BS EN 15837-2009 Ethanol as a blending component for petrol - Determination of phosphorus copper and sulfur content - Direct method by inductively coupled plasma optical emission s.pdf

1、BS EN 15837:2009BS 2000-581:2009ICS 75.160.20NO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBRITISH STANDARDEthanol as a blending component for petrol Determination of phosphorus, copper and sulfur content Direct method by inductively coupled plasma optical emission spectromet

2、ry (ICP OES)Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIThis British Standard was published under the authority of the Standards Policy and Strategy Committee on 31 January 2010 BSI 2010ISBN 978 0 580 62966 2Amendments/corrigenda issued since pu

3、blicationDate CommentsBS EN 15837:2009National forewordThis British Standard is the UK implementation of EN 15837:2009. 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 be o

4、btained onrequest to its secretary.Energy Institute, under the brand of IP, publishes and sells all Parts ofBS 2000, and all BS EN petroleum test methods that would be Part of BS 2000, both in its annual publication “Standard methods for analysis and testing of petroleum and related products and Bri

5、tish Standard 2000 Parts” and individually.Further information is available from:Energy Institute, 61 New Cavendish Street, London W1G 7AR.Tel: 020 7D67 7100. Fax: 020 7255 1D72.This publication does not purport to include all the necessary provisionsof a contract. Users are responsible for its corr

6、ect application. Compliance with a British Standard cannot confer immunityfrom legal obligations.Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIBS EN 15837:2009EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15837 December 2009 ICS 75.160.20 E

7、nglish Version Ethanol as a blending component for petrol - Determination of phosphorus, copper and sulfur content - Direct method by inductively coupled plasma optical emission spectrometry (ICP OES) Ethanol comme base de mlange lessence - Dtermination de la teneur en phosphore, en cuivre et en sou

8、fre - Mthode directe par spectromtrie dmission atomique par plasma couplage inductif (ICP OES) Ethanol zur Verwendung als Blendkomponente in Ottokraftstoff - Bestimmung des Gehalts an Phosphor, Kupfer und Schwefel - Direktes Verfahren durch optische Emissionsspektrometrie mit induktiv gekoppeltem Pl

9、asma (ICP OES) This European Standard was approved by CEN on 7 November 2009. 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 and bibl

10、iographical 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 translation under the responsibility

11、 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, Germany, Greece, Hungary, Iceland, Ir

12、eland, 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 NORMUNG Management Centre: Avenue Marnix

13、 17, B-1000 Brussels 2009 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15837:2009: ELicensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIBS EN 15837:2009EN 15837:2009 (E) 2 Contents

14、Page Foreword 31 Scope 42 Normative references 43 Principle 44 Reagents .45 Apparatus .56 Sampling .67 Preparation of calibration solutions 68 Calibration 68.1 Preparation of the instrumentation 68.2 Execution of the calibration 68.3 Check of calibration 79 Sample analysis .710 Calculation 811 Expre

15、ssion of results 812 Precision .812.1 General 812.2 Repeatability, r .812.3 Reproducibility, R 913 Test report 9Annex A (normative) Ethanol density 10Bibliography . 11Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIBS EN 15837:2009EN 15837:2009 (E)

16、3 Foreword This document (EN 15837:2009) 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 the status of a nation

17、al standard, either by publication of an identical text or by endorsement, at the latest by June 2010 and conflicting national standards shall be withdrawn at the latest by June 2010. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights

18、. 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 following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Cyprus, Czec

19、h 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 United Kingdom. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STAND

20、ARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIBS EN 15837:2009EN 15837:2009 (E) 4 1 Scope This European Standard specifies an inductively coupled plasma optical emission spectrometry (ICP OES) method for the direct determination of elements content in ethanol, namely phosphorus in the range (0,1

21、3 to 1,90) mg/kg, copper in the range (0,050 to 0,300) mg/kg, and sulfur in the range (2,0 to 15,0) mg/kg. WARNING The use of this method may involve hazardous equipment, materials and operations. This method does not purport to address to all of the safety problems associated with its use, but it i

22、s the responsibility of the user to search and establish appropriate safety and health practices and determine the applicability of regulatory limitations prior to use. NOTE For the purposes of this document, the terms “% (m/m)” and “% (V/V)“ are used to represent respectively the mass fraction (w)

23、and volume fraction (). 2 Normative references The following referenced documents are indispensable for the application 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

24、 ISO 3170, Petroleum liquids Manual sampling (ISO 3170:2004) EN ISO 3675, Crude petroleum and liquid petroleum products Laboratory determination of density Hydrometer method (ISO 3675:1998) EN ISO 3696, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) EN ISO 12185,

25、Crude petroleum and petroleum products Determination of density Oscillating U-tube method (ISO 12185:1996) 3 Principle A portion of a sample is directly injected into the spray-chamber of an inductively coupled plasma emission spectrometer. The element content is determined by comparing the emission

26、 of the element in the test portion with the emission of the calibration solutions at the same wavelength. The calibration solutions are prepared from suitable compounds dissolved in ethanol. 4 Reagents Use only reagents of recognized analytical grade, unless otherwise specified. 4.1 Phosphorus stan

27、dard solution, ready-made commercially available phosphorus aqueous standard solution, 1 000 mg/l. 4.2 Copper standard solution, ready-made commercially available copper aqueous standard solution, 1 000 mg/l. 4.3 Sulfur standard solution, which shall be either 4.3.1 or 4.3.2. 4.3.1 Sulfur standard s

28、olution, ready-made commercially available sulfur aqueous standard solution, 1 000 mg/l, or Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIBS EN 15837:2009EN 15837:2009 (E) 5 4.3.2 Tetrabutylammonium hydrogen -sulfate (CH3CH2CH2CH2)4N(HSO4), (MW 33

29、9,53 g/mol). If tetrabutylammonium hydrogen sulfate is used, weigh 264,5 mg in a 25 ml volumetric flask (5.3). Bring to the mark with ethanol (4.5) and homogenise. The actual concentration of sulfur shall be calculated, as 1 000 mg/l only represents a target concentration. NOTE If a ready-made sulfu

30、r aqueous standard solution is employed, the solubility in ethanol of the sulfur compound should be checked. For instance, ammonium sulphate, used in most commercially available solutions, is insoluble in ethanol. 4.4 Water, for analytical laboratory use, conforming to grade 3 of EN ISO 3696. 4.5 Et

31、hanol, 99 % minimum purity. 4.6 Argon, regulated compressed gas of 99,996 % minimum purity for the ICP spectrometer. 5 Apparatus 5.1 Inductively coupled plasma optical emission spectrometer, capable of monitoring one of the following wavelengths of each element, according to Table 1. NOTE 1 Waveleng

32、ths are expressed as vacuum lines or as air lines (in brackets) according to the expression of the different manufacturers of ICP spectrometers. NOTE 2 The copper line at 213,598 nm can interfere with the phosphorus line at 213,618 nm, but the low concentration range of copper does not show apprecia

33、ble interference in phosphorus measurements. A cooled spray-chamber set at 2 C may be used, provided that the temperature is controlled ( 1 C), if the plasma is not stable with ethanol. Table 1 ICP-OES wavelength capability Element Wavelength nm Phosphorus 177,499 (177,434) (213,618) 178,287 (178,22

34、2) Copper 324,754 327,395 Sulfur 180,731 (180,669) 182,034 (181,972) 182,624 (182,562) 5.2 Balance, capable of weighing to the nearest 0,1 mg. 5.3 Glassware, 25 ml, 50 ml and 100 ml volumetric flasks. In order to avoid contamination due to phosphates contained in the detergents used for glassware cl

35、eaning, wash the flasks at least twice with an approximate 5 mol/l solution of nitric acid. Rinse with water (4.4) and dry. 5.4 Graduated pipettes or variable volume automatic pipettes, fitted with disposable polypropylene tips. 5.5 Ultrasonic bath, able to contain 100 ml flasks. Licensed Copy: Wang

36、 Bin, ISO/EXCHANGE CHINA STANDARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIBS EN 15837:2009EN 15837:2009 (E) 6 6 Sampling Unless otherwise specified, obtain samples in accordance with the procedures given in EN ISO 3170 and/or in accordance with the requirements of national standards or regulat

37、ions for the sampling of the product under test. High density polyethylene containers (HDPE) shall be used. The containers shall be carefully cleaned and rinsed with water (4.4) to avoid contamination, and then dried. Thoroughly mix the samples in their containers immediately prior to withdrawal of

38、the test portions. 7 Preparation of calibration solutions Dilute the standard solution (4.1 to 4.3) with ethanol (4.5) in five 100 ml volumetric flasks to obtain calibration solutions having the element concentrations as specified in Table 2. Table 2 Concentrations for calibration solutions Solution

39、 Phosphorus mg/l Copper mg/l Sulfur mg/l 1 (blank) 0 0 0 2 0,1 0,05 1,0 3 0,5 0,10 5,0 4 1,0 0,20 10,0 5 1,5 0,40 20,0 The solutions shall be freshly prepared for each series of analyses. 8 Calibration 8.1 Preparation of the instrumentation Since instrumentations stemming from diverse manufacturers

40、have different configurations and settings, it is difficult to specify an exact procedure. Follow the manufacturers instructions for setting up the instrument with organic solutions. The choice of the instrumental parameters shall be determined so as to obtain the best signal/background ratio for al

41、l elements. The analytical lines recommended in Table 1 shall be used. A background correction shall be performed using wavelengths close to each analytical line, but not affected by other lines. It is important to ensure that analytical lines and background wavelengths used in calibration also matc

42、h exactly the ones used in the check of calibration (8.3) and samples analysis (9). 8.2 Execution of the calibration Conduct the aspiration of the calibration solutions 1 to 5 (see Table 2). Read out the intensity of the analytical lines and the corresponding background wavelengths chosen for copper

43、, phosphorus and sulfur of each solution. Licensed Copy: Wang Bin, ISO/EXCHANGE CHINA STANDARDS, 06/04/2010 03:35, Uncontrolled Copy, (c) BSIBS EN 15837:2009EN 15837:2009 (E) 7 Calculate the net intensities of the analytical lines by subtracting the intensities of the corresponding background wavele

44、ngths. Some instruments are equipped with software which allows the automatic correction for the background. Carry out three measurements (x) for each solution. Calculate the arithmetical mean of the three measurements, x . Calculate the relative standard deviation (RSD) in percent of each mean acco

45、rding to: ()xnxxRSD1)(1002=(1) where n is the number of measurements (i.e. n = 3). The RSD of calibration solutions 2 to 5 (Table 2) for all elements shall be lower than 5 %. If this is not the case, refer to manufacturers instructions for better instrumental parameters. Construct the calibration cu

46、rve of each element from these means using linear regression, by plotting the emission intensity values versus the concentrations of the element. The regression coefficient of the linear regression shall be at least 0,995. If not, the procedure should be corrected in case of errors and, if necessary

47、, the calibration procedure should be repeated from Clause 7 onward. 8.3 Check of calibration A Quality Control (QC) sample shall be freshly prepared for each series of analyses. The concentration of the QC sample is set in accordance with the specification level to be checked. The QC sample shall b

48、e prepared from certified reference materials or other sources of certified stock solutions in order to verify sensitivity and accuracy of the calibration curve. The QC sample concentration shall be measured after the calibration has been established. If the QC check differs from the reference value

49、s for copper, phosphorus or sulfur by more than R/1,41 (reproducibility divided by 1,41), verify that the concentration is correct by preparing a new QC sample. If the new QC sample differs from the given values, a new calibration shall be established. The values obtained with the QC sample shall be measured with a RSD (8.2) lower than 5 %. 9 Sample analysis Shake vigorously the sample container and homogenise using the ultrasonic bath (5.5) for 1 minute prior