EN 16476-2014 en Liquid petroleum products - Determination of Sodium Potassium Calcium Phosphorus Copper and Zinc contents in diesel fuel - Method via Inductively Coupled Plasma Op.pdf

1、BSI Standards PublicationBS EN 16476:2014Liquid petroleum products Determination ofSodium, Potassium, Calcium,Phosphorus, Copper andZinc contents in diesel fuel Method via InductivelyCoupled Plasma OpticalEmission Spectrometry (ICPOES)BS EN 16476:2014 BRITISH STANDARDNational forewordThis British St

2、andard is the UK implementation of EN 16476:2014.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/13, Petroleum Testing and Terminology.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to

3、 include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 79742 2ICS 75.160.20Compliance with a British Standard cannot confer immunity fromlegal obligations.This

4、British Standard was published under the authority of theStandards Policy and Strategy Committee on 31 August 2014.Amendments issued since publicationDate Text affectedBS EN 16476:2014EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16476 May 2014 ICS 75.160.20 English Version Liquid petroleum p

5、roducts - Determination of Sodium, Potassium, Calcium, Phosphorus, Copper and Zinc contents in diesel fuel - Method via Inductively Coupled Plasma Optical Emission Spectrometry (ICP OES) Produits ptroliers liquides - Dtermination des concentrations en sodium, potassium, calcium, phosphore, cuivre et

6、 zinc dans le gazole - Mthode par spectromtrie dmission atomique par plasma couplage inductif (ICP OES) Flssige Minerallerzeugnisse - Bestimmung des Gehalts an Natrium, Kalium, Calcium, Phosphor, Kupfer, Zink in Dieselkraftstoffen - Direkte Bestimmung durch optische Emissionsspektrometrie mit indukt

7、iv gekoppeltem Plasma (ICP OES) This European Standard was approved by CEN on 20 March 2014. 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 alteration. Up-to-date

8、 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 version in any other language made by translation u

9、nder 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, Czech Republic, Denmark, Estonia, Finland, Forme

10、r 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 and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT E

11、UROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16476:2014 EBS EN 16476:2014EN 16476:2014 (E) 2 Contents P

12、age Foreword 3 Introduction . 4 1 Scope 5 2 Normative references 5 3 Principle 5 4 Reagents . 5 5 Apparatus . 6 6 Sampling . 8 7 Preparation of calibration solutions 8 7.1 General 8 7.2 Internal Standard solution 8 7.3 Calibration solutions . 8 7.4 Calibration check solution 9 8 Calibration 9 8.1 Ge

13、neral 9 8.2 Calibration of the ICP OES spectrometer 9 8.3 Procedure A 10 8.4 Procedure B 10 8.5 Check of calibration 10 9 Sample analysis . 11 9.1 Sample preparation . 11 9.2 Sample measurement 11 10 Calculation 12 11 Expression of result 12 12 Precision . 12 12.1 General 12 12.2 Repeatability . 12

14、12.3 Reproducibility . 12 13 Test report 13 Bibliography 14 BS EN 16476:2014EN 16476:2014 (E) 3 Foreword This document (EN 16476:2014) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the sec

15、retariat of which is 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 November 2014 and conflicting national standards shall be withdrawn at the latest by November 2014. Attention is d

16、rawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. According to the CEN-CENELEC Internal Regulations, the national standards organizations of the follo

17、wing countries are bound to implement this European Standard: Austria, 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, N

18、orway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. BS EN 16476:2014EN 16476:2014 (E) 4 Introduction This document specifies a method for determining concentration of the six most essential ash forming elements. The number of six was chose

19、n in order to limit the complexity of the test and to be able to determine a decent method precision. The six elements were specified by the vehicle manufacturers. The test provides additional information to the more common ash concentration determination methods which do aim towards filter problems

20、. Metals have more impact on the durability of modern DPF exhaust gas after-treatment systems in diesel vehicles than ash in general. BS EN 16476:2014EN 16476:2014 (E) 5 1 Scope This European Standard specifies an inductively coupled plasma optical emission spectrometry (ICP OES) method for the dete

21、rmination of sodium, potassium, calcium, phosphorus, copper and zinc concentrations of diesel fuels, including those containing up to 30 % (V/V) fatty acid methyl ester (FAME), in the range detailed in Table 1. These six elements are considered as the most essential ash forming elements. Table 1 App

22、lication ranges for ash forming elements Element Range mg/kg Sodium 1,2 to 2,5 Potassium 0,9 to 2,5 Calcium 0,3 to 2,5 Phosphorus 0,9 to 2,5 Copper 0,2 to 2,5 Zinc 0,2 to 2,5 NOTE For the purposes of this European Standard, the term “% (V/V)” is used to represent the volume fraction, . WARNING The u

23、se of this European Standard may involve hazardous materials, operations and equipment. 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 European Standard to establish appropriate safety and health pra

24、ctices and determine the applicability of regulatory limitations prior to use. 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

25、 references, the latest edition of the referenced document (including any amendments) applies. EN ISO 1042, Laboratory glassware - One-mark volumetric flasks (ISO 1042) EN ISO 3170, Petroleum liquids - Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids - Automatic pipeline sampling (ISO 3171)

26、 3 Principle A weighed amount of diesel fuel sample is diluted with an organic solvent. The solution is then introduced directly into an ICP OES spectrometer. Sodium, potassium, calcium, phosphorous, copper and zinc concentrations are determined by comparison with calibration solutions. An Internal

27、Standard is employed to correct viscosity effects. 4 Reagents If not specified otherwise, only chemicals of a known high degree of purity shall be used. BS EN 16476:2014EN 16476:2014 (E) 6 4.1 Kerosene, boiling range between 175 C and 250 C, elements free. The solvent shall contain less than 0,1 mg/

28、kg of each of the element under test. NOTE In case of unstable plasma or in case of special laboratory requirements, kerosene can be substituted by other suitable solvents, provided that they are free of analytes. 4.2 Sodium Standard solution, commercially available in oil, containing, e.g. 1 000 mg

29、/kg sodium. 4.3 Potassium Standard solution, commercially available in oil, containing, e.g. 1 000 mg/kg potassium. 4.4 Calcium Standard solution, commercially available in oil, containing, e.g. 1 000 mg/kg calcium. 4.5 Phosphorus Standard solution, commercially available in oil, containing, e.g. 1

30、000 mg/kg phosphorus. 4.6 Copper Standard solution, commercially available in oil, containing, e.g. 1 000 mg/kg copper. 4.7 Zinc Standard solution, commercially available in oil, containing, e.g. 1 000 mg/kg zinc. 4.8 Sodium, potassium, calcium, phosphorus, copper and zinc intermediate working Stand

31、ard (50 mg/kg each). Weigh (1,00 g 0,01) g of each element Standard solution (4.2), (4.3), (4.4), (4.5), (4.6), (4.7) into a 50 ml bottle (5.2). Add kerosene (4.1) to (20,00 0,20) g. Each mass shall be weighed to the nearest 0,001 g. In the case of using several mono-element Standard solutions, atte

32、ntion-shall be paid to ensure that they are free of other analyte elements. Some commercial element Standard solutions are furnished with higher concentration on the market. Those solutions may be used instead of the required solutions, but in this case an initial mass to mass dilution shall be done

33、 according to recommendations given in 7.1. Ready-made commercial multi-element Standard solutions may be used instead of the single element Standard solutions (4.2, 4.3, 4.4, 4.5, 4.6 and 4.7) as the method is designed to avoid interference at the wavelengths specified. 4.9 Internal Standard soluti

34、on (cobalt, scandium, yttrium), commercially available in oil (analyte free), for example with 1 000 mg/kg per element, available as single element Standard. NOTE The internal Standard solutions are commonly available as single element Standards with various element concentrations. 4.10 Argon, with

35、a mass fraction w (Ar) 99,996 %. Small amounts of oxygen may be added to the argon gas stream using a metering valve (for example 30 ml/min to 100 ml/min) to prevent carbon deposits in the area of the plasma torch. 5 Apparatus 5.1 Volumetric flasks, 25 ml and 250 ml, according to EN ISO 1042, with t

36、aper sleeve and plug. To avoid contamination of the test samples, all solutions shall be prepared in plastic containers. Surfaces which can come in contact with the solutions shall not be touched by hand. BS EN 16476:2014EN 16476:2014 (E) 7 To avoid phosphorus contamination due to the phosphates con

37、tained in the detergents used for washing the flasks, rinse the latter at least twice with an approximate 5 mol/l solution of nitric acid. Then rinse with distilled water and dry. The use of borosilicate glass containers is not recommended due to the risk of sodium contamination. 5.2 Bottles, 50 ml,

38、 with screw caps, polyethylene PE. To avoid phosphorus contamination due to the phosphates contained in the detergents used for washing the bottles, rinse the latter at least twice with an approximate 5 mol/l solution of nitric acid. Then rinse with distilled water and dry. 5.3 Analytical balance, c

39、apable of weighing to the nearest 0,000 1 g. 5.4 ICP OES spectrometer 5.4.1 General ICP OES spectrometer equipped for the analysis of organic liquids. The use of a feed pump for sample introduction into the nebuliser is required. Pump tubing shall be suitable for organic use. Both setup and operatio

40、n of the ICP OES spectrometer shall be done in accordance with operating instructions of the manufacturer. The use of vertically oriented plasma, radially observed ICP OES is recommended to avoid carbon residue formation and minimize matrix interference due to the presence of carbon in the plasma. 5

41、.4.2 Recommended wavelengths The recommended wavelengths of sodium, potassium, calcium, phosphorus, copper and zinc, cobalt, scandium and yttrium are given in Table 2. Table 2 Recommended wavelengths Element Wavelength anm Sodium 589,592 588,995 Potassium 766,491 769,897 Calcium 317,933 184,006 (183

42、,944) 315,887 396,847 393,366 Phosphorus 177,499 (177,434) 178,287 (178,222) 213,618b214,914 Copper 324,754 327,396 224,700 Zinc 206,200 213,856 202,548 bCobalt 238,892 258,033 Scandium 361,383 Yttrium 224,306 371,029 360,073 aWavelengths are expressed as vacuum lines or as air lines (in brackets) a

43、ccording to the expression of the different manufacturers of ICP OES spectrometers. bCan be slightly interfered by Cu at the same wavelength. BS EN 16476:2014EN 16476:2014 (E) 8 6 Sampling Unless otherwise specified in the commodity specification, samples shall be taken as described in EN ISO 3170 o

44、r EN ISO 3171 and/or in accordance with the requirements of national regulations for the sampling of the product under test. Collect and store samples in sample bottles made of plastic material (HDPE, FEP, PP, or PFA) or metallic epoxy coated containers. 7 Preparation of calibration solutions 7.1 Ge

45、neral In order to avoid inhomogeneity, the intermediate working Standard (4.8) shall be thoroughly shaken before use. The masses given correspond to a nominal element concentration of 1 000 mg/kg in the single element solutions (4.2, 4.3, .4.4, 4.5, 4.6 and 4.7) and the element Internal Standard sol

46、ution (4.9). If solutions with other element concentrations are used, these masses shall be adjusted accordingly in order to establish the given nominal concentrations as closely as possible. Calculate the exact concentrations of the calibration solutions, taking into account the exact masses. It is

47、 strongly advised to use freshly prepared calibration solutions. 7.2 Internal Standard solution Weigh approximately 5 g of cobalt, scandium or yttrium stock solution (4.9) in a 250 ml volumetric flask (5.1). Fill with kerosene (4.1) to the mark. The solution shall be homogenized by vigorous shaking.

48、 The same Standard batch shall be used for all samples and calibration Standards. 7.3 Calibration solutions Prepare the calibration solutions as indicated in Table 3. Each intermediate mass of elements for the working Standards (4.8) shall be weighed to the nearest 0,001 g into a 25 ml volumetric fl

49、ask (5.1). Add 5,0 ml of the Internal Standard solution (7.2). Fill with kerosene (4.1) to the mark. All prepared solutions shall be homogenized by vigorous shaking. The exact concentration of each element in the calibration solution shall be calculated considering the exact weighed portion. Table 3 Calibration solutions Calibration solution Sodium concentration mg/l Potassium concentration mg/l Calcium concentration mg/l Phosphorus concentration mg/l Copper concentration mg/l Zinc concentration mg/l Intermediate working Standard g 1 (blank) 0