1、December 2007DEUTSCHE NORM English price group 8No 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!$K#a“1400062www
2、.din.deDDIN EN ISO 14596Petroleum products Determination of sulfur content Wavelength-dispersive X-ray fluorescence spectrometry(ISO 14596:2007)English version of DIN EN ISO 14596:2007-12Minerallerzeugnisse Bestimmung des Schwefelgehaltes Wellenlngendispersive Rntgenfluoreszenz-Analyse (ISO 14596:20
3、07)Englische Fassung DIN EN ISO 14596:2007-12SupersedesDIN EN ISO 14596:1998-08www.beuth.deDocument comprises 13 pagesDIN EN ISO 14596:2007-12 2 National foreword This standard falls in the domain of Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleu
4、m, synthetic and biological origin” (Secretariat: NEN, Netherlands). This standard has been prepared by Technical Committee ISO/TC 28 “Petroleum products and lubricants” (Secretariat: ANSI, USA) in collaboration with Technical Committee CEN/TC 19. The responsible German body involved in its preparat
5、ion was the Normenausschuss Materialprfung (Materials Testing Standards Committee), Technical Committee NA 062-06-81 AA Gasfrmige und flssige Kraft- und Brennstoffe, Schmierstoffe und verwandte Produkte mit minerallstmmiger, synthetischer oder biologischer Herkunft of the Fachausschuss Minerall- und
6、 Brennstoffnormung (FAM). The DIN Standards corresponding to the International Standards referred to in the EN are as follows: ISO 3170:2004 DIN EN ISO 3170:2004-06 ISO 3171:1988 DIN EN ISO 3171:2000-11 Amendments This standard differs from DIN EN ISO 14596:1998-08 as follows: a) The content has bee
7、n brought into line with the International Standard. b) Normative references have been updated. c) Precision data have been updated. Previous editions DIN 51450-3: 1974-10 DIN 51400-6: 1978-02, 1990-12 DIN EN ISO 14596: 1998-08 National Annex NA (informative) Bibliography DIN EN ISO 3170:2004-06, Pe
8、troleum liquids Manual sampling (ISO 3170:2004) DIN EN ISO 3171:2000-11, Petroleum liquids Automatic pipeline sampling (ISO 3171:1988) EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 14596 September 2007 ICS 75.080 Supersedes EN ISO 14596:1998English Version Petroleum products - Determinati
9、on of sulfur content - Wavelength-dispersive X-ray fluorescence spectrometry (ISO 14596:2007) Produits ptroliers - Dtermination de la teneur en soufre - Spectromtrie de fluorescence X dispersive en longueur donde (ISO 14596:2007) Minerallerzeugnisse - Bestimmung des Schwefelgehaltes -Wellenlngendisp
10、ersive Rntgenfluoreszenz-Analyse (ISO 14596:2007) This European Standard was approved by CEN on 8 September 2007. 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 a
11、lteration. Up-to-date lists and bibliographical references concerning such national standards 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
12、translation under the responsibility of a CEN member into its own language and notified to the CEN Management Centre has the same status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,Ge
13、rmany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMU
14、NG Management Centre: rue de Stassart, 36 B-1050 Brussels 2007 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 14596:2007: EContents Page 2 EN ISO 14596:2007 (E) Foreword 3 1 Scope. 4 2 Normative references 4 3 Principle . 5 4
15、Reagents and materials . 5 5 Apparatus 5 6 Samples and sampling 6 7 Calibration solutions 6 8 Calibration. 8 9 Procedure 10 10 Calculation 10 11 Expression of results. 10 12 Precision . 10 13 Test report. 11 Foreword This document (EN ISO 14596:2007) has been prepared by Technical Committee ISO/TC 2
16、8 “Petroleum products and lubricants“ in collaboration with 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
17、 standard, either by publication of an identical text or by endorsement, at the latest by March 2008, and conflicting national standards shall be withdrawn at the latest by March 2008. This document supersedes EN ISO 14596:1998. According to the CEN/CENELEC Internal Regulations, the national standar
18、ds organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Port
19、ugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Endorsement notice The text of ISO 14596:2007 has been approved by CEN as a EN ISO 14596:2007 without any modification. 3 EN ISO 14596:2007 (E) WARNING The use of this International Standard may involve hazardous m
20、aterials, operations and equipment. This International Standard does not purport to address all of the safety problems associated with its use. It is the responsibility of the user of this International Standard to establish appropriate safety and health practices and determine the applicability of
21、regulatory limitations prior to use. 1 Scope This International Standard specifies a method for the determination of the sulfur content of liquid petroleum products, additives for petroleum products, and semi-solid and solid petroleum products that are either liquefied by moderate heating or soluble
22、 in organic solvents (see 4.1) of negligible or accurately known sulfur content. The method is applicable to products or additives having sulfur contents in the range 0,001 % (m/m) to 2,50 % (m/m); higher contents can be determined by appropriate dilution. Other elements do not interfere at concentr
23、ations anticipated in the materials subject to this analysis. NOTE For the purposes of this International Standard, the term “% (m/m)” is used to represent the mass fraction of a material. High concentrations of phosphorus or chlorine typically above 3 % (m/m) can cause bias in the sulfur result by
24、absorbing Zr-L and S-K to different extents. It is necessary in these cases to carry out studies to determine whether this potential interference is significant. When larger amounts of molybdenum are present (typically above 50 mg/kg to 100 mg/kg), increased background radiation and spectral overlap
25、 with the sulfur signal can occur. It is necessary in these cases to inspect the relevant spectral regions, for example, to investigate the significance of this potential source of bias. 2 Normative references The following referenced documents are indispensable for the application of this document.
26、 For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. ISO 3170:2004, Petroleum liquids Manual sampling ISO 3171:1988, Petroleum liquids Automatic pipeline sampling 4 EN ISO 14596:2007 (E) 3 Pri
27、nciple The test portion and a zirconium solution as internal standard are mixed in a given mass ratio and exposed, in a sample cell, to the primary radiation of an X-ray tube. The count rates of the S-K at 0,537 3 nm and Zr-L1 at 0,607 0 nm fluorescence thus excited and the count rate of the backgro
28、und radiation at 0,545 nm are measured and the ratio of these net count rates calculated. The sulfur content of the sample is determined from a calibration curve prepared on the basis of sulfur calibration standards. NOTE The Siegbahn X-ray line notation (S-K) is used in this International Standard;
29、 the corresponding IUPAC X-ray line notation is S K-L2,3. 4 Reagents and materials 4.1 White oil (light paraffin oil, paraffinum perliquidum), high-purity grade, sulfur content 1 mg/kg maximum. 4.2 Sulfur compounds, of sulfur content accurately known to the nearest 0,01 % (m/m), used for the prepara
30、tion of the primary standards. The compounds given in 4.2.1 to 4.2.3 are suitable, and their nominal sulfur contents are given. Where the purity of these compounds is less than 99 %, certified materials are required, or the nature of all impurities and their contents should be accurately known to th
31、e nearest 0,01 % (m/m). 4.2.1 Dibenzothiophene (DBT), with a nominal sulfur content of 17,399 % (m/m). 4.2.2 Dibutyl sulfide (DBS), with a nominal sulfur content of 21,915 % (m/m). 4.2.3 Thionaphthene (benzothiophene) (TNA), with a nominal sulfur content of 23,890 % (m/m). 4.3 Certified sulfur refer
32、ence materials. Use materials from a national standards body or accredited suppliers, if available. 4.4 Zirconium solution A. Zirconium octoate solution with a zirconium content in the range of 12 % (m/m) to 18 % (m/m) or another oil-soluble, sulfur-free zirconium compound dissolved in white oil (4.
33、1) to provide a zirconium mass fraction in the range of 12 % (m/m) to 18 % (m/m). 4.5 Zirconium solution B. Dissolve the zirconium solution A (4.4) with white oil (4.1) to provide a zirconium mass fraction of approximately 1 % (m/m). 5 Apparatus 5.1 Wavelength-dispersive X-ray fluorescence (WDXRF) s
34、pectrometer, consisting of any suitable spectrometer that incorporates the design features listed in Table 1. It shall be set up according to the manufacturers instructions. 5 EN ISO 14596:2007 (E) Table 1 General requirements of spectrometer Component Requirement Anode Rhodium, scandium or chromium
35、 target Voltage a30 kV to 50 kV Current a30 mA to 70 mA Collimator Coarse Analysing crystal Germanium, pentaerythritol, or graphite Optical path Helium Cell window Polyester or polypropylene film, sulfur-free, thickness 2 m to 6 m Detector Gas-flow proportional counter with a pulse-height analyser a
36、A lower-power system may be used, provided that it has been validated to meet the requirements specified in 8.3 and Clause 12. 5.2 Analytical balance, capable of weighing to the nearest 0,1 mg. 5.3 Homogenizer, non-aerating, high-speed shear type, or heatable magnetic stirrer or, for example, an ult
37、rasonic stirrer. 5.4 Flasks, 50 ml capacity, narrow-necked, conical, made of borosilicate glass and fitted with a ground-glass stopper. Use flasks of higher capacity for stock solutions (7.2). 6 Samples and sampling 6.1 Unless otherwise specified, samples shall be taken in accordance with the proced
38、ure described in ISO 3170 or ISO 3171. 6.2 Test portions from the samples shall be drawn after thorough mixing and subdivision. Heat viscous samples to a temperature that renders the sample liquid and homogenize, using the homogenizer (5.3) as necessary. NOTE For the purpose of this procedure, the t
39、erm “sample” also includes solutions prepared from additives, semi-solid or solid petroleum products that have been appropriately pre-treated and/or diluted. 7 Calibration solutions 7.1 General Use either certified reference materials (4.3) or primary standards prepared from sulfur compounds (4.2) d
40、issolved in white oil (4.1) as a basis for the preparation of the appropriate range of sulfur stock solutions. 7.2 Preparation of stock solutions Weigh, to the nearest 0,1 mg, a quantity of sulfur compound (4.2) or certified reference material (4.3) to prepare stock solutions of approximately 2,50 %
41、 (m/m) and 0,10 % (m/m) sulfur content, calculated to the nearest 0,001 % (m/m), and dissolve in white oil (4.1) at room temperature. Mix the contents thoroughly using a homogenizer (5.3). 6 EN ISO 14596:2007 (E) The approximate quantities of sulfur compounds (4.2) for addition to 100 g of white oil
42、 (4.1) to prepare the stock solutions are as follows: DBT (4.2.1): 16,75 g 2,5 % (m /m) and 0,5 g 0,1 % (m/m) DBS (4.2.2): 12,85 g 2,5 % ( m/m) and 0,45 g 0,1 % (m/m) TNA (4.2.3): 11,65 g 2,5 % ( m/m) and 0,40 g 0,1 % (m/m) It is recommended that a polytetrafluoroethylene or glass-coated magnetic st
43、irrer and stirring device be used to mix the contents of the flask. Calculate the exact sulfur content, wS,2, as a percentage by mass, to three decimal places, in each case from the amounts of white oil and sulfur compound used as given in Equation (1): CS,1S,2COmwwmm=+(1) where mCis the mass of the
44、 sulfur compound, expressed in grams; wS,1is the sulfur content of the sulfur compound, expressed as a percentage by mass; mOis the mass of white oil, expressed in grams. 7.3 Preparation of standard solutions 7.3.1 High range 0,1 % (m/m) to 2,5 % (m/m) Into 50 ml flasks (5.4), weigh to the nearest 0
45、,1 mg, the appropriate quantity of the 2,5 % (m/m) stock solution (7.2) to produce approximately 25 g of each standard solution of sulfur contents approximately 2,0 % (m/m), 1,5 % (m/m), 1,0 % (m/m), 0,7 % (m/m), and 0,4 % (m/m). Add white oil (4.1) to make up to approximately 25 g and re-weigh to t
46、he nearest 0,1 mg. Calculate the sulfur content, wS,3, of the standard solution to the nearest 0,001 % (m/m), using Equation (2): 21S,2S,331()mmwwmm=(2) where m1is the mass of the flask, expressed in grams; m2is the mass of the flask plus stock solution, expressed in grams; m3is the mass of the flas
47、k plus stock solution plus white oil, expressed in grams; wS,2is the sulfur content of the stock solution, expressed as a percentage by mass. 7.3.2 Low range 0,001 0 % (m/m) to 0,1 % (m/m) Prepare standard solutions in the same manner as described in 7.3.1 using the 0,1 % (m/m) stock solution (7.2)
48、to give standard solutions of approximately 0,075 % (m/m), 0,05 % (m/m), 0,025 % (m/m), 0,010 % (m/m), 0,005 % (m/m) and 0,001 % (m/m). Calculate the sulfur content to the nearest 0,000 1 % (m/m) using the Equation (2). 7 EN ISO 14596:2007 (E) 7.4 Preparation of calibration solutions 7.4.1 High rang
49、e 0,1 % (m/m) to 2,5 % (m/m) Weigh 20,00 g 0,01 g of each of the standard solutions (7.3.1) and the two stock solutions (7.2) into separate flasks (5.4), and add 5,00 g 0,01 g of the zirconium solution A (4.4). Mix thoroughly at room temperature (18 C to 28 C) using a homogenizer (5.3). 7.4.2 Low range 0,001 0 % (m/m) to 0,1 % (m/m) Weigh 20,00 g 0,01 g of the low sulfur stock solution and each of the standard solutions (7.3.2) into separate flasks (5.4) and add 2,00 g 0,01 g of the zirconium solution
