1、BS EN ISO 16994:2016Solid biofuels Determinationof total content of sulfur andchlorine (ISO 16994:2016)BSI Standards PublicationWB11885_BSI_StandardCovs_2013_AW.indd 1 15/05/2013 15:06BS EN ISO 16994:2016 BRITISH STANDARDNational forewordThis British Standard is the UK implementation of EN ISO16994:
2、2016. It supersedes BS EN ISO 16994:2015 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/17, Solid biofuels.A list of organizations represented on this committee can beobtained on request to its secretary.This publication does not purport to include
3、 all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2016. Published by BSI StandardsLimited 2016ISBN 978 0 580 92380 7ICS 27.190; 75.160.10Compliance 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 2016.Amendments issued since publicationDate Text affectedEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN ISO 16994 August 2016 ICS 75.160.10; 27.190 Supersedes EN ISO 16994:2015English
5、 Version Solid biofuels - Determination of total content of sulfur and chlorine (ISO 16994:2016) Biocombustibles solides - Dtermination de la teneur totale en soufre et en chlore (ISO 16994:2016) Biogene Festbrennstoffe - Bestimmung des Gesamtgehaltes an Schwefel und Chlor (ISO 16994:2016) This Euro
6、pean Standard was approved by CEN on 27 July 2016. 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 bibliographical references conc
7、erning 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 the responsibility of a CEN member in
8、to 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 Yugoslav Republic of Macedonia, France,
9、Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey andUnited Kingdom. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE
10、 FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2016 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN ISO 16994:2016 EBS EN ISO 16994:2016EN ISO 16994:2016 (E) 3 European foreword This document (EN ISO 1
11、6994:2016) has been prepared by Technical Committee ISO/TC 238 “Solid biofuels“ in collaboration with Technical Committee CEN/TC 335 “Solid biofuels” the secretariat of which is held by SIS. This European Standard shall be given the status of a national standard, either by publication of an identica
12、l text or by endorsement, at the latest by February 2017, and conflicting national standards shall be withdrawn at the latest by February 2017. Attention is drawn 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 r
13、esponsible for identifying any or all such patent rights. This document supersedes EN ISO 16994:2015. 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, Croatia,
14、 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, Slovenia, Spain, Sweden, Switzerland, Turkey and the U
15、nited Kingdom. Endorsement notice The text of ISO 16994:2016 has been approved by CEN as EN ISO 16994:2016 without any modification. BS EN ISO 16994:2016ISO 16994:2016(E)Foreword ivIntroduction v1 Scope . 12 Normative references 13 Terms and definitions . 14 Principle 24.1 General . 24.2 Decompositi
16、on of the biofuel . 24.3 Determination of sulfate and chloride in the decomposition solution . 24.4 Automatic equipment 25 Reagents 36 Apparatus . 36.1 General . 36.2 Method A 36.3 Method B 47 Preparation of the test sample . 48 Procedure. 48.1 Decomposition 48.1.1 Method A: Combustion in a closed c
17、ombustion vessel . 48.1.2 Method B: Digestion in a closed vessel . 58.1.3 Blank test 68.2 Detection methods . 68.2.1 Ion chromatography . 68.2.2 Other detection methods 68.3 Calibration of the apparatus 68.4 Analyses of the decomposition solutions . 69 Expression of results 79.1 General . 79.2 Total
18、 chlorine 79.3 Total sulfur 710 Performance characteristics 711 Test report . 8Annex A (informative) Performance data . 9Bibliography .11 ISO 2016 All rights reserved iiiContents PageBS EN ISO 16994:2016ISO 16994:2016(E)ForewordISO (the International Organization for Standardization) is a worldwide
19、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 established has the right to be represented on that c
20、ommittee. 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 standardization.The procedures used to develop this document
21、 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 accordance with the editorial rules of the ISO/IEC Directives,
22、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 any patent rights identified during the development of
23、 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 endorsement.For an explanation on the meaning of ISO specific t
24、erms 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 responsible for this document is ISO/TC 238, Solid biofuels.This
25、 second edition cancels and replaces the first edition (ISO 16994:2015), of which it constitutes a minor revision.iv ISO 2016 All rights reservedBS EN ISO 16994:2016ISO 16994:2016(E)IntroductionSulfur and chlorine are present in solid biofuels in varying concentrations. During the combustion process
26、, they are usually converted to sulfur-oxides and chlorides. The presence of these elements and their reaction products can contribute significantly to corrosion and to environmentally harmful emissions.Chlorine can be present in different organic and inorganic compounds and is to exceed or equal th
27、e water soluble amount that can be determined by ISO 16995.Combustion in an oxygen atmosphere in a closed combustion vessel is the preferred method to digest biomass samples for a determination of the total content of sulfur and chlorine. An advantage of the method is that the digestion can be carri
28、ed out in connection with the determination of the calorific value according to ISO 181251). Decomposition in closed vessels is an appropriate alternative method. Other analytical techniques (e.g. high-temperature combustion in a tube furnace and Eschka method) may also be used. The determination of
29、 the resultant chlorine and sulfur compounds can be done by different techniques, e.g. ion chromatography, ICP, titrimetry.Automatic equipment and alternative methods may be used when these methods are validated with biomass reference samples of an adequate type and also meet the requirements of Cla
30、use 10.A list with typical sulfur and chlorine contents of solid biofuels can be found in ISO 17225-1:2014, Annex B.1) To be published. ISO 2016 All rights reserved vBS EN ISO 16994:2016BS EN ISO 16994:2016Solid biofuels Determination of total content of sulfur and chlorine1 ScopeThis International
31、Standard describes methods for the determination of the total sulfur and total chlorine content in solid biofuels. This International Standard specifies two methods for decomposition of the fuel and different analytical techniques for the quantification of the elements in the decomposition solutions
32、. The use of automatic equipment is also included in this International Standard, provided that a validation is carried out as specified and that the performance characteristics are similar to those of the method described in this International Standard.2 Normative referencesThe following documents,
33、 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 any amendments) applies.ISO 10304-1, Water quality Deter
34、mination of dissolved anions by liquid chromatography of ions Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfateISO 11885, Water quality Determination of selected elements by inductively coupled plasma optical emission spectrometry (ICP-OES)ISO 147802), Sol
35、id biofuels Sample preparationISO 16559, Solid biofuels Terminology, definitions and descriptionsISO 16967:2015, Solid biofuels Determination of major elements Al, Ca, Fe, Mg, P, K, Si, Na and TiISO 181252), Solid biofuels Determination of calorific valueISO 18134-3, Solid biofuels Determination of
36、moisture content Oven dry method Part 3: Moisture in general analysis sampleCEN Guide 13:2008, Validation of environmental test methods3 Terms and definitionsFor the purposes of this document, the terms and definitions given in ISO 16559 and the following apply.3.1reference materialRMmaterial or sub
37、stance one or more of whose property values are sufficiently homogeneous and well-established to be used for the calibration of an apparatus, the assessment of a measurement method, or for assigning values to materials2) To be published.INTERNATIONAL STANDARD ISO 16994:2016(E) ISO 2016 All rights re
38、served 1BS EN ISO 16994:2016ISO 16994:2016(E)3.2certified reference materialCRMreference material, accompanied by a certificate, one or more of whose property values are certified by a procedure which establishes traceability to an accurate realization of the unit in which the property values are ex
39、pressed, and for which each certified value is accompanied by an uncertainty at a stated level of confidence3.3NIST standard reference materialSRMCRM issued by NIST that also meets additional NIST-specific certification criteria and is issued with a certificate or certificate of analysis that report
40、s the results of its characterisations and provides information regarding the appropriate use(s) of the material4 Principle4.1 GeneralThe determination of total sulfur and total chlorine content is performed in two steps (4.2 and 4.3) or by using automatic equipment (see 4.4).4.2 Decomposition of th
41、e biofuel Combustion in an oxygen atmosphere in a combustion vessel and absorption of the acidic gas components in an absorption solution (method A). Digestion in closed vessels as described in ISO 16967:2015, Part A (method B).4.3 Determination of sulfate and chloride in the decomposition solution
42、Ion chromatography, in accordance with the principles of ISO 10304-1. ICP, in accordance with the principles of ISO 11885 (determination as sulfur and chlorine).4.4 Automatic equipmentAutomatic equipment may be used when the method is validated with biomass reference samples of an adequate biomass t
43、ype. If automatic equipment is used, sulfur and chlorine compounds may be detected as gaseous components (e.g. by infrared methods). Examples for automatic analysers include elemental analysers, AOX-analysers.If automatic equipment or X-ray fluorescence are used, the method shall be validated for th
44、e respective main origin based biomass group (see ISO 17225-1:2014, Table 1: woody biomass, herbaceous biomass, or fruit biomass) according to CEN Guide 13:2008, Clause 3 validation of alternative methods with one of the following two approaches: full validation as applies to reference methods; rela
45、tive validation in which a comparison is made to the reference method, e.g. by participation in inter-laboratory comparison tests.NOTE Equipment validated only with, for example, straw reference materials, is not automatically suitable for the determination of sulfur and chlorine in, for example, wo
46、od samples, because of the usually significant lower concentrations of the elements in wood and/or the unknown influences of the different matrix.2 ISO 2016 All rights reservedBS EN ISO 16994:2016ISO 16994:2016(E)5 ReagentsThe reagents listed below relate to the digestion method specified in 8.1.1 (
47、method A). Reagents for the digestion method B and the different detection methods according to 8.2 are specified in the corresponding standards.5.1 GeneralAll reagents shall be at least of analytical grade and suitable for their specific purpose. Particularly, they shall contain negligible amounts
48、of chlorine and sulfur, i.e. amounts that do not contribute significantly to the determination.5.2 Water, de-ionized water will normally fulfil the requirements of 5.15.3 Oxygen, pure oxygen with an assay of at least 99,5 % (V/V).5.4 Combustion aid/enhancer, various substances may be used, e.g. benz
49、oic acid, paraffin oil, acetobutyrate capsules, polyethylene bags.5.5 Use of certified reference materials (CRM or SRM).Use certified reference materials to check if the accuracy of the calibration meets the required performance characteristics. Examples of certified reference materials are SRM 1570 spinach leaves, SRM 1571 orchard leaves, SRM 1573 tomato leaves, and SRM 1575 pine needles.When, due to matrix effects or concentration range limitations, no good recoveries for the certified reference materials can be obtained, calibr
