DIN EN 16423-2014 Liquefied petroleum gases - Determination of dissolved residue - Gas chromatographic method using liquid on-column injection German version EN 16423 2013《液化石油气 溶解.pdf

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1、February 2014 Translation by DIN-Sprachendienst.English price group 13No 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).I

2、CS 75.160.20!%,BQ“2093146www.din.deDDIN EN 16423Liquefied petroleum gases Determination of dissolved residue Gas chromatographic method using liquid, on-column injection;English version EN 16423:2013,English translation of DIN EN 16423:2014-02Flssiggas Bestimmung gelster Rckstnde Gaschromatographisc

3、hes Prfverfahren durch Direkteinspritzung von Flssigkeit auf dieSule;Englische Fassung EN 16423:2013,Englische bersetzung von DIN EN 16423:2014-02Gaz de ptrole liqufi Dtermination des rsidus dissous Mthode par chromatographie en phase gazeuse avec injection liquide on-column;Version anglaise EN 1642

4、3:2013,Traduction anglaise de DIN EN 16423:2014-02www.beuth.deDocument comprises 26 pagesIn case of doubt, the German-language original shall be considered authoritative.01.14DIN EN 16423:2014-02 2 A comma is used as the decimal marker. National foreword This document (EN 16423:2013) has been prepar

5、ed by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” (Secretariat: NEN, Netherlands). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Materials Testing Standards C

6、ommittee), Working Committee NA 062-06-31 AA Anforderungen an Flssiggase of the Fachausschuss Minerall- und Brennstoffnormung (FAM). EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16423 October 2013 ICS 75.160.20 English Version Liquefied petroleum gases - Determination of dissolved residue -G

7、as chromatographic method using liquid, on-column injectionGaz de ptrole liqufi - Dtermination des rsidus dissous - Mthode par chromatographie en phase gazeuse avec injection liquide on-column Flssiggas - Bestimmung gelster Rckstnde - Gaschromatographisches Prfverfahren durch Direkteinspritzung von

8、Flssigkeit auf die Sule This European Standard was approved by CEN on 31 August 2013. 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 alteration. Up-to-date lists

9、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 by translation under th

10、e 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, Finland, Former Yugos

11、lav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN

12、DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2013 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16423:2013: EEN 16423:2013 (E) 2 Contents Page Foreword 3 Introdu

13、ction .4 1 Scope 5 2 Normative references 5 3 Terms and definitions .5 4 Principle 5 5 Reagents and materials 5 6 Apparatus .6 7 Sampling 10 8 Preparation of apparatus . 10 9 Test procedure 11 9.1 Safety and hazards . 11 9.2 Summary of the method . 11 9.3 Calibration . 11 9.4 Procedure 12 10 Calcula

14、tions . 13 11 Quality control . 14 12 Expression of results . 14 13 Precision 14 13.1 General . 14 13.2 Repeatability 14 13.3 Reproducibility 15 14 Test report . 15 Annex A (normative) Density calculation of the LPG and correction of the result . 16 Annex B (informative) Quality control monitoring 1

15、9 Annex C (informative) Analysis of benzene, toluene and hydrocarbons C7through C10. 20 Annex D (informative) Analysis of di-iso-propanolamine 22 Annex E (informative) FID linearity check 23 Bibliography . 24 DIN EN 16423:2014-02 EN 16423:2013 (E) 3 Foreword This document (EN 16423:2013) has been pr

16、epared 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 t

17、ext or by endorsement, at the latest by April 2014 and conflicting national standards shall be withdrawn at the latest by April 2014. 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

18、 for identifying any or all such patent rights. 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, Fo

19、rmer Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 16423:2014-02 EN 16423:2013 (E)

20、4 Introduction Control over the residue content as specified in EN 589 is of considerable importance in end-use applications of Liquefied Petroleum Gas (LPG). Dissolved residual matter, also known as evaporation residue, in LPG is contamination which can occur during production, transportation or st

21、orage. This standard has been developed as a potential replacement of the commonly used methods, as this method of determination: is quicker and much more sensitive than manual methods, such as ASTM D2158 1 or EN 15471 2, which are based on evaporation of (large) sample volumes followed by visual or

22、 gravimetric estimation of residue content; provides enhanced sensitivity in measurements of heavier (evaporation) residues compared to EN 15470 3, with a quantification limit of 10 mg/kg total residue; gives both quantitative results and information about contaminant composition such as boiling poi

23、nt range and fingerprint, which can be very useful in tracing the source of a particular contaminant. DIN EN 16423:2014-02 EN 16423:2013 (E) 5 1 Scope This European Standard specifies a method for the determination of the dissolved residual matter, also known as evaporation residue, in liquefied pet

24、roleum gases (LPG), by gas chromatography in the range of (10 to 600) mg/kg (ppm mass). This test method quantifies soluble organic compounds (hydrocarbon materials), sometimes called evaporation residue, which can be present in liquefied petroleum gases and which are substantially less volatile tha

25、n the LPG product, i.e. with a boiling point between 174 C and 522 C (C10to C40). Higher boiling materials, or materials that adhere permanently to the chromatographic column, will not be detected. WARNING This standard does not purport to address all of the safety concerns, if any, associated with

26、its use. It is the responsibility of the user of this standard to establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document

27、 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 amendments) applies. EN 589, Automotive fuels LPG Requirements and test methods EN ISO 4257, Liquefied petroleum gase

28、s Method of sampling (ISO 4257) EN ISO 8973:1999, Liquefied petroleum gases Calculation method for density and vapour pressure (ISO 8973:1997) ISO 1998-1, Petroleum industry Terminology Part 1: Raw materials and products 3 Terms and definitions For the purposes of this document, the terms and defini

29、tions given in EN 589, ISO 1998-1, and the following apply. 3.1 high pressure liquefied gas injector sample introduction device which injects liquefied gas samples under pressure and at room temperature directly onto the chromatographic column thereby maintaining the sample in liquid phase during th

30、e injection process 3.2 pressure station device that supplies high pressure inert gas to a suitable sample cylinder and therefore maintains sample in the liquid phase during the injection procedure 4 Principle A small quantity of LPG is directly transferred in liquid phase from the sample cylinder o

31、n to a GC column using a high pressure liquefied gas injector. The mixture is then analysed by capillary gas chromatography and the dissolved residue content is quantified by the external standard method. 5 Reagents and materials IMPORTANT Standards that are prepared in pentane, normally liquid at r

32、oom temperature, shall be stored under refrigeration and transferred to sample cylinders prior to use. Alternatively, they can be stored in air tight cylinders. DIN EN 16423:2014-02 EN 16423:2013 (E) 6 5.1 Mineral oil in LPG calibration mixture. One of the following mixtures shall be selected for ca

33、libration: 5.1.1 Mineral oil in LPG calibration mixture, certified calibration mixture with about 50 mg/kg mineral oil in LPG. 5.1.2 Mineral oil in pentane calibration mixture. Prepare a calibration standard of mineral oil in pentane. Record the exact weighed value to the nearest mg of mineral oil a

34、nd calculate the concentration in mg/kg. The concentration of the mineral oil shall be close to the expected concentration of the contamination in the LPG sample. 5.1.3 Mineral oil or local hydrocarbon fraction, boiling point range approximately C10to C40. Alternatively, a well characterised local h

35、ydrocarbon fraction, within the range C10to C40, can be used to provide quantitative and qualitative comparison to the contaminant in the sample. Care should be taken to ensure no significant fraction falls outside the C10to C40range. 5.2 Validation standard, mineral oil in pentane. Prepare a valida

36、tion standard of mineral oil in pentane. Record the exact weighed value to the nearest mg of mineral oil and calculate the concentration in mg/kg. The concentration of the mineral oil shall be close to the expected concentration of the contamination in the LPG sample. 5.3 n-Alkane retention time sta

37、ndard, mixture containing at least C10and C40in a concentration of (nominally) 5 mg/l each, dissolved in pentane or heptane. 5.4 Solvent, GC grade pentane. 6 Apparatus NOTE Successfully used columns and conditions are given in Table 1. 6.1 Gas chromatograph, equipped with a Large Volume Cold on Colu

38、mn Injector (LVOCI), linear temperature programmable column oven, and a flame ionisation detector (FID), with data acquisition and processing system. For checking the linearity of the FID one may use Annex E. 6.2 Solvent vent, controlled to allow venting the major part of the matrix. 6.3 Retention g

39、ap, uncoated stainless steel capillary. 6.4 Retaining pre-column, a column with a polydimethylsiloxane stationary phase. 6.5 Analytical column, a column with a polydimethylsiloxane stationary phase. 6.6 Column coupler, coupling device suitable for leak free coupling of the retention gap to the retai

40、ning pre-column. See Figure 1 for a schematic overview of the couplings inside the GC oven and the couplings to the solvent vent valve. DIN EN 16423:2014-02 EN 16423:2013 (E) 7 Table 1 Typical column configuration Equipment part Typical operation conditions Oven program 35 C for 3 min, 35 C to 340 C

41、 at 25 C/min, 340 C for 10 min Inlet program Type: cool on-column Temp: 55 C for 3 min, 55 C to 340 C at 25 C/min, 340 C for 9 min Detector settings Air flow: 400 ml/min Hydrogen flow: 40 ml/min Make up gas flow: 20 ml/min Temperature: 350 C Data rate: 20 Hz Column Retention gap: Sulfinert1 )stainle

42、ss steel capillary with inner diameter 0,53 mm and length of 5 m Retaining pre-column: 3 m HP-1, 0,53 mm, 2,65 m Analytical column: HP-1, 30 m, 0,32 mm, 0,25 m Pressure station Sample flow: 2 ml/min Nitrogen pressure: 2 500 kPa Nitrogen purge pressure: 500 kPa Liquefied gas injector Injection: 25 ms

43、 1) Sulfinert is a stainless steel treatment system from Restek Co., 110 Benner Circle, Bellefonte, PA 16823, USA. This information is given for the convenience of users of this European Standard and does not constitute an endorsement by CEN of the product named. Equivalent products may be used if t

44、hey can be shown to lead to the same results. DIN EN 16423:2014-02 EN 16423:2013 (E) 8 6.7 Column splitter, suitable for leak-free coupling of the retaining pre-column to one side of the analytical column and the deactivated capillary on the other side. See Figure 1 for a schematic overview of the c

45、ouplings inside the GC oven and the couplings to the solvent vent valve. Key A solvent vent valve B cool on-column inlet C detector D column splitter E retention gap F retaining pre-column G analytical column Figure 1 Column overview DIN EN 16423:2014-02 EN 16423:2013 (E) 9 6.8 High pressure liquefi

46、ed gas injector, a high pressure valve as in Figure 2, directly connected to a needle which is inserted in the injection port of the GC, after which the valve is triggered in order to introduce a representative aliquot into the GC system without sample discrimination. Key A electrical attachment B s

47、olenoid on C valve spring D spray tip E pressurised fuel injection F injector casing G plunger Figure 2 High pressure valve DIN EN 16423:2014-02 EN 16423:2013 (E) 10 6.9 Pressure station, ensuring a sample in liquid phase at a constant pressure, with a typical configuration as in Figure 3. Key A sam

48、ple cylinder B sample line in C injection device D cool on column inlet E gas chromatograph F sample line out G rotometer H vaporiser I waste systemFigure 3 Typical configuration of the pressure station 7 Sampling Unless otherwise specified in the commodity specification, samples shall be taken as d

49、escribed in EN ISO 4257 and/or in accordance with the requirements of national regulations for the sampling of the product under test. 8 Preparation of apparatus CAUTION Take all the necessary safety measures and, in particular, earth the equipment in order to eliminate the risks associated with static electricity. 8.1 Gas chromatograph: install and verify performance in accordance with the manufacturers instructions. Typical operating conditions are shown in Table 1. 8.2 Pressure station