1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 15944:2010BS 2000-587:2010Liquid petroleum products Determination of nickel and vanadium content Inductively coupled plasma optical emission spectrometry method (ICP OES)Li
2、censed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN 15944:2010. The UK participation in its preparation was entrusted to TechnicalCommittee PTI/13, Petr
3、oleum Testing and Terminology.A list of organizations represented on this committee can beobtained on request to its secretary.Energy Institute, under the brand of IP, publishes and sells all Partsof BS 2000, and all BS EN petroleum test methods that would bePart of BS 2000, both in its annual publi
4、cation “Standard methodsfor analysis and testing of petroleum and related products andBritish Standard 2000 Parts” and individually.Further information is available from:Energy Institute, 61 New Cavendish Street, London W1G 7AR.Tel: 020 7467 7100. Fax: 020 7255 1472.This publication does not purport
5、 to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2010 ISBN 978 0 580 67374 0 ICS 75.100 Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard was published under the authority of theStandards
6、Policy and Strategy Committee on 30 November 2010. Amendments issued since publicationDate T e x t a f f e c t e dLicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15944 November 201
7、0 ICS 75.100 English Version Liquid petroleum products - Determination of nickel and vanadium content - Inductively coupled plasma optical emission spectrometry method (ICP OES) Produits ptroliers liquides - Dtermination de la teneur en nickel et vanadium - Mthode directement par spectromtrie dmissi
8、on atomique couplage inductif par plasma (SOD-PCI) Flssige Minerallerzeugnisse - Bestimmung des Gehaltes an Nickel und Vanadium - Optische Emissionsspektralanalyse mit induktiv gekopppeltem Plasma (ICP OES) This European Standard was approved by CEN on 9 October 2010. CEN members are bound to comply
9、 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 and bibliographical references concerning such national standards may be obtained on application to the CEN-CENELEC M
10、anagement 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 the responsibility of a CEN member into its own language and notified to the CEN-CENELEC Management Centre has the same
11、 status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Por
12、tugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2010 CEN All rights of exploitation in any form and by any mean
13、s reserved worldwide for CEN national Members. Ref. No. EN 15944:2010: ELicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010EN 15944:2010 (E) 2 Contents Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatu
14、s .56 Sampling .67 Preparation of calibration solutions 67.1 General 67.2 Calibration solutions .67.3 Internal standard solution .77.4 Working solutions78 Calibration 78.1 General 78.2 Calibration of the ICP OES spectrometer 78.3 Procedure A 78.4 Procedure B 88.5 Check of calibration 89 Sample analy
15、sis .89.1 Sample preparation .89.2 Sample measurement 910 Calculation 910.1 Procedure A 910.2 Procedure B 911 Expression of results . 1012 Precision 1012.1 General . 1012.2 Repeatability, r 1012.3 Reproducibility, R . 1013 Test report . 10Bibliography . 11Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA
16、STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010EN 15944:2010 (E) 3 Foreword This document (EN 15944:2010) has been prepared by Technical Committee CEN/TC 19 “Gaseous and liquid fuels, lubricants and related products of petroleum, synthetic and biological origin”, the secretar
17、iat 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 May 2011, and conflicting national standards shall be withdrawn at the latest by May 2011. Attention is drawn to the po
18、ssibility 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. The method described in this document is based on DIN 51790-6 1. It has been developed originally as an alternativ
19、e to (second part of) EN 13131 2, but as the method enables the use of an instrumental technique more and more employed in analytical laboratories, it was decided to have it as a stand-alone method. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the follow
20、ing countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovak
21、ia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010EN 15944:2010 (E) 4 1 Scope This European Standard specifies an inductively coupled plasma optical emission spectrometry
22、 (ICP OES) method for the determination of nickel content in the range 4 mg/kg to 55 mg/kg and of vanadium content in the range 4 mg/kg to 150 mg/kg in fuel oils and residual fuel oils. NOTE 1 Nickel content can be determined from 2 mg/kg to 4 mg/kg and vanadium content can be determined from 1 mg/k
23、g to 4 mg/kg. However, the precision was not established as no samples with nickel and vanadium contents in these ranges were included in the interlaboratory test. Nickel and vanadium contents higher than those reported can be determined after sample dilution. However, the precision was not establis
24、hed for diluted samples. NOTE 2 For the purposes of this European Standard, the term “% (V/V)” is used to represent the volume fraction (). 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
25、 associated with its use. It is the responsibility of the user 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 applicat
26、ion 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 ISO 1042, Laboratory glassware One-mark volumetric flasks (ISO 1042:1998) EN ISO 3170, Petroleum liquids Manual sam
27、pling (ISO 3170:2004) EN ISO 3171, Petroleum liquids Automatic pipeline sampling (ISO 3171:1988) 3 Principle The sample is diluted with an organic solvent. The solution is then introduced directly into the ICP OES spectrometer. Vanadium and nickel contents are determined by comparison with calibrati
28、on solutions. An internal standard is employed to correct viscosity effects. 4 Reagents 4.1 Paraffin oil, with viscosity between 1,5 mm2/s and 6,0 mm2/s, Pharmacopeia (EUPHARM EP5), e.g. Merck 107174 1). 4.2 Kerosene, boiling range included between 150 C and 325 C, e.g. Aldrich 32.946-0 1). 4.3 Xyle
29、ne, analytical reagent grade. 4.4 2-Ethyl hexanoic acid, analytical reagent grade or other suitable stabilizer for element standard solution. 1) This information is given for the convenience of the users of this European Standard and does not constitute an endorsement by CEN of these products. Equiv
30、alent products may be used if they can be shown to lead to the same results. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010EN 15944:2010 (E) 5 4.5 Element standard solutions, dissolved in oil, for example with 500 mg/kg per element
31、, available as single element standards, or at least partially as multi-element standards. NOTE Some commercial element standard solutions on the market are furnished with higher content. Those solutions may be used instead of the required solutions, but an initial mass to mass dilution should be do
32、ne according to recommendations given in 7.1. 4.6 Argon, with minimum purity (Ar) = 99,996 % (V/V). NOTE Small amounts of oxygen (minimum purity (O2) 99,995 % (V/V) may be added to the argon gas stream using a metering valve (30 ml/min to 100 ml/min) to prevent carbon deposits in the area of the pla
33、sma torch. 5 Apparatus 5.1 Laboratory equipment All glassware shall be cleaned carefully before use to remove soluble constituents. Fill new glass vessels with xylene (4.3) and allow to stand for at least two days. 5.1.1 Glassware 5.1.1.1 Beakers, tall type, 150 ml. 5.1.1.2 Erlenmeyer flasks with wi
34、de neck and plug, 50 ml. 5.1.1.3 Volumetric flasks, 500 ml, according to EN ISO 1042, with narrow neck and plug. 5.1.2 Sample containers, storage bottles with screw cap, brown glass. 5.1.3 Graduated pipettes or variable volume automatic pipettes, fitted with disposable polypropylene tips. 5.2 Balanc
35、e, capable of weighing to the nearest 0,001 g. 5.3 ICP OES spectrometer, equipped with organic sample introduction system. 5.3.1 General Simultaneous and equally suitable sequential ICP OES spectrometer equipped for the analysis of organic liquids, with a high-frequency generator and a nebulizer sui
36、table for organic solvents. The use of a feed pump for sample introduction into the nebulizer is required. Both setup and operation of the ICP OES spectrometer shall be done in accordance with operating instructions of the manufacturer. 5.3.2 Recommended wavelengths The recommended wavelengths for n
37、ickel, vanadium and internal standard element are reported in Table 1. Organometallic yttrium has performed well as an internal standard for this test method and is recommended. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010EN 1594
38、4:2010 (E) 6 Table 1 Recommended wavelengths Element Wavelength nm Nickel 216,555 231,604 221,647 Vanadium 292,401 309,310 Cobalt Scandium Yttrium 238,892 361,383 224,306 371,029 360,073 NOTE The line at 227,021 nm may be used for nickel, but this line suffers from interference with tungsten. Lines
39、at 268,796 nm and 311,070 nm may be used for vanadium, but these lines suffer from interference with molybdenum and manganese respectively. 6 Sampling 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
40、 the sampling of the product under consideration. The samples shall be filled into clean containers. The containers shall be rinsed with xylene (4.3) at least twice and then dried before use. 7 Preparation of calibration solutions 7.1 General In order to avoid inhomogeneity, the standard solutions (
41、4.5) shall be shaken vigorously before use. The masses given correspond to a nominal element content of 500 mg/kg per element in the multi-element solutions (4.5). If solutions with other element contents or single element standards are used, these masses shall be adjusted accordingly in order to es
42、tablish the given nominal concentrations as closely as possible. Calculate the exact concentrations of the calibration solutions, taking into account the exact masses. 7.2 Calibration solutions For each calibration solution, weigh stock standard solution (4.5), stabiliser (4.4), and paraffin oil (4.
43、1) to the nearest 0,001 g in 50 ml Erlenmeyer flasks (5.1.1.2) as indicated in Table 2. All solutions shall be homogenized by vigorous shaking. Table 2 Calibration solutions Calibration solutionElement contentmg/kg Standard solutiong Stabilizerg Paraffin oil g 1 0 (blank) - 0,15 24,85 2 5 0,25 0,15
44、24,60 3 10 0,50 0,15 24,35 4 20 1,00 0,15 23,85 5 100 5,00 0,15 19,85 6 200 10,00 0,15 14,85 Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 04/03/2011 06:26, Uncontrolled Copy, (c) BSIBS EN 15944:2010EN 15944:2010 (E) 7 7.3 Internal standard solution Weigh 5 g of cobalt, scandium or yttrium
45、stock solution (4.5) with a precision of 0,001 g in a 500 ml volumetric flask (5.1.1.3). Add 3 g of stabilizer (4.4) and fill up to 500 ml with a mixture of kerosene/xylene solvent having a volume ratio of 2:1 (4.2 and 4.3). The solution shall be homogenized before use by vigorous shaking. NOTE 1 Th
46、e use of a mixture of xylene and kerosene is necessary to avoid precipitation of asphaltene fractions occurring when kerosene only is employed, and to reduce the build-up of carbon on the tip of the torch. NOTE 2 Experience from daily practice with yttrium used as internal standard has shown that in
47、ternal standard solutions can be used for about two weeks. 7.4 Working solutions For each calibration solution (7.2), weigh (1,0 0,001) g in a 50 ml Erlenmeyer flask (5.1.1.2). Add 10 ml of internal standard solution (7.3). All prepared solutions shall be homogenized by vigorous shaking. 8 Calibrati
48、on 8.1 General The ICP OES spectrometer setup with organic solutions and the instrument check are performed according to the instructions of the manufacturer. The choice of the instrumental parameters is made to obtain the best signal/background ratio for all elements. Net intensity of analytical li
49、nes shall be calculated by subtracting the intensity measured at appropriate background wavelengths. Some instruments are equipped with software which allows the automatic correction of the background. A separate calibration function for each element under investigation shall be established. 8.2 Calibration of the ICP OES spectrometer The calibration of the ICP OES spectrometer shall be done by the measur
