DIN EN 15199-4-2015 Petroleum products - Determination of boiling range distribution by gas chromatography method - Part 4 Light fractions of crude oil German version EN 15199-4 20.pdf

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1、December 2015 English price group 12No 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 75.080!%Iu“2385682www.din.deDIN

2、 EN 15199-4Petroleum products Determination of boiling range distribution by gas chromatography method Part 4: Light fractions of crude oil;English version EN 15199-4:2015,English translation of DIN EN 15199-4:2015-12Minerallerzeugnisse Gaschromatographische Bestimmung des Siedeverlaufes Teil 4: Lei

3、chte Fraktionen des Rohls;Englische Fassung EN 15199-4:2015,Englische bersetzung von DIN EN 15199-4:2015-12Produits ptroliers Dtermination de la rpartition dans lintervalle de distillation par mthode de chromatographie en phase gazeuse Partie 4 : Lumire fractions du ptrole brut;Version anglaise EN 1

4、5199-4:2015,Traduction anglaise de DIN EN 15199-4:2015-12www.beuth.deDTranslation by DIN-Sprachendienst.In case of doubt, the German-language original shall be considered authoritative.Document comprises 23 pages 11.15 DIN EN 15199-4:2015-12 2 A comma is used as the decimal marker. National foreword

5、 This document (EN 15199-4:2015) has been prepared 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 DIN-Normenausschu

6、ss Materialprfung (DIN Standards Committee Materials Testing), Working Committee NA 062-06-14 AA Chromatographische Analyse of the Fachausschuss Minerall- und Brennstoffnormung (FAM). DIN EN 15199 Petroleum products Determination of boiling range distribution by gas chromatography method consists of

7、: Part 1: Middle distillates and lubricating base oils Part 2: Heavy distillates and residual fuels Part 3: Crude oil Part 4: Light fractions of crude oil EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15199-4 September 2015 ICS 75.080 English Version Petroleum products - Determination of boil

8、ing range distribution by gas chromatography method - Part 4: Light fractions of crude oil Produits ptroliers - Dtermination de la rpartition dans lintervalle de distillation par mthode de chromatographie en phase gazeuse - Partie 4 : Lumire fractions du ptrole brut Minerallerzeugnisse - Gaschromato

9、graphische Bestimmung des Siedeverlaufes - Teil 4: Leichte Fraktionen des Rohls This European Standard was approved by CEN on 1 August 2015. 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 nati

10、onal 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 versions (English, French, German). A ver

11、sion 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, Belgium, Bulgaria, Croatia, Cyprus,

12、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, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom.

13、 EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2015 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15199-4:201

14、5 EEN 15199-4:2015 (E) 2 Contents Page European foreword 3 1 Scope . 4 2 Normative references . 4 3 Terms and definitions 4 4 Principle 4 5 Reagents and materials 4 6 Apparatus 5 6.1 Analytical balance 5 6.2 Gas chromatograph . 5 6.3 Detector . 5 6.4 Pre-column configurations . 5 6.4.1 Heated valve

15、switching box (see Figure B.1) 5 6.4.2 Injection port (see Figure B.2 and B.3) . 6 6.5 Analytical column 6 6.5.1 General . 6 6.5.2 Resolution . 7 6.6 Skewness . 7 6.7 Data collection . 8 7 Sampling and sample handling . 8 8 Calculation of response factors . 8 9 Procedure 9 9.1 Sample preparation . 9

16、 9.2 Determination of backflush time 9 9.2.1 Initial work . 9 9.2.2 Analytical column 9 9.2.3 Accelerated analytical column 9 9.3 Sample analysis 10 9.3.1 Initial work 10 9.3.2 Calculation of individual components results 10 9.3.3 Boiling point distribution of fraction up to and including nonane . 1

17、1 10 Reporting . 11 11 Precision . 11 11.1 General 11 11.2 Repeatability, r . 11 11.3 Reproducibility, R . 11 12 Test report . 12 Annex A (informative) Analysis assistance . 13 Annex B (informative) Apparatus configuration 19 Bibliography 21 DIN EN 15199-4:2015-12 EN 15199-4:2015 (E) 3 European fore

18、word This document (EN 15199-4:2015) has been prepared 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 s

19、tandard, either by publication of an identical text or by endorsement, at the latest by March 2016, and conflicting national standards shall be withdrawn at the latest by March 2016. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights.

20、 CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. EN 15199 consists of the following parts, under the general title Petroleum products Determination of boiling range distribution by gas chromatography method: Part 1: Middle distillates and lubricating b

21、ase oils Part 2: Heavy distillates and residual fuels Part 3: Crude oil Part 4: Light fractions of crude oil This part of the standard is based on IP 601 1 and describes the determination of boiling range distribution of hydrocarbons up to n-nonane in crude oil. The results of this test method can b

22、e combined with those from EN 15199-3, to give a full boiling point distribution of crude oil. Part 4 is harmonized with ASTM D7900 2. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Aus

23、tria, Belgium, 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, Slovakia, Slovenia, Spain, Swed

24、en, Switzerland, Turkey and the United Kingdom. DIN EN 15199-4:2015-12 EN 15199-4:2015 (E)4 1 Scope This European Standard describes a method for the determination of the boiling range distribution of petroleum products by capillary gas chromatography using flame ionization detection. This European

25、Standard is applicable to stabilized crude oils and for the boiling range distribution and the recovery up to and including n-nonane. A stabilized crude oil is defined as having a Reid Vapour Pressure equivalent to or less than 82,7 kPa as determined by IP 481 3. NOTE For the purposes of this Europe

26、an Standard, the terms “% (m/m)” and “% (V/V)” are used to represent respectively the mass fraction, , and the volume fraction, . WARNING The use of this European Standard can involve hazardous materials, operations and equipment. This European Standard does not purport to address all of the safety

27、problems associated with its use. It is the responsibility of the user of this standard to take appropriate measures to ensure 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

28、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 amendments) applies. EN ISO 3170, Petroleu

29、m liquids Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171) 3 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1 recovery combined mass percentages of all light hydrocarbon peaks (except the internal

30、standard peak) in the sample up to and including n-nonane 4 Principle An amount of internal standard is quantitatively added to an aliquot of the stabilized crude oil. A portion of this mixture is injected into a pre-column in series via a splitter with a capillary analytical column. When the n-nona

31、ne has quantitatively passed to the analytical column, the pre-column is back-flushed to vent the higher boiling components. The individual components are identified by comparison with reference chromatograms and a database of hydrocarbon compounds (see Annex A). The boiling point distribution and r

32、ecovery up to and including n-nonane (n-C9) is calculated. 5 Reagents and materials 5.1 Stationary phase for columns, with a bonded polydimethylsiloxane (PDMS) stationary phase for both the pre-column and the analytical capillary column. 5.2 Compressed gases DIN EN 15199-4:2015-12 EN 15199-4:2015 (E

33、) 5 5.2.1 Carrier gas, helium or hydrogen of at least 99,995 % (V/V) purity or higher is required. Any oxygen present shall be removed by a suitable chemical filter. CAUTION If hydrogen is used as carrier gas, follow the safety instructions from the GC instrument manufacturer. 5.2.2 Combustion gases

34、, hydrogen and clean air for the flame ionization detector, and suitable filters shall be used to ensure adequate gas cleanliness. 5.3 Internal standard, having a baseline resolution from any adjacent eluting peaks (Hexene-1 or 3,3-dimethylbutene-1 (99 % pure) have been found to be suitable). 5.4 Va

35、lve switching mixture, a qualitative mixture of approximately 1 % (m/m) of each normal alkane from pentane to decane. 5.5 Carbon disulphide (CS2), purity 99,7 % (V/V) minimum. WARNING Extremely flammable and toxic by inhalation. 6 Apparatus 6.1 Analytical balance Capable of weighing with an accuracy

36、 of 0,1 mg. 6.2 Gas chromatograph The typical operational characteristics of the gas chromatograph are described in Table 1. Two different pre-column configurations are possible: The first configuration (A) employs a 1-metre column contained in a temperature controlled valve box, separately controll

37、ed. The valve box in this configuration is isothermal. The second configuration (B) is a short pre-column (a packed injection port liner), that fits into the injection port. The injection port will be temperature programmed. 6.3 Detector Flame Ionization Detector with sufficient sensitivity to detec

38、t 1 % mass n-heptane with a peak height of at least 10 % full-scale deflection under the conditions given in the method. When operating at this sensitivity level, detector stability shall be such that a baseline drift of not more than 1 % per hour is obtained. The detector shall be connected to the

39、column carefully to avoid any cold spots. The detector shall be capable of operating at a temperature equivalent to the maximum column temperature used. 6.4 Pre-column configurations 6.4.1 Heated valve switching box (see Figure B.1) For the isothermal 1 metre pre-column, a heated valve box is needed

40、 with its own temperature control. The box will contain an automated six-port valve which is used to back-flush the pre-column. The six-port valve should be made out of material which will not be corroded by the sample (Some crude oils contain high amounts of sulfur components). The valve shall be s

41、ituated in a heated isothermal oven and be attached to the injector, pre-column, splitter, analytical column and the detector without any cold spots. DIN EN 15199-4:2015-12 EN 15199-4:2015 (E) 6 6.4.2 Injection port (see Figure B.2 and B.3) A temperature programmable injection port capable of contai

42、ning a 7,5 cm pre-column, and this injection port shall be equipped with a back-flush option. This injector can be connected directly to the capillary column (Figure B.2) or via a splitter (Figure B.3). Table 1 Typical chromatographic conditions Pre-column A Pre-column B Analytical Accelerated Analy

43、tical Column length m 1,0 0,075 50 or 100 40 Column internal diameter mm 2 2,5 0,25 0,10 Column material polydimethylsiloxane Phase loading % 5 10 Film thickness m 0,5 Injection volume L 0,1 0,1 Injector split ratio 100: 1 600: 1 Injector temperature C 300 100 Pre-column temperature C 200 100 Inject

44、or program rate C/min 50 Final injector temperature C 300 Initial oven temperature C 35 35 Hold time min 30 2,6 Oven program rate C/min 2 50 45 C (hold time 3 min) 5 60 C (hold time 3 min) 9,5 200 C Final oven temperature C 200 (hold time 20 min) 200 (hold time 1 min) Flame Ionization Detector C 300

45、 300 6.5 Analytical column 6.5.1 General The column elutes hydrocarbons in a boiling point order. The eluate from the injector passes through the pre-column before eluting onto the analytical column. DINEN15199-4:2015-12EN 15199-4:2015 (E) 7 6.5.2 Resolution Determine the resolution between the inte

46、rnal standard and the nearest n-paraffin peak as per Formula (1). ( )( )2112699,12wwtt+= (1) Where P is the column resolution; t1is the retention time of the first peak (peak 1, see Figure 1); t2is the retention time of the second peak (peak 2, see Figure 1); wlis the peak width at half height of pe

47、ak 1; w2is the peak width at half height of peak 2. With Hexene-1 as I.S., the resolution is determined between the I.S and n-hexane. The resolution shall be at least 2,0. Figure 1 Determination of resolution 6.6 Skewness Determine the skew of the n-hexane peak by measuring the width of the leading

48、part of the peak at 5 % peak height (A) and the width of the following part of the peak at 5 % peak height (B). The ratio (B)/(A) shall be not less than 1 or more than 4. See Figure 2 for further clarification. DINEN15199-4:2015-12EN 15199-4:2015 (E) 8 Figure 2 Calculation of peak skewness 6.7 Data

49、collection A PC based chromatography data system or integrator with suitable software may be used. For systems using the analytical column, a data -sampling rate of 5 Hz is the recommended minimum. For systems using the accelerated analytical column, a data-sampling rate of 20 Hz is required. 7 Sampling and sample handling Take samples in accordance with either