1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 15408:2011Solid recovered fuels Methods for the determinationof sulphur (S), chlorine (Cl),fluorine (F) and bromine (Br)contentBS EN 15408:2011 BRITISH STANDARDNational for
2、ewordThis British Standard is the UK implementation of EN 15408:2011. Itsupersedes DD CEN/TS 15408:2006 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/17, Solid biofuels.A list of organizations represented on this committee can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 reques
3、t to its secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. BSI 2011ISBN 978 0 580 67709 0ICS 75.160.10Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standar
4、d was published under the authority of theStandards Policy and Strategy Committee on 31 March 2011.Amendments issued since publicationDate Text affectedBS EN 15408:2011EUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15408 March 2011 ICS 75.160.10 Supersedes CEN/TS 15408:2006English Version Soli
5、d recovered fuels - Methods for the determination of sulphur (S), chlorine (Cl), fluorine (F) and bromine (Br) content Combustibles solides de rcupration - Mthodes pour la dtermination de la teneur en soufre (S), en chlore (Cl), en fluor (F), et en brome (Br) Feste Sekundrbrennstoffe - Verfahren zur
6、 Bestimmung des Gehaltes an Schwefel (S), Chlor (Cl), Fluor (F) und Brom (Br) This European Standard was approved by CEN on 22 January 2011. 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 nati
7、onal standard without any alteration. Up-to-date lists 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 ver
8、sion 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 status as the official versions. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus,
9、Czech 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. EUROPEAN COMMITTEE FOR STANDARDIZATION COMIT
10、EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG Management Centre: Avenue Marnix 17, B-1000 Brussels 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 15408:2011: EBS EN 15408:2011EN 15408:2011 (E) 2 Contents Page Forewo
11、rd 3Introduction .41 Scope 52 Normative references 53 Terms and definitions .54 Safety remarks .65 Principle 66 Apparatus .67 Reagents .78 Interferences and sources of error 89 Procedure .89.1 Sample conservation and pre-treatment .89.2 Sample preparation89.3 Bomb combustion 89.4 Calibration 99.5 An
12、alysis of calibrations samples 99.6 Analysis of samples .910 Calculation and evaluation .910.1 General 910.2 Total chlorine or total fluorine or total bromine . 1010.3 Total sulphur . 1011 Quality control . 1012 Performance characteristics . 1113 Test report . 11Annex A (normative) Guidelines - Char
13、acteristics of the laboratory sample for chemical analysis of SRF 12Annex B (informative) Data on performance characteristics 14Annex C (informative) Major results of ruggedness testing 17Bibliography . 18BS EN 15408:2011EN 15408:2011 (E) 3 Foreword This document (EN 15408:2011) has been prepared by
14、 Technical Committee CEN/TC 343 “Solid recovered fuels”, the secretariat of which is held by SFS. 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 September 2011, and conflicting national standards
15、 shall be withdrawn at the latest by September 2011. This document supersedes CEN/TS 15408:2006. 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 responsible for identifying any or all such pate
16、nt rights. This document has been prepared under a mandate given to CEN by the European Commission and the European Free Trade Association. This document differs from CEN/TS 15408:2006 only editorially. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the fo
17、llowing 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, Sl
18、ovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. BS EN 15408:2011EN 15408:2011 (E) 4 Introduction Determination of total sulphur, chlorine, fluorine and bromine content of solid recovered fuels (SRF) is necessary for environmental and technical reasons both in the production and comb
19、ustion stage. During the combustion process they are usually converted to sulphates and halides. These reaction products contribute significantly to corrosion and environmentally harmful emissions. This method consists of an oxygen combustion procedure followed by trapping of sulphur, chloride, fluo
20、ride and bromide in an absorbing solution and subsequent determination by different techniques. Alternatively, direct automatic techniques can be used for S and Cl determination. Other methods could also be used provided that it is demonstrated that they give the same results. BS EN 15408:2011EN 154
21、08:2011 (E) 5 1 Scope This European Standard specifies the determination of S, Cl, F and Br in solid recovered fuels of various origin and composition after combustion in oxygen atmosphere. This method is applicable for concentrations over 0,025 g/kg, depending on the element and on the determinatio
22、n technique. In the case of fluorine this method is applicable for concentration over 0,015 g/kg. Insoluble halides and sulphate present in the original sample or produced during the combustion step are not completely determined by these methods. This European Standard provides recommendations conce
23、rning standardised methods for determination of halides and sulphate in the solution obtained after combustion. 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 referenc
24、es, the latest edition of the referenced document (including any amendments) applies. EN 15357:2011, Solid recovered fuels Terminology, definitions and descriptions EN 154131), Solid recovered fuels Methods for the preparation of the test sample from the laboratory sample EN 15414-3, Solid recovered
25、 fuels Determination of moisture content using the oven dry method Part 3: Moisture in general analysis sample EN ISO 3696:1995, Water for analytical laboratory use Specification and test methods (ISO 3696:1987) EN ISO 10304-1:2009, Water quality Determination of dissolved anions by liquid chromatog
26、raphy of ions Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate (ISO 10304-1:2007) EN ISO 17294-2, Water quality Application of inductively coupled plasma mass spectrometry (ICP-MS) Part 2: Determination of 62 elements (ISO 17294-2:2003) ISO 9297, Water qu
27、ality Determination of chloride Silver nitrate titration with chromate indicator (Mohrs method) ISO 10359-1, Water quality Determination of fluoride Part 1: Electrochemical probe method for potable and lightly polluted water 3 Terms and definitions For the purposes of this document, the terms and de
28、finitions given in EN 15357:2011 and the following apply. 3.1 halogen content sum of halogens contained as organic and inorganic compounds in the solid recovered fuels, which can be converted to halides (fluoride, chloride, bromide, iodide) by combustion and then absorbed or dissolved in aqueous sol
29、ution 1)To be published. BS EN 15408:2011EN 15408:2011 (E) 6 NOTE The above definition is valid for this empirical European Standard only and do not comply with scientific definitions of halogen content. 3.2 oxygen combustion combustion of material in oxygen atmosphere 4 Safety remarks The safety in
30、 handling of potentially hazardous materials is dealt with relevant national and European regulations, which every laboratory should refer to. In addition the following information is given: only experienced personnel can use the oxygen combustion apparatus, following the operating instructions desc
31、ribed in the manufacturer manual; precautions shall be taken by the operator for reactive gas (oxygen) at high temperature and high pressure. 5 Principle The determination of S, Cl, F and Br is carried out in two steps or by using automatic equipment: the sample is oxidized by combustion in a bomb c
32、ontaining oxygen under pressure. Halogenated and sulphur compounds are converted respectively to fluoride, chloride, bromide and sulphate which are absorbed and/or dissolved in an absorption solution (water or KOH 0,2 mol/l solution); analysis of Cl, F and S and Br by ion chromatography or other sui
33、table technique, are reported in the reference documents listed in Clause 2: for Cl, F, S and Br in EN ISO 10304-1, for F only in ISO 10359-1. Br is preferably determined by “Inductively Coupled Plasma Mass Spectrometry” (ICP-MS) according to EN ISO 17294-2 since several oxidation states of Br occur
34、 after oxygen combustion. 6 Apparatus Apart ordinary laboratory apparatus, the following devices are required: 6.1 Oxygen combustor Equipped with a combustion bomb made of stainless steel or any other material that will not be affected by the combustion process or products (the materials used may ad
35、sorb or react with acid gases formed during combustion or it may be not possible to clean the bomb completely between combustions). The bomb is equipped with oxygen inlet and safety valve and electrical contacts for spark generation. Many commercially available systems can be used. The combustion bo
36、mb may be the same as used for the determination of the calorific value. Carefully check the characteristics of the combustion bomb, in order to be sure that it is suitable for the processing of materials with significant chlorine content (chlorine resistant combustion bombs are commercially availab
37、le). The combustion apparatus is equipped with automatic ignition system and oxygen gas supply. BS EN 15408:2011EN 15408:2011 (E) 7 6.2 Balances Analytical balance resolution 0,1 mg; balance accuracy 0,1 g. 6.3 Ion chromatograph An ion chromatograph with suitable anion separator column, pre-column,
38、background suppressor and conductivity cell. 6.4 Apparatus for titrimetry Any suitable apparatus can be used, with colorimetric or potentiometric final point determination. 6.5 Inductively Coupled Plasma Mass Spectrometry (ICP-MS) Any suitable apparatus with normal resolution and pneumatic sample in
39、troduction system. 6.6 Automatic analyzer Commercial instruments for S and Cl determination. 7 Reagents All reagents shall be at least of analytical grade and suitable for their specific purposes. Particularly, they shall be free of sulphur and halogens. 7.1 Water of grade 1 as specified by EN ISO 3
40、696. 7.2 Oxygen Should be free of combustion material, minimum 99,99 % purity. 7.3 Nitrogen Should be chromatographic grade for the ion chromatograph. 7.4 Eluent for ion chromatography Carbonate/hydrogen carbonate mixed solution is suitable as eluent for ion chromatographic separation. Other eluents
41、 can be used, following the working instruction with the particular column used. 7.5 Absorbing solution Water is appropriate for most application. If the content of chlorine is 1 % or if bromine shall be determined, alkaline KOH 0,2 mol/l solution is more efficient for trapping the gases. As a preli
42、minary check, XRF analysis can be used to check for the presence of Br or high chlorine content. 7.6 Stock standard solutions 1 000 mg/l chlorine, fluorine, bromine and sulphate commercially available standard solutions are used to prepared working and calibration solution by properly dilution. BS E
43、N 15408:2011EN 15408:2011 (E) 8 7.7 Certified reference material (CRMs) The trapping yield can be checked using a material with characteristic similar to SRF, e.g. a solid waste certified reference material. 7.8 Control mixtures To create an appropriate control mixture, choose the control substances
44、 in combination so that all elements that shall be determined in the samples are represented. The amount of halogen and sulphur contents shall be in the same range of the element contents of the samples and approximately in the middle of the working range of the determination techniques. The mixture
45、 of the control substances needs to be homogenized using a pebble mill. EXAMPLE An example of a mixture of control substances for the determination of fluorine, chlorine, bromine and sulphur is: 0,50 g 4-fluoro-benzoic acid; 2,0 g 4-chloro-benzoic acid; 0,25 g 4-bromo-benzoic acid; 0,25 g 4-iodo-ben
46、zoicacid; 2,0 g sulphanilic acid and 55,0 g cellulose are mixed. The mixture is homogenized, e.g. in a pebble mill. This mixture contains 1,13 g/kg fluorine; 7,547 g/kg chlorine; 1,656 g/kg bromine; 2,132 g/kg iodine and 6,17 g/kg sulphur. 8 Interferences and sources of error The container in which
47、the sample is delivered and stored can be a source of errors. Its material shall be chosen according to the elements to be determined. Grinding or milling samples includes a risk of contamination of the sample by the environment. NOTE In fuels with high contents of sulphur bound to iron, the method
48、can show different result. 9 Procedure 9.1 Sample conservation and pre-treatment The laboratory samples shall be stored according to guidelines defined in Annex A. 9.2 Sample preparation The test portion shall be prepared from the laboratory sample according to EN 15413. In addition, for the purpose
49、s of this method, the target size should be 1 mm or below. The amount of test portion is usually 1 g. For some instruments it may be necessary to weigh a lower amount: in this case a nominal size less than 1 mm is required in order to ensure the homogeneity of the test portion, according to EN 15413. Whereas the determination is carried out on dry basis, the moisture content shall be determined according to EN 15414-3. NOTE In some cas
