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 62697-1:2012National forewordThis British Standard is the UK implementation of EN 62697-1:2012. 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 r
3、epresented on this committee can be obtained on request to its secretary.This publication does not purport to 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
4、0 580 72658 3 ICS 29.040.01Compliance with a British Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2013. Amendments issued since publicationDate Text affectedBRITISH STANDARD
5、BS EN 62697-1:2012EUROPEAN STANDARD EN 62697-1 NORME EUROPENNE EUROPISCHE NORM November 2012 CENELEC European Committee for Electrotechnical Standardization Comit Europen de Normalisation Electrotechnique Europisches Komitee fr Elektrotechnische Normung Management Centre: Avenue Marnix 17, B - 1000
6、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 of corrosive sulfur compounds in unused and used insulating liquids - Part 1: Test
7、 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: Mthode dessai pour la dtermination quantitative du disulfure de dibenzyle (DBDS)
8、 (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 (DBDS)(IEC 62697-1:2012) This European Standard was approved by CENELEC on 2012-09
9、-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 lists and bibliographical references concerning such national standards may be obta
10、ined 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 under the responsibility of a CENELEC member into its own language and notified t
11、o 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, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece
12、, 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 62697-1:2012EN 62697-1:2012 - 2 - Foreword The text of document 10/887/FDIS, future editi
13、on 1 of IEC 62697-1, prepared 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
14、an identical national standard 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. CENE
15、LEC and/or CEN shall not be 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 not
16、es have to be added for the 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 62697-1:2012- 3 - EN 62697-1:2012 Annex ZA (normative) Normative references to international publications with their correspondi
17、ng European publications The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any ame
18、ndments) applies. NOTE When an international publication has been modified by common modifications, indicated by (mod), the relevant EN/HD applies. Publication Year Title EN/HD Year IEC 60475 - Method of sampling insulating liquids EN 60475 - IEC 62535 2008 Insulating liquids - Test method for detec
19、tion of potentially corrosive sulphur in used and unused insulating oil EN 62535 2009 BS EN 62697-1:2012 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 definitions 9 3.2 Abbreviations 13 4 Sampling 13 5 Proce
20、dure 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 Interference from the matrix . 14 5.4 Apparatus 15 5.4.1
21、 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 disulfide (DPDS) . 16 5.6.3 Blank oil 16 5.7 Standard sol
22、utions 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 AED detection . 18 6.1.7 MS detection . 18 6.1.8 MS/M
23、S detection . 18 6.2 Calibration . 19 6.2.1 General . 19 6.2.2 Calibration procedure 19 BS EN 62697-1:201262697-1 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
24、pre-treatment 20 6.3.2 Sample injection 20 6.3.3 Chromatographic 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 Repo
25、rt 22 Annex A (informative) Figures with typical chromatograms 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 k
26、g1DBDS and DPDS (IS) in white mineral oil . 24 Figure A.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
27、 mineral insulating oil with known DBDS contamination fortified 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 finger
28、prints of a commercial mineral insulating oil with no known 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/
29、z 218 and DBDS molecular ion m/z 246 in white mineral fortified 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 i
30、on 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 white mineral fortified with DBDS (4 mg/kg) 28 BS EN 62697-1:2012 4 62697-1 IEC:2012 Figure A.12 Extracted ion chromatograms m/z 109 derived from CID of DPDS (IS)
31、 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 temperature programming parameters . 18 Table 2 Mass spectrometer parameters . 18 Table 3 Repeatability limit 22 Table 4 Reproducibility l
32、imit . 22 BS EN 62697-1:201262697-1 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 isomers and homologous can run in
33、to 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 naphthenic oils, synthetic iso- pa
34、raffins 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 antioxidants such as the p
35、olysulfides, 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. Specifically, sulfur compoun
36、ds 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. Therefore, the IEC standar
37、d 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 sulfur compound, DBDS. This
38、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 for detection of corrosive
39、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 quantitative results in regard to the
40、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 that do not contain a metal pa
41、ssivator 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 with relative high acidity),
42、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 should be analyzed by other met
43、hods (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 t
44、hree 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 total mercaptans and disulfides (TMD) and other targeted corrosive sulf
45、ur species. _ 1Figures in square brackets refer to the bibliography. BS EN 62697-1:2012 8 62697-1 IEC:2012 Health and safety This part of IEC 62697 does not purport to address all the safety problems associated with its use. It is the responsibility of the user of the standard to establish appropria
46、te health and safety practices and determine the applicability of regulatory limitations prior to use. The insulating liquids which are the subject of this standard should be handled with due regard to personal hygiene. Direct contact with eyes may cause slight irritation. In the case of eye contact
47、, irrigation with copious quantities of clean running water should be carried out and medical advice sought. Some of the tests specified in this standard involve the use of processes that could lead to a hazardous situation. Attention is drawn to the relevant standard for guidance. Environment This
48、standard involves mineral insulating oils, natural ester insulating liquids, chemicals and used sample containers. The disposal of these items should be carried out in accordance with current national legislation with regard to the impact on the environment. Every precaution should be taken to preve
49、nt the release of chemicals used during the test into the environment. BS EN 62697-1:201262697-1 IEC:2012 9 TEST METHODS FOR QUANTITATIVE DETERMINATION OF CORROSIVE SULFUR COMPOUNDS IN UNUSED AND USED INSULATING LIQUIDS Part 1: Test method for quantitative determination of dibenzyldisulfide (DBDS) 1 Scope This part of IEC 62697 specifies a test method for the quantitative determination of corrosive sulfur compounds-dibenzyl disulfide (DBDS) in used and unused insu
