1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationTest methods for quantitative determination of corrosive sulfur compounds in unused and used insulating liquidsPart 1: Test method for quantitative determination of dibenzyldisul
2、fide (DBDS)BS EN 62697-1:2012Copyright European Committee for Electrotechnical Standardization Provided by IHS under license with CENELECNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-National forewordThis British Standard is the UK implementation of EN 62697-1:20
3、12. It is identical to IEC 62697-1:2012.The UK participation in its preparation was entrusted to Technical Committee GEL/10, Fluids for electrotechnical applications.A list of organizations represented on this committee can be obtained on request to its secretary.This publication does not purport to
4、 include all the necessary provisions of a contract. Users are responsible for its correct application. The British Standards Institution 2013Published by BSI Standards Limited 2013 ISBN 978 0 580 72658 3 ICS 29.040.01Compliance with a British Standard cannot confer immunity from legal obligations.T
5、his British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2013. Amendments issued since publicationDate Text affectedBRITISH STANDARDBS EN 62697-1:2012Copyright European Committee for Electrotechnical Standardization Provided by IHS under lic
6、ense with CENELECNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-EUROPEAN STANDARD EN 62697-1 NORME EUROPENNE EUROPISCHE NORM November 2012 CENELEC European Committee for Electrotechnical Standardization Comit Europen de Normalisation Electrotechnique Europisches K
7、omitee fr Elektrotechnische Normung Management Centre: Avenue Marnix 17, B - 1000 Brussels 2012 CENELEC - All rights of exploitation in any form and by any means reserved worldwide for CENELEC members. Ref. No. EN 62697-1:2012 E ICS 29.040 English version Test methods for quantitative determination
8、of corrosive sulfur compounds in unused and used insulating liquids - Part 1: Test method for quantitative determination of dibenzyldisulfide (DBDS) (IEC 62697-1:2012) Mthodes dessai pour la dtermination quantitative des composs de soufre corrosif dans les liquides isolants usags et neufs - Partie 1
9、: Mthode dessai pour la dtermination quantitative du disulfure de dibenzyle (DBDS) (CEI 62697-1:2012) Prfverfahren zur quantitativen Bestimmung von Verbindungen korrosiven Schwefels in neuen und gebrauchten Isolierflssigkeiten - Teil 1: Prfverfahren zur quantitativen Bestimmung von Dibenzyldisulfid
10、(DBDS)(IEC 62697-1:2012) This European Standard was approved by CENELEC on 2012-09-28. CENELEC members 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 l
11、ists and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC Management Centre or to any CENELEC member. This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
12、 under the responsibility of a CENELEC member into its own language and notified to the CEN-CENELEC Management Centre has the same status as the official versions. CENELEC members are the national electrotechnical committees of Austria, Belgium, Bulgaria, Croatia, Cyprus, the Czech Republic, Denmark
13、, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, the Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 62697-1
14、:2012Copyright European Committee for Electrotechnical Standardization Provided by IHS under license with CENELECNot for ResaleNo reproduction or networking permitted without license from IHS-,-,-EN 62697-1:2012 - 2 - Foreword The text of document 10/887/FDIS, future edition 1 of IEC 62697-1, prepar
15、ed by IEC/TC 10 “Fluids for electrotechnical applications“ was submitted to the IEC-CENELEC parallel vote and approved by CENELEC as EN 62697-1:2012. The following dates are fixed: latest date by which the document has to be implemented at national level by publication of an identical national stand
16、ard or by endorsement (dop) 2013-06-28 latest date by which the national standards conflicting with the document have to be withdrawn (dow) 2015-09-28 Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CENELEC and/or CEN shall not be
17、 held responsible for identifying any or all such patent rights. Endorsement notice The text of the International Standard IEC 62697-1:2012 was approved by CENELEC as a European Standard without any modification. In the official version, for Bibliography, the following notes have to be added for the
18、 standards indicated: IEC 60296 NOTE Harmonised as EN 60296. IEC 60422 NOTE Harmonised as EN 60422. IEC 60567 NOTE Harmonised as EN 60567. BS EN 62697-1:2012Copyright European Committee for Electrotechnical Standardization Provided by IHS under license with CENELECNot for ResaleNo reproduction or ne
19、tworking permitted without license from IHS-,-,- 3 - EN 62697-1:2012 Annex ZA (normative) Normative references to international publications with their corresponding European publications The following documents, in whole or in part, are normatively referenced in this document and are indispensable
20、for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. NOTE When an international publication has been modified by common modifications, indicated by (mod), the relevant EN/H
21、D applies. Publication Year Title EN/HD Year IEC 60475 - Method of sampling insulating liquids EN 60475 - IEC 62535 2008 Insulating liquids - Test method for detection of potentially corrosive sulphur in used and unused insulating oil EN 62535 2009 BS EN 62697-1:2012Copyright European Committee for
22、Electrotechnical Standardization Provided by IHS under license with CENELECNot for ResaleNo reproduction or networking permitted without license from IHS-,-,- 2 62697-1 IEC:2012 CONTENTS INTRODUCTION . 7 1 Scope . 9 2 Normative references . 9 3 Terms, definitions and abbreviations 9 3.1 Terms and de
23、finitions 9 3.2 Abbreviations 13 4 Sampling 13 5 Procedure 13 5.1 Principle 13 5.2 Significance and use . 13 5.3 Interferences . 14 5.3.1 Co-eluting compounds . 14 5.3.2 Electron capture detector (ECD) 14 5.3.3 Atomic emission detector (AED) 14 5.3.4 Mass spectrometer (MS) 14 5.3.5 MS/MS 14 5.3.6 In
24、terference from the matrix . 14 5.4 Apparatus 15 5.4.1 Balance . 15 5.4.2 Gas chromatography system . 15 5.4.3 Data system 16 5.5 Reagents and materials . 16 5.5.1 Purity of reagents 16 5.5.2 Gases 16 5.5.3 Solvents 16 5.6 Standard materials 16 5.6.1 Dibenzyl disulfide (DBDS) . 16 5.6.2 Diphenyl dis
25、ulfide (DPDS) . 16 5.6.3 Blank oil 16 5.7 Standard solutions 17 5.7.1 Stock solution 17 5.7.2 Internal standard (IS) solution 17 6 Instrument set-up . 17 6.1 Gas chromatograph . 17 6.1.1 General . 17 6.1.2 Carrier gas 17 6.1.3 Injector 17 6.1.4 Separation parameters 17 6.1.5 ECD detection . 18 6.1.6
26、 AED detection . 18 6.1.7 MS detection . 18 6.1.8 MS/MS detection . 18 6.2 Calibration . 19 6.2.1 General . 19 6.2.2 Calibration procedure 19 BS EN 62697-1:2012Copyright European Committee for Electrotechnical Standardization Provided by IHS under license with CENELECNot for ResaleNo reproduction or
27、 networking permitted without license from IHS-,-,-62697-1 IEC:2012 3 6.2.3 Response factor determination (ECD and AED) . 19 6.2.4 Response factor determination (MS) 19 6.2.5 Response factor determination (MS/MS) 20 6.3 Analysis 20 6.3.1 Sample pre-treatment 20 6.3.2 Sample injection 20 6.3.3 Chroma
28、tographic run . 20 6.3.4 Peak integration 20 6.4 Calculations 21 6.4.1 ECD and AED 21 6.4.2 Mass spectrometer (MS) 21 6.4.3 MS/MS 21 6.5 Results 21 7 Precision data 21 7.1 Detection limit . 21 7.2 Repeatability . 22 7.3 Reproducibility 22 8 Report 22 Annex A (informative) Figures with typical chroma
29、tograms and results 23 Annex B (informative) Operating parameters for other suitable detectors . 30 Bibliography 31 Figure A.1 GC-ECD chromatogram of 2 mg kg1DBDS and DPDS (IS) in white mineral oil . 23 Figure A.2 GC-ECD chromatogram of 200 mg kg1DBDS and DPDS (IS) in white mineral oil . 24 Figure A
30、.3 GC-ECD chromatogram of commercial mineral insulating oil with a known DBDS contamination . 24 Figure A.4 GC-ECD chromatogram of commercial mineral insulating oil with no known DBDS contamination 25 Figure A.5 GC-ECD chromatogram of commercial mineral insulating oil with known DBDS contamination f
31、ortified with acommercial polychlorinated biphenyls (PCBs) formulation 25 Figure A.6 Carbon and sulfur (C-S) oil finger prints of a commercial mineral insulating oil with known DBDS contamination obtained with GC-AED 26 Figure A.7 C-S oil fingerprints of a commercial mineral insulating oil with no k
32、nown DBDS contamination obtained with GC-AED . 26 Figure A.8 C-S oil fingerprints of a commercial mineral insulating oil with known DBDS contamination obtained with GC-AED . 27 Figure A.9 Extracted ion chromatograms of DPDS (IS) molecular ion m/z 218 and DBDS molecular ion m/z 246 in white mineral f
33、ortified with DBDS, concentration 4 mg kg1. 27 Figure A.10 Extracted ion chromatograms DPDS (IS) molecular ion m/z 218 and DBDS molecular ion m/z 246 in commercial mineral insulating oil with known DBDS contamination . 28 Figure A.11 Extracted ion chromatograms m/z 109 derived from CID of DPDS (IS)
34、molecular ion m/z 218 and m/z 91 derived from CID of DBDS molecular ion m/z 246 in white mineral fortified with DBDS (4 mg/kg) 28 BS EN 62697-1:2012Copyright European Committee for Electrotechnical Standardization Provided by IHS under license with CENELECNot for ResaleNo reproduction or networking
35、permitted without license from IHS-,-,- 4 62697-1 IEC:2012 Figure A.12 Extracted ion chromatograms m/z 109 derived from CID of DPDS (IS) molecular ion m/z 218 and m/z 91 derived from CID of DBDS molecular ion m/z 246 in a commercial mineral oil with known DBDS contamination 29 Table 1 Column oven te
36、mperature programming parameters . 18 Table 2 Mass spectrometer parameters . 18 Table 3 Repeatability limit 22 Table 4 Reproducibility limit . 22 BS EN 62697-1:2012Copyright European Committee for Electrotechnical Standardization Provided by IHS under license with CENELECNot for ResaleNo reproductio
37、n or networking permitted without license from IHS-,-,-62697-1 IEC:2012 7 INTRODUCTION Sulfur can be present in insulating liquids in various forms, including elemental sulfur, inorganic sulfur compounds and organic sulfur compounds. The number of diverse sulfur species comprised of different isomer
38、s and homologous can run into hundreds. The total sulfur(TS) concentration in insulating liquids depends on the origin of the liquid, refining processes and the degree of refining and formulation including addition of additives to the base oils. Base oils include mineral based paraffinic and naphthe
39、nic oils, synthetic iso- paraffins obtained through gas to liquid conversion process (GTL-Fischer-Tropsch), esters, poly alpha olefins, poly alkylene glycols, etc. Additives can be comprised of electrostatic discharge depressants, metal deactivators, metal passivators, phenolic and sulfur containing
40、 antioxidants such as the polysulfides, disulfides, dibenzyl disulfide (DBDS), etc. Certain sulfur compounds present in the insulating liquids exhibit antioxidant and metal deactivating properties without being corrosive, whereas other sulfur compounds have been known to react with metal surfaces. S
41、pecifically, sulfur compounds such as mercaptans are very corrosive to metallic components of electrical devices. Presence of these corrosive sulfur species has been linked to failures of electrical equipment used in generation, transmission and distribution of electrical energy for several decades.
42、 Therefore, the IEC standard for mineral insulating oils states that corrosive sulfur compounds shall not be present in unused and used insulating liquids (see IEC 60296) 51. Recently, the serious detrimental impact of corrosive sulfur has been linked to the presence of a specific highly corrosive s
43、ulfur compound, DBDS. This compound has been found in certain mineral insulating oils 1, 14, 15, 16; presence of this compound has been shown to result in copper sulfide formation on the surfaces of copper conductors under normal operating conditions of transformers 2. Current standard test methods
44、for detection of corrosive sulfur (ASTM D1275, methods A and B, and DIN 51353) and potentially corrosive sulfur in used and unused insulating oil (IEC 62535) are empirical and qualitative. These methods rely on visual and subjective perception of colour profiles. The methods do not yield quantitativ
45、e results in regard to the concentration of DBDS or other corrosive sulfur compounds present in insulating liquids. Furthermore, methods for corrosive sulfur and potentially corrosive sulfur in insulating liquids (ASTM D1275, method B and IEC 62535) are applicable only to mineral insulating oils tha
46、t do not contain a metal passivator additive, the methods otherwise can yield negative results even when corrosive sulfur compounds are present in the insulating liquids thus providing a false negative test result. On the other hand, the test method when used with aged insulating oils (e.g. those wi
47、th relative high acidity), may give ambiguous results and lead to a false positive test result. Further analysis of insulating liquids is stipulated, e.g. IEC 62535 specifies that if there are any doubts in the interpretation of the results of inspection of paper, the composition of precipitate shou
48、ld be analyzed by other methods (for example by SEM-EDX). For this reason, IEC TC 10 WG 37 was set up to prepare test methods for the unambiguous quantitative determination of corrosive sulfur compounds in unused and used insulating liquids. Because of the complexity of such determinations, the test methods are divided into three parts: Part 1 Test method for quantitative determination of dibenzyldisulfide (DBDS). Part 2 Test methods for quantitative determination of total corrosive sulfur (TCS). Part 3 Test methods for quantitative determination of to
