1、July 2007DEUTSCHE NORM English price group 11No part of this standard 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!,yg“9866895www.din
2、.deDDIN EN 15553Petroleum products and related materials Determination of hydrocarbon types Fluorescent indicator adsorption methodEnglish version of DIN EN 15553:2007-07Minerallerzeugnisse und verwandte Produkte Bestimmung der Kohlenwasserstofftypen Adsorptionsverfahren mit Fluoreszenz-IndikatorEng
3、lische Fassung DIN EN 15553:2007-07www.beuth.deDocument comprises 21 pages09.07DIN EN 15553:2007-07 2 National foreword This standard has been prepared by CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin” (Secretariat: the Netherlands
4、). The responsible German body involved in its preparation was the Normenausschuss Materialprfung (Mate-rials Testing Standards Committee), Technical Committee 062-06-81 AA, Spiegelausschuss zu CEN/TC 19, Gasfrmige und flssige Kraft- und Brennstoffe, Schmierstoffe und verwandte Produkte mit minerall
5、stm-miger, synthetischer oder biologischer Herkunft of the Fachausschuss Minerall- und Brennstoffnormung (FAM). EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15553April 2007ICS 75.080English VersionPetroleum products and related materials - Determination ofhydrocarbon types - Fluorescent indicat
6、or adsorption methodProduits ptroliers et produits connexes - Dterminationdes groupes dhydrocarbures - Mthode par adsorption enprsence dindicateur fluorescentMinerallerzeugnisse und verwandte Produkte -Bestimmung der Kohlenwasserstofftypen - Adsorptionsverfahren mit Fluoreszenz-IndikatorThis Europea
7、n Standard was approved by CEN on 24 February 2007.CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references conce
8、rning such nationalstandards may be obtained on application to the CEN 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 translationunder the responsibility of a CEN member into its own l
9、anguage and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, L
10、uxembourg, Malta, Netherlands, Norway, Poland, Portugal,Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rig
11、hts of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15553:2007: EEN 15553:2007 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Terms and definitions .5 4 Principle5 5 Reagents and materials 5 6 Apparatus .6 7 Sampling and sample
12、handling9 8 Apparatus preparation 9 9 Procedure .10 10 Calculation12 11 Expression of results 13 12 Precision.13 12.1 Repeatability, r .13 12.2 Reproducibility, R 13 13 Test report 15 Annex A (normative) Specification for silica gel .16 Annex B (informative) Standard adsorption column .17 Bibliograp
13、hy 19 EN 15553:2007 (E) 3 Foreword This document (EN 15553:2007) 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 give
14、n the status of a national standard, either by publication of an identical text or by endorsement, at the latest by October 2007, and conflicting national standards shall be withdrawn at the latest by October 2007. This European Standard is based on IP 156/06 1. It is developed as an alternative met
15、hod to ASTM D1319 2, in which a de-pentanization step is described, which is not used in this European Standard and the EU environment. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Au
16、stria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EN 15553:20
17、07 (E) 4 1 Scope This European Standard specifies a fluorescent indicator adsorption method for the determination of hydrocarbon types over the concentration ranges from 5 % (V/V) to 99 % (V/V) aromatic hydrocarbons, 0,3 % (V/V) to 55 % (V/V) olefinic hydrocarbons, and 1 % (V/V) to 95 % (V/V) satura
18、ted hydrocarbons in petroleum fractions that distil below 315 C. This method may be applicable to concentrations outside these ranges, but the precision has not been determined. When samples containing oxygenated blending components are analysed, the hydrocarbon type results can be reported on an ox
19、ygenate-free basis or, when the oxygenate content is known, the results can be corrected to a total-sample basis. This test method is for use with full boiling range products. Cooperative data have established that the precision statement does not apply to petroleum fractions with narrow boiling ran
20、ges near the 315 C limit. Such samples are not eluted properly, and results are erratic. Samples containing dark-coloured components that interfere with reading the chromatographic bands cannot be analysed. NOTE 1 The oxygenated blending components methanol, ethanol, tert-butyl methyl ether (MTBE),
21、methyl tert-pentyl ether (TAME) and tert-butyl ethyl ether (ETBE) do not interfere with the determination of hydrocarbon types at concentrations normally found in commercial blends. These oxygenated compounds are not detected since they elute with the alcohol desorbent. The effects of other oxygenat
22、ed compounds should be individually verified. NOTE 2 For the purposes of this European 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 may involve hazardous materials, operations and e
23、quipment. This European Standard does not purport to address all of the safety problems associated with 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 Normat
24、ive references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 1601, Liquid petroleum products
25、 Unleaded petrol Determination of organic oxygenate compounds and total organically bound oxygen content by gas chromatography (O-FID) EN 13132, Liquid petroleum products Unleaded petrol Determination of organic oxygenate compounds and total organically bound oxygen content by gas chromatography usi
26、ng column switching EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171:1988) EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) EN 15553:2007 (E) 5 3 Terms and definitions Fo
27、r the purposes of this document, the following terms and definitions apply. 3.1 saturates saturated hydrocarbons volume percentage of alkanes plus cycloalkanes 3.2 olefins olefinic hydrocarbons volume percentage of alkenes plus cycloalkenes plus some alkadienes 3.3 aromatics aromatic hydrocarbons vo
28、lume percentage of monocyclic and polycyclic aromatic hydrocarbons plus aromatic olefinic hydrocarbons, some dienes, compounds containing sulfur or nitrogen, or higher-boiling oxygenated compounds 4 Principle Approximately 0,75 ml of sample is introduced into a special glass adsorption column packed
29、 with activated silica gel. A small layer of the silica gel contains a mixture of fluorescent dyes. When all the sample has been adsorbed onto the gel, alcohol is added to desorb the sample down the column. The hydrocarbons are separated, according to their adsorption affinities, into aromatics, ole
30、fins and saturates. The fluorescent dyes are also separated selectively with the hydrocarbon types, and render the boundaries of the aromatic, olefin and saturate zones visible under ultraviolet light. The volume percentage of each hydrocarbon type is calculated from the length of each zone in the c
31、olumn. 5 Reagents and materials Use only chemicals and reagents of recognised analytical grade and water conforming to grade 3 of EN ISO 3696. 5.1 Silica gel, manufactured to conform to the specifications given in Annex A. NOTE 1 Grace Davison silica gel Grade 923 meets the requirements of this spec
32、ification. Before use, dry the gel in a shallow vessel at 175 C for at least 3 h. Transfer the dried gel to an airtight container while still hot, and protect it from atmospheric moisture. NOTE 2 Some batches of silica gel that otherwise meet specifications have been found to produce olefin-boundary
33、 fading. The exact reason for this phenomenon is unknown but will affect accuracy and precision. 5.2 Fluorescent indicator-dyed gel, a standard dyed gel, consisting of a mixture of re-crystallized Petrol Red AB4 and purified portions of olefin and aromatic dyes obtained by chromatographic adsorption
34、 following a definite, uniform procedure, and deposited on silica gel1). Store the dyed gel in a dark place under an atmosphere of nitrogen. NOTE When stored under these conditions, dyed gel can have a shelf life of at least five years. It is recommended that portions of the dyed gel be transferred
35、as required to a smaller working vial from which the dyed gel is routinely taken for analyses. 1)A list of suppliers is available from the Energy Institute, London. EN 15553:2007 (E) 6 5.3 Propan-2-ol, 99 % (V/V) 5.4 3-methylbutan-1-ol, 99 % (V/V) (optional) 5.5 Acetone, reagent grade 5.6 Pressurizi
36、ng gas, air (or nitrogen) capable of being delivered to the top of the column at controllable pressures over the range from 0 kPa gauge to 103 kPa gauge. NOTE 6 Apparatus 6.1 Adsorption column, with precision bore tubing conforming to the specification given in Table 1 and as shown in Figure 1, part
37、 b), made of glass and consisting of a charger section with a capillary neck, a separator section and an analyzer section. NOTE For routine/non-specification compliance analysis adsorption columns with standard wall tubing conforming to the specification given in Annex B and as shown in Figure 1, pa
38、rt a), may be used. In addition, the length of a thread of liquid approximately 100 mm long, which shall not vary in length by more than 0,3 mm in any part of the analyzer section. A special valve with possibility to regulate this pressure to 2 kPaways have this possibility. is advised as common val
39、ves do not al-EN 15553:2007 (E) 7 Table 1 Precision bore column dimensions and tolerance limits Charger section Inside diameter 12 mm 2 mm Overall length 150 mm 5 mm Neck section Inside diameter 2 mm 0,5 mm Overall length 50 mm 5 mm Separator section Inside diameter 5 mm 0,5 mm Overall length 190 mm
40、 5 mm Analyzer section Inside diameter 1,60 mm to 1,65 mm Overall length 1 200mm 30 mm Tip Overall length 30 mm 5 mm EN 15553:2007 (E) 8 Key 1 charger 2 neck 3 separator 4 tip 5 analyzer 6 pressuring gas 7 spherical joint S29 8 pack gel to this level 9 long taper 10 dyed gel 11 zone measuring device
41、 (optional) 12 long taper 13 polyvinyl tubing 14 precision bore capillary tubing 15 standard wall tubing 16 spherical joint S13 17 tip drawn out to fine capillary Figure 1 Adsorption columns with a) standard wall and b) precision bore tubing in analyzer section EN 15553:2007 (E) 9 Glass-sealing of t
42、he various sections to each other shall be done with long-taper connections rather than shouldered connections. The silica gel shall be supported with a small piece of glass wool located between the ball socket of the 12/2 spherical joint and covering the analyzer outlet. The column tip attached to
43、the 12/2 socket shall be approximately 2 mm inside diameter. The ball and socket joints shall be clamped together to ensure that the tip does not tend to slide from a position in a direct line with the analyzer section during the packing and subsequent use of the column. 6.2 Zone-measuring-device Ei
44、ther a metre rule mounted adjacent to the column, fitted with four movable metal index clips, for measuring the length of each zone, see Figure 1 and 9.9, or glass-writing pencils for marking zone boundaries and metre rule for measuring the length of each zone. 6.3 Ultraviolet light source, with rad
45、iation predominantly at wavelength 365 nm. NOTE alongside the apparatus adjusted to give the best fluorescence. 6.4 Electric vibrator, for vibrating the individual columns or for vibrating the frame supporting multiple columns. 6.5 Hypodermic syringe, capacity 1 ml, graduated to 0,01 ml or 0,02 ml f
46、itted with a needle 102 mm 2 mm in length having an inside diameter of 0,7 mm to 1,2 mm. NOTE Needles of No. 18 gauge, 20 gauge or 22 gauge have been found to be satisfactory. 6.6 Glass funnel, with a stem of less than 10 mm external diameter. 7 Sampling and sample storage 7.1 Samples shall be taken
47、 as described in EN ISO 3170 or EN ISO 3171 and/or in accordance with the requirements of national standards or regulations for the sampling of unleaded petrol. 7.2 Store the sample in the dark at a temperature of 2 C to 4 C until ready for analysis. 8 Apparatus preparation 8.1 Mount the apparatus a
48、ssembly in a room or area darkened to facilitate observations of zone boundaries. For multiple determinations, assemble an apparatus that includes the ultraviolet source, a rack to hold the columns and a gas manifold system with spherical joints to connect to the desired number of columns. 8.2 Freel
49、y suspend the column from a loose-fitting clamp placed immediately below the spherical joint of the charger section. Place the glass funnel (6.6) in the column. Using the vibrator (6.4) vibrate the column along its entire length and add small increments of silica gel (5.1) through the glass funnel into the charger section until the separator section is half full. Stop the vibrator and add a 3 mm to 5 mm layer of dyed gel (5.2). Re-start the vibrator and vibrate the column while adding silica gel until the tightly pa
