DIN 51619-2004 Testing of mineral oil hydrocarbons - Determination of the composition of liquid petroleum gases - Gas chromatographic analysis under special consideration of 1 3-bu.pdf

1、February 2004 English price group 6No 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 75.160.30!%dt“2655981www.din.deD

2、IN 51619Testing of mineral oil hydrocarbons Determination of the composition of liquid petroleum gases Gas chromatographic analysis under special consideration of 1,3-butadiene with mass fractions 0,1 % (m/m),English translation of DIN 51619:2004-02Prfung von Minerall-Kohlenwasserstoffen Bestimmung

3、der Zusammensetzung von Flssiggas Gaschromatographische Analyse unter besonderer Bercksichtigung von 1,3-Butadien mit Massenanteilen 0,1 % (m/m),Englische bersetzung von DIN 51619:2004-02Essai des huiles minrales Dtermination de la composition des gaz de ptrole liqufis Analyse par chromatographie en

4、 phase gazeuse avec considration spciale du 1,3-butadine avec fractions de masse 0,1 % (m/m),Traduction anglaise de DIN 51619:2004-02SupersedesDIN 51619:1985-08www.beuth.deDocument comprises 9 pagesDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered

5、authoritative.04.17 DIN 51619:2016-07 2 A comma is used as the decimal marker. Contents Page Foreword . 3 1 Scope 4 2 Normative references 4 3 Symbols and abbreviations 4 4 Principle 4 5 Apparatus . 5 6 Sampling . 5 7 Procedure . 5 7.1 Test preparation 5 7.2 Analysis sample preparation 6 7.3 Sample

6、injection and analysis . 6 7.4 Tests for the quantitative evaluation of the gas chromatogram 7 8 Quantitative evaluation . 7 9 Expression of results 8 10 Precision . 9 10.1 General 9 11 Test report . 9 DIN 51619:2016-07 3 Foreword This standard has been prepared by DIN-Normenausschuss Materialprfung

7、 (DIN Standards Committee Materials Testing), Working Group NA 062-06-41 AA “Testing of liquefied petroleum gases”, of the Fachausschuss Minerall und Brennstoffnormung (Standardization Committee for Petroleum, Fuels, Lubricants and Related Products). Amendments This standard differs from DIN 51619:1

8、985-08 as follows: a) the measuring range for the analysis by gas chromatography has been extended taking 1,3-butadiene into particular account; b) a new subclause 7.2 “Preparation of the analysis sample” has been included; c) the text has been modified to take the extended measuring range into acco

9、unt and has been revised in form and substance. The normative standards have also been updated. Previous editions DIN 51611: 1955-04, 1956-03 DIN 51619: 1964-11, 1985-08 DIN 51619:2016-07 4 1 Scope This standard applies to liquid petroleum gases according to DIN 51622 taking into account the Gefahre

10、nstoffverordnung (GefStoffV Ordinance on Hazardous Substances) of 15 October 1999. The method of analysis only deals with hydrocarbons with a boiling point of up to 100 C. The limits for inert components additionally stipulated in DIN 51622 can be checked by means of a gaschromatographic method usin

11、g a thermal conductivity detector. 2 Normative references 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 refer

12、enced document (including any amendments) applies. DIN 1333, Presentation of numerical data DIN 51405, Testing of mineral oil hydrocarbons, similar liquids and solvents for paints and varnishes Analysis by gas chromatography General working principles DIN 51610, Testing of liquefied petroleum gases

13、Sampling DIN 51618, Testing of liquefied petroleum gases Calculation of density at 15 C, 20 C and 50 C DIN 51622, Liquefied petroleum gases Propane, propene, butane, butene and their mixtures Requirements DIN 51640, Testing of liquified petroleum gases Calculation of vapour pressure at 40 C and 70 C

14、 DIN EN ISO 4259, Petroleum products Determination and application of precision data in relation to methods of test GefStoffV1), Gefahrstoffverordnung (German Ordinance on Hazardous Substances) from October 15, 1999 (BGBl. (German Federal Law Gazette) 1999, pp. 2233-2281) 3 Symbols and abbreviations

15、 g/(100 g); given as a mass fraction in % 4 Principle A gaseous analysis sample is made from a homogenous liquid petroleum gas sample by complete evaporation of a sufficient proportion of the liquid phase. It is then passed through a suitable separation column (e.g. capillary separation column) via

16、a carrier gas. In the separation column, the individual constituents (referred to as “components” in this standard) contained in the liquid petroleum gas are separated as a result of either their different distribution coefficients or their adsorption coefficients. The components exiting the separat

17、ion column together with the carrier gas are registered by a detector and the displayed data is recorded. The mass fractions of the components are determined by suitable measurement of the peak areas and subsequent correction using the applicable calibration factors. 1) Obtainable from: Deutsches In

18、formationszentrum fr technische Regeln (DITR), DIN Deutsches Institut fr Normung e. V., 10772 Berlin. Street address: Burggrafenstr. 6, 10787 Berlin. DIN 51619:2016-07 5 5 Apparatus Gas chromatograph and evaluation scheme according to DIN 51405. Flame ionization detectors (FID) shall be used. Evapor

19、ators shall be stainless steel capillaries with the following dimensions: a) for propane: length: 3,5 m, inner diameter: 0,5 mm; b) for butane: length: 3,0 m, inner diameter: 1,0 mm. A minimum of 80 % of the relevant capillaries shall be heated. 6 Sampling Sampling shall be according to DIN 51610. 7

20、 Procedure 7.1 Test preparation The test preparation shall be according to DIN 51405. Example of the apparatus and conditions required for the analysis of liquid petroleum gas (determination of hydrocarbons): separation column capillary quartz column stationary phase: Al2O3/KCl film thickness: 10 m

21、length: 50 m inner diameter: 0,53 mm carrier gas: nitrogen nominal inlet pressure of carrier gas: 410 kPa gas flow rate: 3 ml N2/min split ratio: 1:50 temperature programme: according to Figure 1 Figure 1 Temperature programme DIN 51619:2016-07 6 7.2 Analysis sample preparation The sample is taken f

22、rom a gas cylinder according to DIN 51610 with the valve completely open because, in the gas cylinder, the composition of the phase above the liquid phase is generally different from that of the liquid phase2). The sample is then transferred via an evaporator to a gas collection vessel (see Figure 2

23、). A gas flow of about 3 l/min should be selected. The evaporator temperature shall be in the range between 70 C and 100 C. DANGER Explosive mixtures can form on contact with air. Measures shall be taken to avoid danger due to explosive mixtures (e.g. by using an explosion-protected temperature cont

24、rol unit or keeping substances separated, etc.). In order to achieve proper cleaning and filling of the gas collection vessel it is sufficient to transfer a volume of sample gas ten times the volume of the collection vessel. The temperature in the gas collection vessel shall be above the dew point o

25、f the hydrocarbons. Key 1 Sample cylinder according to DIN 51610 4 Temperature control unit 2 Valve 5 Overpressure relief valve 3 Evaporator 6 Gas collection vessel with outlets Figure 2 Set-up of the sampling apparatus 7.3 Sample injection and analysis Sample injection and analysis shall be accordi

26、ng to DIN 51405. The sample shall be introduced in its gaseous phase by means of a metering valve or injection syringe with a gas-tight piston. 2) Where samples are taken from diptubes, there is a risk that their composition is not representative of the sample due to the formation of gas bubbles in

27、the diptube. DIN 51619:2016-07 7 7.4 Tests for the quantitative evaluation of the gas chromatogram Testing shall be according to DIN 51405. 8 Quantitative evaluation The evaluation shall be according to DIN 51405. Key t time in min 6 propene 13 iso-butene Y signal voltage 7 ethine 14 cis-butene-2 1

28、methane 8 iso-butane 15 iso-pentane 2 ethane 9 propadiene 16 propine 3 ethene 10 n-butane 17 n-pentane 4 propane 11 trans-butene-2 18 1,3-butadiene 5 cyclopropane 12 butene-1 Figure 3 Example for a gas chromatogram meeting the conditions of 7.1 DIN 51619:2016-07 8 The sum of the peak areas of all de

29、tected components is standardized to a mass fraction of 100 %. The mass fraction wiof the sample component i, given in %, is obtained from Equation (1): =kAfAfw1iiiiii(1) where Aiis the peak area of component i; fiis the FID mass calibration factor of the peak area of component i; k is the number of

30、 components within the mixture. In addition it shall be ensured that all hydrocarbons up to heptane are eluted The calibration factor takes into account the fact that equal amounts of different components result in unequal signals. The calibration factors fishall be calculated using Equation (2): St

31、ciicStiMnMnf= (2) where nciis the number of carbon atoms of component i; ncStis the number of carbon atoms of the standard component (e.g. n-butane); Miis the molar mass of component i; MStis the molar mass of the standard component. Since the calibration factors are only independent of the technica

32、l design of the detector in the first approximation, they shall be checked using calibration gas mixtures. 9 Expression of results Results shall be given as a mass fraction in % (m/m), making reference to this standard. The content of components shall be given to one decimal place, with the exceptio

33、n of the butadiene content, which shall be given to two decimal places. DIN 1333 shall be considered when rounding to the last significant figure. Components with a content less than 0,1 % (m/m) shall not be indicated. DIN 51619:2016-07 9 10 Precision 10.1 General According to DIN EN ISO 4259. As a

34、result of the statistical evaluation of interlaboratory tests, the precision of the method is as follows: Repeatability The difference between successive results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material will exceed the valu

35、es shown in the table only in one case in twenty when the test method is correctly used under normal conditions. Reproducibility The difference between two single and independent results, obtained by different operators working in different laboratories on identical test materials will exceed the va

36、lues shown in the table only in one case in twenty when the test method is correctly used under normal conditions. Table 1 Repeatability and reproducibility Content of component Repeatability r Reproducibility R Mass fraction in % up to 0,1a0,01a0,04aover 0,1 to 1 0,05 0,2 over 1 to 5 0,1 0,4 over 5

37、 to 30 0,2 0,8 over 30 0,3 1,5 aThese values only apply for the component 1,3-butadiene. 11 Test report The test report shall contain at least the following information: a) the type and identification of the product tested; b) a reference to this standard; c) the result of the test according to Clause 9; d) any deviation, agreed or not agreed, from the stipulated procedures; e) the date of the test.