1、BSI Standards Publication PD ISO/TS 17307:2016 Petroleum products Biodiesel Determination of total esters content by gas chromatographyPD ISO/TS 17307:2016 PUBLISHED DOCUMENT National foreword This Published Document is the UK implementation of ISO/TS 17307:2016 The UK participation in its preparati
2、on was entrusted to Technical Committee PTI/2, Liquid Fuels. A list of organizations represented on this committee can be obtained on request to its secretary. This publication does not purport to include all the necessary provisions of a contract. Users are responsible for its correct application.
3、The British Standards Institution 2016. Published by BSI Standards Limited 2016 ISBN 978 0 580 88915 8 ICS 75.160.20 Compliance with a British Standard cannot confer immunity from legal obligations. This British Standard was published under the authority of the Standards Policy and Strategy Committe
4、e on 29 February 2016. Amendments/corrigenda issued since publication Date T e x t a f f e c t e dPD ISO/TS 17307:2016 ISO 2016 Petroleum products Biodiesel Determination of total esters content by gas chromatography Produits ptroliers Biodiesel Dosage de la teneur en esters totale par chromatograph
5、ie en phase gazeuse TECHNICAL SPECIFICATION ISO/TS 17307 Reference number ISO/TS 17307:2016(E) First edition 2016-02-01PD ISO/TS 17307:2016ISO/TS 17307:2016(E)ii ISO 2016 All rights reserved COPYRIGHT PROTECTED DOCUMENT ISO 2016, Published in Switzerland All rights reserved. Unless otherwise specifi
6、ed, no part of this publication may be reproduced or utilized otherwise in any form or by any means, electronic or mechanical, including photocopying, or posting on the internet or an intranet, without prior written permission. Permission can be requested from either ISO at the address below or ISOs
7、 member body in the country of the requester. ISO copyright office Ch. de Blandonnet 8 CP 401 CH-1214 Vernier, Geneva, Switzerland Tel. +41 22 749 01 11 Fax +41 22 749 09 47 copyrightiso.org www.iso.orgPD ISO/TS 17307:2016ISO/TS 17307:2016(E)Foreword iv 1 Scope . 1 2 Normative references 1 3 T erms
8、and definitions . 1 4 Principle 1 5 Apparatus . 2 6 Reagents and materials . 2 7 Sampling 3 8 Procedure. 3 8.1 Preparation of the apparatus 3 8.2 Preparation of the calibration curve 4 8.3 Sample preparation 4 8.4 Procedure 4 9 Expression of results 5 10 Precision . 5 10.1 General . 5 10.2 Repeatabi
9、lity, r 5 10.3 Reproducibility, R .5 11 Test report . 6 Annex A (informative) Examples of chromatograms . 7 Annex B (informative) Preparation of standard solutions .10 Bibliography .11 ISO 2016 All rights reserved iii Contents PagePD ISO/TS 17307:2016ISO/TS 17307:2016(E) Foreword ISO (the Internatio
10、nal Organization for Standardization) is a worldwide federation of national standards bodies (ISO member bodies). The work of preparing International Standards is normally carried out through ISO technical committees. Each member body interested in a subject for which a technical committee has been
11、established has the right to be represented on that committee. International organizations, governmental and non-governmental, in liaison with ISO, also take part in the work. ISO collaborates closely with the International Electrotechnical Commission (IEC) on all matters of electrotechnical standar
12、dization. The procedures used to develop this document and those intended for its further maintenance are described in the ISO/IEC Directives, Part 1. In particular the different approval criteria needed for the different types of ISO documents should be noted. This document was drafted in accordanc
13、e with the editorial rules of the ISO/IEC Directives, Part 2 (see www.iso.org/directives). Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. ISO shall not be held responsible for identifying any or all such patent rights. Details of
14、 any patent rights identified during the development of the document will be in the Introduction and/or on the ISO list of patent declarations received (see www.iso.org/patents). Any trade name used in this document is information given for the convenience of users and does not constitute an endorse
15、ment. For an explanation on the meaning of ISO specific terms and expressions related to conformity assessment, as well as information about ISOs adherence to the WTO principles in the Technical Barriers to Trade (TBT) see the following URL: Foreword - Supplementary information The committee respons
16、ible for this document is ISO/TC 28, Petroleum products and related products of synthetic or biological origin, Subcommittee SC 7, Liquid biofuels.iv ISO 2016 All rights reservedPD ISO/TS 17307:2016TECHNICAL SPECIFICATION ISO/TS 17307:2016(E) Petroleum products Biodiesel Determination of total ester
17、s content by gas chromatography W A R N I N G T h e u s e o f t h i s T e c h n i c a l S p e c i f i c a t i o n m i g h t i n v o l v e t h e u s a g e o f d a n g e r o u s materials and equipment. It is the responsibility of the user to establish the appropriate security, health and environmenta
18、l practices, and to determine the applicability of regulatory limitations before their use. 1 Scope This Technical Specification establishes a method for determining the total methyl ester content in fatty acid methyl ester (FAME) by gas chromatography and using an external standard. The method is s
19、uitable for biodiesel which contains esters between C6 and C26. This method allows verifying that the total ester content is greater than 96,5 % (m/m). NOTE 1 The method also allows determination of the total ethyl ester content in FAEE, but precision for this has not been established. This Technica
20、l Specification does not determine the linolenic nor the poly-unsaturated alkyl ester content. Alternative techniques, such as EN 14103 1and EN 15779 2 , respectively, are available for this. NOTE 2 For the purposes of this Technical Specification, the term “% (m/m)” is used to represent the mass fr
21、action, . 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 references, the latest edition of the referenced document (including
22、 any amendments) applies. ISO 3170, Petroleum liquids Manual sampling ISO 3171, Petroleum liquids Automatic pipeline sampling ISO 4259, Petroleum products Determination and application of precision data in relation to methods of test 3 T erms a nd definiti ons For the purposes of this document, the
23、following terms and definitions apply. 3.1 biodiesel fuel comprised of monoalkyl esters of fatty acids, derived from vegetable oils or animal fat 3.2 total esters sum of concentration of all esters (C6 C26) 4 Principle A sample is analysed by gas chromatography using an external calibration method t
24、o quantify the esters present in biodiesel regardless of the raw material used in its production. ISO 2016 All rights reserved 1PD ISO/TS 17307:2016ISO/TS 17307:2016(E) The quantification of biodiesel samples with C18 carbon chains is performed using an analytical curve prepared with methyl or ethyl
25、 octadecanoate. If there is presence of esters with carbon chain shorter than C 14 , in addition methyl or ethyl dodecanoate is used for quantifying these esters in the sample. It is recommended to consult the chromatograms presented in Annex A to facilitate the identification of different matrices
26、of biodiesel. 5 Apparatus 5.1 Gas chromatograph equipped with flame ionization detector (FID), an on-column injector (or equivalent) and oven with temperature programming. 5.2 Data acquisition system, an electronic instrument to obtain and record the peak area in the chromatograms. 5.3 Column, fused
27、 silica capillary column, 30 m 0,32 mm 0,1 m, with stationary phase 95 % dimethylpolysiloxane and 5 % phenyl-methylpolysiloxane for high temperature (up to 400 C). Any column with better or equivalent efficiency and selectivity may be used. Their usefulness should be observed by comparing the chroma
28、togram obtained with chromatograms presented in Annex A. NOTE A retention gap of 0,53 mm of internal diameter can be used. 5.4 Automatic sampler. 5.5 Balance, with resolution of 0,1 mg. 5.6 Flask, with the capacity of 50 mL, with lid. 5.7 Micro syringe, with the capacity for 1,0 l. 5.8 Pasteur pipet
29、tes. 5.9 Beaker of 50 ml. 6 Reagents and materials 6.1 n-heptane, (CAS 1)N o142-82-5), minimum purity of 99 %. 6.2 Methyl dodecanoate (CAS 1)N o111-82-0) or ethyl dodecanoate (CAS 1)N o106-33-2), minimum purity of 99 %. 6.3 Methyl octadecanoate (CAS 1)N o112-61-8) or ethyl octadecanoate (CAS 1)N o11
30、1-61-5), minimum purity of 99 %. 6.4 Carrier gas, hydrogen or helium, minimum purity of 99,999 %, as carrier gas (for detector gas a FID suitable grade is allowed). 6.5 Nitrogen, minimum purity of 99,999 %, grade suitable for FID. 1) Represents the register of chemical substances catalogued in the C
31、AS system. CAS numbers have no chemical meaning, these are numbers designated in sequential order for each substance added to the system.2 ISO 2016 All rights reservedPD ISO/TS 17307:2016ISO/TS 17307:2016(E) 6.6 Synthetic air, minimum purity of 99,999 %, grade suitable for FID. 7 Sampling Unless oth
32、erwise specified, obtain representative samples for analysis in accordance with the procedures given in ISO 3170, ISO 3171 or an equivalent International Standard. 8 Procedure 8.1 Preparation of the apparatus 8.1.1 Install the column according to the instructions of the manufacturer. 8.1.2 Establish
33、 a flow of about 3,0 ml/min of helium (pressure around 180 kPa and average linear velocity around 0,54 m/s and) or hydrogen (pressure around 105 kPa and average linear velocity around 0,70 m/s). 8.1.3 Adjust the following typical operation conditions on the gas chromatograph: a) programming the oven
34、 temperature: Heating rate C/min Temperature C Holding time min 50 1 15 180 0 7 230 0 20 380 10 b) carrier gas: helium or hydrogen; c) detector temperature: 380 C; d) injector temperature: oven tracking; e) nitrogen flow for the detector (make-up gas): 30 ml/min; f) hydrogen flow for the detector: 3
35、5 ml/min; g) synthetic air flow for the detector: 350 ml/min; h) volume to be injected: 0,5 l; i) approximate time of analysis: 35 min. NOTE The detector flows recommended by the manufacturer can also be used. 8.1.4 Evaluate the stability of the baseline running a blank. 8.1.5 After the system stabi
36、lizes baseline subtraction or electronic compensation of the signal, following the procedures inside the equipments manual may be applied to eliminate the deviation of the baseline due to the temperature programming of the oven. ISO 2016 All rights reserved 3PD ISO/TS 17307:2016ISO/TS 17307:2016(E)
37、8.2 Preparation of the calibration curve 8.2.1 For biodiesel samples containing mainly fatty acids with C 16and C 18carbon chains, a calibration curve shall be prepared with methyl or ethyl octadecanoate. 8.2.2 In samples that contain fatty acids with carbon chains less than C 14 , two calibration c
38、urves are required; one using methyl or ethyl dodecanoate to quantify these esters and another using methyl or ethyl octodecanoate to quantify all the others esters. 8.2.3 Prepare a minimum of six standard solutions for any calibration curve, each one corresponding to a point in the curve. An exampl
39、e of preparation procedure for six points of standard solutions of methyl or ethyl octadecanoate is found in Annex B. 8.2.4 Inject 0,5 l of the standard solution, at least two times. Identify the peaks according to the chromatograms in Annex A and obtain the area of each component. NOTE Depending on
40、 the construction of different instruments, there is a risk that the linear range of the FID is exceeded. Check the peak shape to secure that the detector/amplifier has not become overloaded/saturated. 8.2.5 Obtain the calibration curve of each component of the solution by plotting the area in (y) a
41、xis versus concentration in mass percentage in (x) axis. A calibration curve is acceptable if its regression coefficient is 0,999. 8.3 Sample preparation 8.3.1 Add approximately 0,1 g with an accuracy of 0,1 mg of sample to a 50 ml beaker (5.9) and record the mass. 8.3.2 Dilute with 26,8 g of n-hept
42、ane and determine the total mass of solution. Homogenize and transfer to the vial of automatic sampler. 8.4 Procedure 8.4.1 Inject 0,5 l of sample solution (see 8.3) at least two times. 8.4.2 Identify and integrate all the peaks of esters of the sample from C6 up to C26. For guidance, see the chroma
43、tograms of Annex A. The identification of peaks relating to esters may be done using a standard chromatogram obtained by gas chromatography/mass spectrometry (GC/MS). In that case, GC/MS and GC/FID configurations shall be equivalent.4 ISO 2016 All rights reservedPD ISO/TS 17307:2016ISO/TS 17307:2016
44、(E) 9 Expression of results Calculate the total ester content with Formula (1): (1) whereC is the mass percentage % (m/m) of total ester content of the sample;A is the sum of peak areas of the identified esters of the sample;a is the slope (angular coefficient) of the calibration curve;b is the inte
45、rcept obtained for the calibration curvem a is the mass of sample used in 8.3 in grams (g);m t is the total mass (mass of sample + mass of n-heptane), in grams (g) Express the results in % (m/m) to the nearest 0,1 % (m/m). 10 Precision 10.1 General The precision given in 10.2 and 10.3 was determined
46、 by statistical examination of interlaboratory test results in accordance with ISO 4259. 10.2 Repeatability, r The difference between two test results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the
47、normal and correct operation of the test method, exceed the values calculated according to Formula (2) only in one case in twenty. r = -53,404 + 0,595 6 X % (2) whereX represents the mean of the two results expressed in % (m/m). 10.3 Reproducibility, R The difference between two single and independe
48、nt test results, obtained by different operators working in different laboratories on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the values calculated according to the Formula (3) only in one case in twenty. R = 17,461 2 + -0,128 9
49、X % (3) whereX represents the mean of the two results expressed in % (m/m). ISO 2016 All rights reserved 5PD ISO/TS 17307:2016ISO/TS 17307:2016(E) 11 Test report The test report shall specify the following: a) the reference to this Technical Specification, i.e. ISO/TS 17307:; b) the type and complete identification of the product tested; c) the used method of sampling; d) the results of the test (see Clause 9); e) all operating details not specified in this Technical Specif
