EN 15470-2017 en Liquefied petroleum gases - Determination of dissolved residues - High temperature Gas chromatographic method.pdf

1、Liquefied petroleum gases - Determination of dissolved residues - High temperature Gas chromatographic methodBS EN 15470:2017BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15470 July 2017 ICS 75.160.20 Supersedes

2、EN 15470:2007English Version Liquefied petroleum gases - Determination of dissolved residues - High temperature Gas chromatographic methodGaz de ptrole liqufi - Dtermination des rsidus dissous - Mthode par chromatographie en phase gazeuse, haute temprature Flssiggas - Bestimmung der gelsten Rckstnde

3、 - Hochtemperatur-Gaschromatographie-Verfahren This European Standard was approved by CEN on 24 April 2017. CEN 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 alterat

4、ion. 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 (English, French, German). A version in any other language made b

5、y 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, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,

6、 Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR

7、STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15470:2017 ENational forewordThis B

8、ritish Standard is the UK implementation of EN 15470:2017. It supersedes BS EN 15470:2007, which is withdrawn.The UK participation in its preparation was entrusted to Technical Committee PTI/15, Natural Gas and Gas Analysis.A list of organizations represented on this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 can be obtained on req

9、uest 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 2017 Published by BSI Standards Limited 2017ISBN 978 0 580 91752 3ICS 75.160.20Compliance with a British

10、 Standard cannot confer immunity from legal obligations.This British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 August 2017.Amendments/corrigenda issued since publicationDate Text affectedBRITISH STANDARDBS EN 15470:2017EUROPEAN STANDARD NORME EUR

11、OPENNE EUROPISCHE NORM EN 15470 July 2017 ICS 75.160.20 Supersedes EN 15470:2007English Version Liquefied petroleum gases - Determination of dissolved residues - High temperature Gas chromatographic methodGaz de ptrole liqufi - Dtermination des rsidus dissous - Mthode par chromatographie en phase ga

12、zeuse, haute temprature Flssiggas - Bestimmung der gelsten Rckstnde - Hochtemperatur-Gaschromatographie-Verfahren This European Standard was approved by CEN on 24 April 2017. CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this Euro

13、pean 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 application to the CEN-CENELEC Management Centre or to any CEN member. This European Standard exists in three official version

14、s (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, Be

15、lgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Swed

16、en, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2017 CEN All rights of exploitation in any form and by any means reserved worldwide for CE

17、N national Members. Ref. No. EN 15470:2017 EBS EN 15470:2017EN 15470:2017 (E) 2 Contents Page European foreword 3 1 Scope . 4 2 Normative references . 4 3 Terms and definitions 4 4 Principle 4 5 Reagents 5 6 Apparatus 5 7 Sampling 5 8 Procedure 6 8.1 Safety 6 8.2 Sample transfer procedure . 6 8.3 Ev

18、aporation procedure 7 8.4 Gas chromatography analysis of the residue . 7 8.4.1 Preparation of the internal standard solution A 7 8.4.2 Determination of the blank 8 8.4.3 Sample analysis . 8 9 Calculations 8 10 Expression of results . 8 11 Precision 9 11.1 General . 9 11.2 Repeatability, r 9 11.3 Rep

19、roducibility, R 9 Annex A (normative) Equipment for sample transfer and evaporation 10 A.1 Sampling set 10 A.2 Venting lines . 10 Annex B (informative) Examples of gas chromatograms . 12 Bibliography 14 BS EN 15470:2017EN 15470:2017 (E) 3 European foreword This document (EN 15470:2017) has been prep

20、ared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretariat of which is held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical tex

21、t or by endorsement, at the latest by January 2018, and conflicting national standards shall be withdrawn at the latest by January 2018. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN shall not be held responsible for identif

22、ying any or all such patent rights. This document supersedes EN 15470:2007. The main changes in this version being: a) numerous changes of both technical and editorial nature have been made to add clarity to the text; b) clarification that the use of a drying agent in the desiccator is not recommend

23、ed; c) the description of the equipment used has been improved; d) Formula (1) has been corrected for an error; e) small changes in the vent line (6.6) and the flasks (6.7) in order to improve the technical safety of the method; f) information contained in Annex B that deemed to be obsolete has been

24、 removed. According to the CEN-CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, F

25、rance, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 15470:2017EN 15470:2017 (E) 4 1 Scope This European Standard sp

26、ecifies a method for determining the dissolved residual matter in liquefied petroleum gases (LPG), in the range of 40 mg/kg to 100 mg/kg. Higher concentrations can be determined by adjusting the sample size. The dissolved residue is the amount of organic compounds which is detectable by gas chromato

27、graphy after evaporation of the sample at ambient temperature and then in an oven at 105 C. This method is not suitable for detecting solid materials or for possibly high molar mass polymers (1 000 g/mol). From the analysis of a limited LPG sample size (50 g to 75 g) this method allows obtaining inf

28、ormation on the potential origin of the residue (gasoil, lubricants, plasticizers, etc.). The precision data of the method have been determined from 20 mg/kg to 100 mg/kg. For a higher content of residue, the precision has not been tested. NOTE An alternative European Standard, EN 15471 1, specifies

29、 a gravimetric method. WARNING The use of this standard can involve hazardous materials, operations and equipment. This standard does not purport to address all of the safety problems associated with its use. It is the responsibility of users of this standard to take appropriate measures to ensure t

30、he safety and health of personnel prior to application of the standard, and fulfil statutory and regulatory requirements for this purpose. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For d

31、ated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 4257, Liquefied petroleum gases - Method of sampling (ISO 4257:2001) 3 Terms and definitions For the purposes of this document, the follow

32、ing term and definition applies. 3.1 liquefied petroleum gas LPG petroleum gas that can be stored and/or handled in the liquid phase under moderate conditions of pressure and at ambient temperature, consisting predominantly of propane and butanes, with small proportions of propene, butenes and penta

33、nes/pentenes 4 Principle A known mass of LPG, between 50 g and 75 g, is sampled and evaporated in a standard small flask. The residue is heated in an oven at 105 C for 1 h. It is then diluted with a solvent and one internal standard is added. The mixture is then analysed by a capillary gas chromatog

34、raphy and quantified by the internal standard method. BS EN 15470:2017EN 15470:2017 (E) 5 5 Reagents 5.1 Propan-2-ol, analytical grade. 5.2 Carbon dioxide, solid for cooling. 5.3 Carbon disulfide, analytical grade (99,9 % minimum). 5.4 Normal Octane, analytical grade (99,9 % minimum), for use as int

35、ernal standard. 5.5 Pentane, analytical grade (99,5 % minimum). 6 Apparatus 6.1 Sample cylinder, of a total mass compatible with the balance used; preferably made of stainless steel fitted with two stainless steel valves free of oily materials, conforming to EN ISO 4257. 6.2 Cooling bath, comprised

36、of a 0,5l to 2l Dewar flask, filled with propan-2-ol (5.1) cooled by adding solid carbon dioxide (5.2), to achieve a temperature of approximately 77 C. 6.3 Sampling set, according to Annex A. 6.4 Balance, for weighing the sample cylinder, maximum weight depending of the sample cylinder weight (for i

37、nstance 16 kg or 30 kg), capable of weighing to the nearest 1 g. 6.5 Analytical balance, capable of weighing to the nearest 0,1 mg. 6.6 Vent line, according to Annex A. The vent line shall have a suitable internal diameter as not to restrict adequate venting of the evaporated LPG; 1/8 inch tubing ha

38、s been found suitable for use. 6.7 Flasks, (100 ml to 150 ml), made of glass and capable of being sealed or closed. Flasks with screw open caps in conjunction with a septum (see 6.8) have been found suitable for use. 6.8 Septum, adapted to the flask, PTFE/silicon. 6.9 Gas chromatograph. 6.10 Capilla

39、ry column, capable of being programmed up to 400 C for which the following characteristics are suggested: weakly polar capillary column (phenyl polycarborane siloxane at 5 %), high temperature, type HT5, 0,53 mm id, 0,15 m, 10 m. 6.11 Oven, of the static type (without fan assisted circulation), expl

40、osion-proof, capable of heating to (105 5) C. 6.12 Desiccator, (a drying agent is not recommended). 7 Sampling Samples shall be taken as described in EN ISO 4257 and/or in accordance with the requirements of national standards or regulations for the sampling of automotive LPG. BS EN 15470:2017EN 154

41、70:2017 (E) 6 8 Procedure 8.1 Safety CAUTION It is essential to work under an explosion-proof hood. In order to remove both the LPG and carbon disulfide vapours, take all the necessary safety measures and, in particular, earth the equipment in order to eliminate the risks associated with static elec

42、tricity. 8.2 Sample transfer procedure a) Put the sample cylinder (6.1) on the balance (6.4); b) assemble the apparatus, using the set shown in Annex A and following Figure A.1, by connecting the liquid phase valve of the sample cylinder to the sampling line comprising: PTFE line; spindle-needle val

43、ve; 1/16” stainless steel injection tubing; c) fix the PTFE line to a support in order that the sampling operations do not disturb the balance; d) prepare a cooling bath (6.2) by filling a beaker or small Dewar with solid carbon dioxide and propan-2-ol; e) clean a flask (6.7) with analytical pentane

44、 (5.5) and dry the flask; f) place the cleaned and dry flask in the cooling bath for at least 1 min before starting the transfer of the sample; NOTE This enables a better introduction of the sample into the glass container. Figure A.1 provides one example of a set-up for transferring a quantity of m

45、aterial from the sample cylinder to the flask, which includes a screw open cap (6.7) and septum (6.8) with 2 small holes permitting passages for a sample introduction line and venting line (A.2). g) close the needle valve; h) open the sample cylinder cautiously and fill/purge the sampling line by op

46、ening the needle valve slightly and progressively; i) close the needle valve when the LPG flows regularly; j) introduce the injection end in the flask; k) record the mass of the sample cylinder, m1; l) transfer the LPG sample slowly by opening the needle valve; m) close the needle valve when approxi

47、mately 75 g product has been transferred; n) record the mass of the sample cylinder, m2; BS EN 15470:2017EN 15470:2017 (E) 7 o) the mass m of the LPG sample in grams is given by the following formula: = 12mm m (1) 8.3 Evaporation procedure Disconnect the sampling line and leave the vaporized gas to

48、exit through the venting line. CAUTION The lower end of the vent line, as shown in Figure A.1 shall never reach into the boiling liquid phase. The evaporation of the sample starts as soon as the sample transfer begins; the flask is left at ambient temperature. The gas is vented through the hood. Whe

49、n the evaporation of the sample from the flask at ambient conditions is completed (no apparent liquid is in the flask), the flask is opened and the residue is further evaporated in the oven for 1 h at 105 C. The flask is then cooled down in a desiccator for 30 min before it is closed with cap and septum. CAUTION Close the flask with the septum with the PTFE side downwards. Store the flask in the upright position. 8.4 Gas chromatography analysis of the residue 8.4.1 Preparation of the internal standard solution A Accurately