DIN EN 16294-2013 Petroleum products and fat and oil derivatives Determination of phosphorus content in fatty acid methyl esters (FAME) Optical emission spectral analysis with indu.pdf

1、February 2013 Translation by DIN-Sprachendienst.English price group 9No 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).IC

2、S 75.160.20!$Fx“1943585www.din.deDDIN EN 16294Petroleum products and fat and oil derivatives Determination of phosphorus content in fatty acid methyl esters(FAME) Optical emission spectral analysis with inductively coupled plasma(ICP OES);English version EN 16294:2012,English translation of DIN EN 1

3、6294:2013-02Minerallprodukte und Erzeugnisse aus pflanzlichen und tierischen Fetten und len Bestimmung des Gehalts an Phosphor in Fettsuremethylestern (FAME) Direkte Bestimmung durch optische Emissionsspektralanalyse mit induktiv gekoppeltemPlasma (ICP OES);Englische Fassung EN 16294:2012,Englische

4、bersetzung von DIN EN 16294:2013-02Produits ptroliers et produits drivs des corps gras Dtermination de la teneur en phosphore des esters mthyliques dacides gras (EMAG) Mthode par spectromtrie dmission atomique par plasma couplage inductif(ICP OES);Version anglaise EN 16294:2012,Traduction anglaise d

5、e DIN EN 16294:2013-02www.beuth.deDocument comprises 14 pagesIn case of doubt, the German-language original shall be considered authoritative.01.13DIN EN 16294:2013-02 2 A comma is used as the decimal marker. National foreword This document (EN 16294:2012) has been prepared by Technical Committee CE

6、N/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 the Normenausschuss Materialprfung (Materials Testing Standards Committee), Working Committee

7、 NA 062-06-32-01 UA Prfung von FAME. The DIN Standards corresponding to the International Standards referred to in this document are as follows: EN ISO 1042 DIN EN ISO 1042 EN ISO 3170 DIN EN ISO 3170 EN ISO 3171 DIN EN ISO 3171 National Annex NA (informative) Bibliography DIN EN ISO 1042, Laborator

8、y glassware One-mark volumetric flasks DIN EN ISO 3170, Petroleum liquids Manual sampling DIN EN ISO 3171, Petroleum liquids Automatic pipeline sampling EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 16294 November 2012 ICS 75.160.20 English Version Petroleum products and fat and oil derivativ

9、es - Determination of phosphorus content in fatty acid methyl esters (FAME) - Optical emission spectral analysis with inductively coupled plasma(ICP OES) Produits ptroliers et produits drivs des corps gras - Dtermination de la teneur en phosphore des esters mthyliques dacides gras (EMAG) - Mthode pa

10、r spectromtrie dmission atomique par plasma couplage inductif (ICP OES) Minerallprodukte und Erzeugnisse aus pflanzlichen und tierischen Fetten und len - Bestimmung des Gehalts an Phosphor in Fettsuremethylestern (FAME) - Direkte Bestimmung durch optische Emissionsspektralanalyse mit induktiv gekopp

11、eltem Plasma (ICP OES) This European Standard was approved by CEN on 13 October 2012. 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 lists

12、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 under th

13、e 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, Former Yugos

14、lav 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 EUROPEN

15、DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2012 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 16294:2012: EEN 16294:2012 (E) 2 Contents Page Foreword 31 Scope 42 Normative

16、 references 43 Principle 44 Reagents .45 Apparatus .56 Sampling .67 Preparation of calibration solutions 67.1 General 67.2 Internal standard solution .67.3 Calibration solutions .68 Calibration 78.1 General 78.2 Calibration of the ICP OES spectrometer 78.3 Procedure A 78.4 Procedure B 88.5 Check of

17、calibration 89 Sample analysis .99.1 Sample preparation .99.2 Sample measurement 910 Calculation . 1010.1 Procedure A . 1010.2 Procedure B . 1011 Expression of result . 1012 Precision 1012.1 General . 1012.2 Repeatability 1012.3 Reproducibility 1113 Test report . 11Bibliography . 12DIN EN 16294:2013

18、-02 EN 16294:2012 (E) 3 Foreword This document (EN 16294:2012) 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

19、the status of a national standard, either by publication of an identical text or by endorsement, at the latest by May 2013, and conflicting national standards shall be withdrawn at the latest by May 2013. Attention is drawn to the possibility that some of the elements of this document may be the sub

20、ject of patent rights. CEN and/or CENELEC shall not be held responsible for identifying any or all such patent rights. This document was first developed to present a determination of both low levels of sulfur and phosphorus in FAME at the same time. However, interlaboratory studies revealed that the

21、 precision for sulfur was not better than for other more common techniques for this element. It was thus decided to rewrite the method for phosphorus solely. According to the CEN/CENELEC Internal Regulations, the national standards organisations of the following countries are bound to implement this

22、 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, Norway, Poland, Portugal, Romania, Slovakia

23、, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. DIN EN 16294:2013-02 EN 16294:2012 (E) 4 1 Scope This European Standard specifies an inductively coupled plasma optical emission spectrometry (ICP OES) method for the determination of phosphorus content of Fatty Acid Methyl Ester

24、s (FAME) in the range of 2,5 mg/kg to 8,0 mg/kg. 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 user of this standard to establis

25、h appropriate safety and health practices 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

26、 edition 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) EN ISO 3170, Petroleum liquids Manual sampling (ISO 3170) EN ISO 3171, Petroleum liquids Automatic

27、 pipeline sampling (ISO 3171) 3 Principle A weighed amount of FAME sample is diluted with kerosene. The solution is then introduced directly into an ICP OES spectrometer. Phosphorus content is determined by comparison with calibration solutions. An internal standard is employed to correct viscosity

28、effects. 4 Reagents If not specified otherwise, only chemicals of a known high degree of purity shall be used. 4.1 Stock oil, having a kinematic viscosity comparable to the test samples. 4.2 Kerosene, boiling range between 175 C and 250 C. NOTE In case of unstable plasma or in case of special labora

29、tory requirements, kerosene can be substituted by other suitable phosphorus free solvents. 4.3 Phosphorus standard solution, dissolved in oil, containing 1 000 mg/kg phosphorus. Some commercial phosphorus element standard solutions are marketed with higher concentrations. Those solutions may be used

30、 instead of the required solutions, but an initial mass to mass dilution has to be done according to recommendations given in 7.1. in order to establish the given nominal concentrations as closely as possible. 4.4 Phosphorus intermediate solution (25 mg/kg). Weigh 0,50 g 0,01 g of phosphorus standar

31、d solution (4.3) into a 50 ml bottle (5.2). Add kerosene (4.2) to 20,00 g 0,01 g. Each mass shall be weighed to the nearest 0,1 mg. DIN EN 16294:2013-02 EN 16294:2012 (E) 5 4.5 Element standard solutions (cobalt, scandium, yttrium), dissolved in oil, for example with 1 000 mg/kg per element, availab

32、le as single element standards. If multi element standard solutions are used, they shall be phosphorus-free. NOTE The element standard solutions are commonly available as single element standards with various element content. 4.6 Argon, with a purity 99,996 %. Small amounts of oxygen may be added to

33、 the argon gas stream using a metering valve (30 ml/min to 100 ml/min) to prevent carbon deposits in the area of the plasma torch. 5 Apparatus 5.1 Volumetric flasks, 20 ml and 500 ml, with taper sleeve and plug, according to EN ISO 1042. 5.2 Bottles, 30 ml, 50 ml and 100 ml, with screw caps, PE. To

34、avoid phosphorus contamination due to the phosphates contained in the detergents used for washing the glassware, rinse the latter at least twice with an approximate 5 mol/l solution of hydrochloric acid. Then rinse with distilled water and dry. To avoid contamination of the test samples, all solutio

35、ns should be prepared in plastic bottles. Surfaces which can come in contact with the solutions should not be touched by hand. 5.3 Analytical balance, capable of weighing to the nearest 0,1 mg. 5.4 ICP OES-spectrometer, as follows: 5.4.1 General Simultaneous and sequential ICP OES spectrometers equi

36、pped for the analysis of organic liquids, with a high-frequency generator and a nebuliser suitable for organic solvents. 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 operation of the ICP OES spectrometer

37、shall be done in accordance with operating instructions of the manufacturer. NOTE The use of a radial ICP-OES is advisable to avoid carbon residue formation and minimise matrix interference due to the presence of carbon in the plasma. 5.4.2 Recommended wavelengths The recommended wavelengths of phos

38、phorus are given in Table 1. Wavelengths are expressed as vacuum lines or as air lines (in brackets) according to the expression of the different manufacturers of ICP spectrometers. DIN EN 16294:2013-02 EN 16294:2012 (E) 6 Table 1 Recommended wavelengths Element Wavelength nm Phosphorus 177,499 (177

39、,434) 178,287 (178,222) 213,618 214,914 Cobalt 238,892 Scandium 361,383 Yttrium 224,306 371,029 360,073 As the magnitude of the background signal highly depends on spectral structures caused by the sample nature and origin, only net intensities have to be recorded. To keep background noise as low as

40、 possible, signal and background shall be measured simultaneously. 6 Sampling Unless otherwise specified in the commodity specification, samples shall be taken 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

41、of the product under test. New or thoroughly cleaned sample bottles made of plastic material (HDPE (high-density polyethylene), FEP (fluorinated ethylene propylene), or PFA (perfluoroalkoxy) are recommended. 7 Preparation of calibration solutions 7.1 General In order to avoid inhomogeneity, the stan

42、dard solutions (4.3 and 4.5) shall be thoroughly shaken before use. The masses given correspond to a nominal element content of 25 mg/kg in the phosphorus intermediate solution (4.4). It is strongly advised to use freshly prepared calibration solutions. 7.2 Internal standard solution Weigh approxima

43、tely 5 g of cobalt, scandium or yttrium element standard solution (4.5) in a 500 ml volumetric flask (5.1). Fill with kerosene (4.2) to the mark. The solution shall be homogenised by vigorous shaking. The same standard batch shall be used for all samples and calibration standards. 7.3 Calibration so

44、lutions For each calibration solution, weigh the mass of phosphorus intermediate solution (4.4) as indicated in Table 2. The mass shall be weighed to the nearest 0,1 mg in a 20 ml volumetric flask (5.1). DIN EN 16294:2013-02 EN 16294:2012 (E) 7 Table 2 Phosphorus calibration solutions Calibration so

45、lution Phosphorus content mg/l Phosphorus Intermediate solution g 1 (blank) 0 - 2 0,25 0,23 0,50 0,44 1,00 0,8 5 2,00 1,6Add 5,00 g of the stock oil (4.1) and 5,00 g of the internal standard solution (7.2). Fill with kerosene (4.2) to the mark. All prepared solutions shall be homogenised by vigorous

46、 shaking. The exact concentration of the calibration solution shall be calculated considering the exact weighed portion. 8 Calibration 8.1 General The ICP OES is started up and checked according to the manufacturers recommendations and user manuals, including functional performance tests. The choice

47、 of the instrumental parameters is made to obtain the best signal/background ratio for all elements. Net intensity of analytical lines shall be calculated by subtracting the intensity measured at appropriate background wavelengths. Some instruments are equipped with software which allows the automat

48、ic correction of the background. 8.2 Calibration of the ICP OES spectrometer The calibration of the ICP OES spectrometer shall be done by the measurement of the blank solution and of the calibration solutions (7.3) using three replicates. For the determination of the elements, the wavelengths recomm

49、ended in Table 1 shall be used. The background subtraction shall be performed at wavelengths not affected by other lines. IMPORTANT Ensure that the wavelengths used in calibration also match exactly the ones used in the sample measurement. Depending on the spectrometer (software), follow either procedure A or B. 8.3 Procedure A Conduct the aspiration of the calibration solutions (7.3). For each calibration solutions, measure the net emission intens