1、Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:16, Uncontrolled Copy, (c) BSIg49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g60g3g38g50g51g60g53g44g42g43g55g3g47g36g58c
2、ontent Ultraviolet fluorescence methodThe European Standard EN 15486:2007 has the status of a British StandardICS 71.080.60Ethanol as a blending component for petrol Determination of sulfur BRITISH STANDARDBS EN 15486:2007 BS 2000-554:2007BS EN 15486:2007Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA S
3、TANDARDS, 12/12/2007 02:16, Uncontrolled Copy, (c) BSIThis BritiThe PTArequest to its EnBSThis British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 October 2007 BSI and Energy Institute 2007ISBN 978 0 580 56674 5Compliance with a British Standard ca
4、nnot confer immunity from legal obligations. Amendments issued since publicationAmd. No. Date Commentsboth in its annual publication “Standard methods for analysis and testing of petroleum and related products and British Standard 2000 Parts” and individually.Further information is available from: E
5、nergy Institute, 61 New Cavendish Street, London W1G 7AR. Tel: 020 7467 7100. Fax: 020 7255 1472.This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.National forewordsh Standard is the UK implementation of EN 1548
6、6:2007.UK participation in its preparation was entrusted to Technical Committee I/13, Petroleum testing and terminology.list of organizations represented on this committee can be obtained on secretary.ergy Institute, under the brand of IP, publishes and sells all Parts of 2000, and all BS EN petrole
7、um test methods that would be Part of BS 2000, EUROPEAN STANDARDNORME EUROPENNEEUROPISCHE NORMEN 15486August 2007ICS 71.080.60English VersionEthanol as a blending component for petrol - Determination ofsulfur content - Ultraviolet fluorescence methodEthanol comme base de mlange lessence - Dosage dus
8、oufre - Mthode par fluorescence ultravioletteEthanol zur Verwendung als Blendkomponente inOttokraftstoff - Bestimmung des Schwefelgehaltes -Ultraviolettfluoreszenz-VerfahrenThis European Standard was approved by CEN on 30 June 2007.CEN members are bound to comply with the CEN/CENELEC Internal Regula
9、tions which stipulate the conditions for giving this EuropeanStandard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such nationalstandards may be obtained on application to the CEN Management Centre or to any CEN member.This Euro
10、pean 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 language and notified to the CEN Management Centre has the same status as theofficial versions.CEN members are the natio
11、nal standards bodies of Austria, 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 Uni
12、ted Kingdom.EUROPEAN COMMITTEE FOR STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGManagement Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. EN 15486:2007: ELi
13、censed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:16, Uncontrolled Copy, (c) BSIEN 15486:2007 (E) 2 Contents Page Foreword3 1 Scope 4 2 Normative references 4 3 Principle4 4 Reagents and materials 4 4.1 Inert gas 4 4.2 Oxygen4 4.3 Solvent 5 4.4 Sulfur compounds .5 4.4.1 General5 4.5
14、 Sulfur stock solution .5 4.6 Calibration standards5 4.7 Quality control samples 6 4.8 Quartz wool 6 5 Apparatus .6 6 Sampling.7 7 Apparatus preparation 7 8 Apparatus calibration and verification 8 8.1 Multi-point calibration .8 8.2 One-point calibration.9 8.3 Verification .10 9 Procedure .10 10 Cal
15、culation11 10.1 Using multi-point calibration11 10.2 Using one-point calibration 11 10.3 Calculation12 11 Expression of results 12 12 Precision.12 12.1 Repeatability, r .12 12.2 Reproducibility, R 13 13 Test report 13 Annex A (normative) Ethanol density .14 Licensed Copy: Wang Bin, ISO/EXCHANGE CHIN
16、A STANDARDS, 12/12/2007 02:16, Uncontrolled Copy, (c) BSIEN 15486:2007 (E) 3 Foreword This document (EN 15486:2007) 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 i
17、s held by NEN. This European Standard shall be given the status of a national standard, either by publication of an identical text or by endorsement, at the latest by February 2008, and conflicting national standards shall be withdrawn at the latest by February 2008. The method described in this doc
18、ument is based on EN ISO 20846 1. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece,
19、Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:16, Uncontrolled Copy, (c) BSIEN 15486:2007
20、(E) 4 1 Scope This document specifies an ultraviolet (UV) fluorescence test method for the determination of the sulfur content of ethanol from 5 mg/kg to 20 mg/kg. Other products may be analysed and higher sulfur contents may be determined according to this test method, however, no precision data fo
21、r products other than ethanol and for results outside the specified range have been established for this document. Halogens interfere with this detection technique at concentrations above approximately 3 500 mg/kg. NOTE For the purposes of this document, the terms “% (m/m)” and “% (V/V)” are used to
22、 represent the mass fraction and the volume fraction of a material respectively. WARNING The use of this standard may 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 the u
23、ser of this standard to establish appropriate safety and health practices and to determine the applicability of regulatory limitations prior to use. 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the editio
24、n cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN ISO 1042, Laboratory glassware one-mark volumetric flasks (ISO 1042:1998) EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) 3 Principle An ethanol sample is dire
25、ctly injected into a UV fluorescence detector. The sample enters into a high temperature combustion tube (1 000 C to 1 100 C), where the sulfur is oxidized to sulfur dioxide (SO2) in an oxygen-rich atmosphere. Water produced during the sample combustion is removed and the sample combustion gases are
26、 exposed to ultraviolet (UV) light. The SO2absorbs the energy from the UV light and is converted to excited sulfur dioxide (SO2*). The fluorescence emitted from the excited SO2* as it returns to a stable state SO2,is detected by a photomultiplier tube and the resulting signal is a measure of the sul
27、fur contained in the sample. CAUTION Exposure to excessive quantities of ultraviolet (UV) light is injurious to health. The operator must avoid exposing any part of his/her person, especially his/her eyes, to not only direct UV light but also to secondary or scattered radiation that may be present.
28、4 Reagents and materials 4.1 Inert gas Argon or helium, high purity grade with a minimum purity of 99,998 % (V/V). 4.2 Oxygen High purity grade with a minimum purity of 99,75 % (V/V). CAUTION Vigorously accelerates combustion. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:16,
29、Uncontrolled Copy, (c) BSIEN 15486:2007 (E) 5 4.3 Solvent 4.3.1 General Use either the solvent specified in 4.3.2 or 4.3.3 or a solvent similar to that occurring in the sample under analysis. Correction for sulfur contribution from solvents used in standard preparation and sample dilution is require
30、d. Alternatively, use of a solvent with non-detectable sulfur contamination relative to the unknown sample makes the blank correction unnecessary. 4.3.2 Ethanol, reagent grade. 4.3.3 Toluene, (optional), reagent grade. CAUTION Flammable solvents. 4.4 Sulfur compounds 4.4.1 General Use compounds with
31、 a minimum purity of 99 % (m/m). Certified reference materials (CRMs) from accredited suppliers are suitable alternatives to the compounds listed in 4.4.2 to 4.4.4. 4.4.2 Dibenzothiophene (DBT), MW 184,26 g/mol with a nominal sulfur content of 17,399 % (m/m). 4.4.3 Dibutylsulfide (DBS), MW 146,29 g/
32、mol with a nominal sulfur content of 21,915 % (m/m). 4.4.4 Thionaphthene (Benzothiophene) (TNA), MW 134,20 g/mol with a nominal sulfur content of 23,890 % (m/m). 4.5 Sulfur stock solution Prepare a stock solution of approximately 1 000 mg/l sulfur content by accurately weighing the appropriate quant
33、ity of sulfur compound (4.4) in a volumetric flask (5.9). Ensure complete dissolution with solvent (4.3). Calculate the sulfur concentration of the stock solution to the nearest 1 mg/l. This stock solution is used for the preparation of calibration standards. As an alternative procedure, a sulfur st
34、ock solution of approximately 1 000 mg/kg can be prepared by accurately weighing the appropriate quantity of sulfur compound (4.4) in a volumetric flask (5.9) and reweighing the volumetric flask once it has been filled to the mark with the solvent (4.3). Take precautions to ensure that evaporation o
35、f the solvent and/or sulfur compounds is not causing weighing errors. NOTE 1 The appropriate mass of sulfur compound described in 4.4.2 to 4.4.4 to add to the 100 ml flask is 0,574 8 g (DBT), 0,456 3 g (DBS) and 0,418 6 g (TNA). NOTE 2 The shelf life of the stock solution is approximately three mont
36、hs when stored at low temperature, typically in a refrigerator. 4.6 Calibration standards Prepare the calibration standards by dilution of the stock solution (4.5) with the selected solvent (4.3). Calculate the exact sulfur content of each calibration standard. Licensed Copy: Wang Bin, ISO/EXCHANGE
37、CHINA STANDARDS, 12/12/2007 02:16, Uncontrolled Copy, (c) BSIEN 15486:2007 (E) 6 Calibration standards with a known sulfur content in milligrams per litre (or milligrams per kilogram) can be obtained with a volume/volume (or mass/mass, respectively) dilution of the stock solution at 1 000 mg/l (or m
38、illigrams per kilogram, respectively). Other practices are possible but these ones above avoid any density correction. NOTE New calibration standards should be prepared on a regular basis depending upon the frequency of use and age. When stored at low temperature, typically in a refrigerator, the ca
39、libration standards, with sulfur content above 30 mg/kg (or mg/l), have a useful life of at least one month. Below this sulfur content (30 mg/kg), the shelf life should be reduced. 4.7 Quality control samples These are stable samples representative of the materials being analysed, that have a sulfur
40、 content that is known by this test method over a substantial period of time. Alternatively, there are standard materials with a certified value commercially available. Ensure before use, that the material is within its shelf life. 4.8 Quartz wool Follow the manufacturers recommendations. 5 Apparatu
41、s 5.1 Furnace, comprising an electric device, capable of maintaining a temperature sufficient to pyrolyse all of the sample and oxidize all sulfur to sulfur dioxide (SO2). It can be set either in a horizontal or vertical position. 5.2 Combustion tube, of quartz, constructed to allow the direct injec
42、tion of the sample into the heated oxidation zone of the furnace (5.1). The combustion tube shall have side arms for the introduction of oxygen and carrier gas. The oxidation section shall be large enough to ensure complete combustion of the sample. It can be set either in a horizontal or vertical p
43、osition. 5.3 Flow controllers, capable of maintaining a constant supply of oxygen and carrier gas. 5.4 Vapour drier, capable of removing water vapour formed during combustion prior to measurement by the detector (5.5). 5.5 UV fluorescence detector, a selective and quantitative detector capable of me
44、asuring UV light emitted from the fluorescence of excited sulfur dioxide. 5.6 Microlitre syringe, capable of accurately delivering between 5 l to 50 l quantities. Follow the manufacturers instructions for determining the length of the needle required. For vertical injection, syringes with a polytetr
45、afluoroethylene (PTFE) plunger are recommended. 5.7 Sample inlet system, either positioned vertically or horizontally. It shall consist of a direct injection inlet system capable of allowing the quantitative delivery of the material to be analysed into an inlet carrier stream which directs the sampl
46、e into the oxidation zone at a controlled and repeatable rate. A syringe drive mechanism, which discharges the sample from the microlitre syringe at a constant rate of approximately 1 l/s maximum, is required. NOTE Boat injection systems may be used if they meet the performance requirements of claus
47、e 12. 5.8 Balance, capable of weighing with an accuracy of at least 0,1 mg. 5.9 Volumetric flasks, Class A one-mark volumetric flasks, conforming to EN ISO 1042, of appropriate capacities, including 100 ml, for the preparation of sulfur stock solution (4.5) and calibration standards (4.6). Licensed
48、Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 12/12/2007 02:16, Uncontrolled Copy, (c) BSIEN 15486:2007 (E) 7 Key 1 UV source 6 inert gas input 2 photomultiplier 7 gases output 3 output signal 8 drier 4 1 000 C to 1 100 C 9 quartz tube 5 oxygen input 10 microlitre syringe Figure 1 Synopsis of the ap
49、paratus 6 Sampling Unless otherwise specified, laboratory samples shall be obtained by the procedures described in EN ISO 3170. High density polyethylene containers shall be used. The containers should be carefully cleaned and rinsed with pure water to avoid contamination. Samples should be analysed as soon as possible after removal from bulk supplies, to prevent loss of sulfur. Thoroughly mix samples in their containers immediately prior to withdrawal of the test portions. CAUTION Samples that are collected at temperatures below room temperature ca
