC signal in response to the reference gas applied V0volume of the dry gas sampled Vmstandard molar volume (22,4 l/mol) xiithmeasured value x average of the measured values xijx average of the measured values at mass concentration level j4CH ,s methane mass concentration at stand
36、ard conditions of temperature and pressure 420CH ,(H O) methane mass concentration at reference conditions of water vapour (dry gas) 42CH ,O methane mass concentration at reference conditions of oxygen jjth mass concentration level 2HO,v density of water vapour 4CH ,cal methane content, as a volume
37、fraction, of the reference gas applied during calibration 4CH ,o methane content, as a volume fraction, at operating conditions 2HO water vapour content, as a volume fraction, in the waste gas 2O,m measured oxygen content, as a volume fraction, in the waste gas 2O,ref reference oxygen content, as a
38、volume fraction 5 Principle The sample gas is extracted from the waste gas duct via a sampling system and pumped into a gas-sampling bag or canister. A portion of the sample is taken off from the gas-sampling bag or canister and introduced into a gas chromatographic system. After separation on a pac
39、ked or capillary column, methane is determined by means of a flame ionization detector. EN ISO 25139:2011 (E) DIN EN ISO 25139:2011-08 76 Equipment 6.1 Sampling system The sampling system shall allow for the extraction of the sample gas from the waste gas duct. It consists in principle of: sampling
40、probe; particle filter; sample gas cooler; sample gas flow meter; sample gas pump; vacuum pump, if necessary; gas-sampling vessel (bag, glass tube or canister), or direct sampling loop to the GC. Several sampling techniques are suitable such as: use of gas-sampling bags with upstream pump (see Figur
41、e 1); use of evacuated gas-sampling vessels made of glass or canisters made of corrosion-resistant materials (e.g. stainless steel) with upstream pump (see Figure 2); use of the “lung principle” with the gas-sampling bag placed in an evacuated container; use of a sampling system as shown in Figure 1
42、 but with the gas-sampling bag replaced by a sampling line directly connected to the loop sampling system of the GC. 58432167 9Key 1 sampling probe, heated (if necessary) 6 flow meter 2 valve for introducing test gases 7 bypass valve for purging the sampling system 3 particle filter, heated 8 sampli
43、ng bag valve 4 sample gas cooler or permeation dryer 9 gas-sampling bag 5 sample gas pump Figure 1 Example of a sampling system with gas-sampling bag EN ISO 25139:2011 (E) DIN EN ISO 25139:2011-08 8843211012695711Key 1 sampling probe, heated (if necessary) 7 throttle element 2 valve for introducing
44、test gases 8 shut-off valve 3 particle filter, heated 9 gas-sampling vessel or canister 4 sample gas cooler or permeation dryer 10 temperature and pressure measuring device 5 control valve 11 shut-off valve 6 sample gas pump 12 vacuum pump (if necessary) Figure 2 Example of a sampling system with ev
45、acuated gas-sampling vessel The sampling line shall be as short as possible. The sampling line shall be installed so as to descend to the cooler. Condensation shall be avoided at any point of the sampling system. The sampling system shall meet the following requirements: the sampling probe shall be
46、a tube made of stainless steel or glass, which can be heated to 150 C, if necessary, equipped with a device (e.g. a valve) for introducing test gases; the dust filter shall be a quartz fibre or ceramic filter in a filter housing and shall be heatable to 150 C, if necessary; the sampling line shall b
47、e made of stainless steel or polytetrafluoroethylene (PTFE) and shall be heatable to 150 C, if necessary; the sample gas cooler or permeation dryer shall be suitable for a flow rate up to 1 l/min; the sample gas pump shall be gas-tight with adjustable flow rate (up to 1 l/min), and shall be heatable
48、, if necessary; vacuum pump for evacuating the gas-sampling vessel down to a residual pressure of 10 hPa to 20 hPa; connecting pieces for components of the sampling apparatus shall be made of an inert tubing material, e.g. PTFE or fluoro rubber (FKM); the flow meter with control valve shall be suita
49、ble for measuring the sampling flow rate; the gas-sampling vessel shall be gas-tight (e.g. a plastic bag with closable filler nozzle or canister of corrosion-resistant materials equipped with valves) with a volume of 5 l to 30 l; all components of the sampling system shall be made of corrosion-resistant material; all components upstream the cooler shall withstand a temperature of 150 C, if necessary. Suitable materials for the storage of methane samples are a
