1、raising standards worldwideNO COPYING WITHOUT BSI PERMISSION EXCEPT AS PERMITTED BY COPYRIGHT LAWBSI Standards PublicationBS EN 15411:2011Solid recovered fuels Methods for the determinationof the content of majorelements (Al, Ca, Fe, K, Mg, Na,P, Si, Ti)BS EN 15411:2011 BRITISH STANDARDNational fore
2、wordThis British Standard is the UK implementation of EN 15411:2011. Itsupersedes DD CEN/TS 15411:2006 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee PTI/17, Solid biofuels.A list of organizations represented on this committee can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 request
3、 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 69794 4ICS 75.160.10Compliance with a British Standard cannot confer immunity fromlegal obligations.This British Standard
4、 was published under the authority of theStandards Policy and Strategy Committee on 30 September 2011.Amendments issued since publicationDate Text affectedEUROPEAN STANDARD NORME EUROPENNE EUROPISCHE NORM EN 15411 September 2011 ICS 75.160.10 Supersedes CEN/TS 15411:2006English Version Solid recover
5、ed fuels - Methods for the determination of the content of trace elements (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Mn, Ni, Pb, Sb, Se, Tl, V and Zn) Combustibles solides de rcupration - Mthodes de dtermination de la teneur en lments ltat de traces (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Mn, Ni, Pb, Sb, Se,
6、 Tl, V et Zn) Feste Sekundrbrennstoffe - Verfahren zur Bestimmung des Gehaltes an Spurelementen (As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mo, Mn, Ni, Pb, Sb, Se, Tl, V und Zn) This European Standard was approved by CEN on 15 July 2011. CEN members are bound to comply with the CEN/CENELEC Internal Regulations
7、 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 Management Centre or to any CEN member. Thi
8、s 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 status as the official versions. CEN memb
9、ers 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, Portugal, Romania, Slovakia, Slovenia, Spain,
10、 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 2011 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Memb
11、ers. Ref. No. EN 15411:2011: EEN 15411:2011 (E) 2 Contents Page Foreword 3Introduction .41 Scope 52 Normative references 53 Terms and definitions .54 Safety remarks .65 Principle 66 Apparatus .67 Reagents .78 Procedure .78.1 Sample conservation and pre-treatment .78.2 Sample preparation .89 Digestio
12、n procedure 89.1 Method A .89.2 Method B (informative) .89.3 Method C (informative) .810 Analysis of the digestion solutions .910.1 Preparation of the solution for analysis 910.2 Analytical step 911 Expression of results 912 Quality control 913 Performance characteristics . 1014 Test report . 10Anne
13、x A (normative) Guidelines - Characteristics of the laboratory sample for chemical analysis of SRF . 11Annex B (informative) Performance data . 13Annex C (informative) Major results of ruggedness testing 22Bibliography . 25EN 15411:2011 (E) 3 Foreword This document (EN 15411:2011) has been prepared
14、by 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 March 2012, and conflicting national standards s
15、hall be withdrawn at the latest by March 2012. 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 patent rights. This document supersedes CEN/TS 15411:2
16、006. This document differs from CEN/TS 15411:2006 only editorially. 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, Cyprus, Czech Republic, Denmark,
17、Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. EN 15411:2011 (E) 4 Introduction Accurate determination of trace e
18、lement content in solid recovered fuels is important for environmental and technical reasons both in the production and combustion stage. After digestion of the solid recovered fuels using different methods, a number of analytical techniques can be used for the quantification of the trace element co
19、ntent. They include Inductively Coupled Plasma with optical or mass detection, graphite furnace Atomic Absorption Spectrometry and, when available, dedicated specific method (e.g. for mercury). EN 15411:2011 (E) 5 1 Scope This European Standard specifies three methods of digestion for solid recovere
20、d fuels: a) microwave assisted digestion with hydrofluoric, nitric and hydrochloric acid mixture; b) hot water bath digestion of with hydrofluoric, nitric and hydrochloric acid mixture, after ashing of the SRFs sample; c) oven digestion with nitric, perchloric and hydrofluoric acid mixture. Instrume
21、ntal determination of As, Ba, Be, Cd, Cr, Co, Cu, Pb, Mn, Mo, Ni, Sb, Se, Tl, V, Zn is performed by Inductively Coupled Plasma with optical or mass detection or graphite furnace Atomic Absorption Spectrometry. Hg can be analysed only after the microwave assisted procedure or, alternatively, by a dir
22、ect analysis method (Hg direct AMA). The effectiveness of the digestion can be verified by qualitative X-ray fluorescence (XRF) analysis on the remaining residue. If necessary, an alternative digestion method (among those proposed) is used. Method a) is recommended for general use, but the amount of
23、 the test portion can be very low in case of high concentration of organic matter. Method b) is recommended for Solid Recovered Fuel (SRF) with high organic matter concentration that can be difficult to digest with the other methods. This method is not suitable for mercury. Method c) is recommended
24、for Solid Recovered Fuel (SRF) samples for which the other methods leave a significant insoluble residue. Alternative digestion methods can be applied if their performance is proved to be comparable with those of the methods mentioned in a) to c) (see Annex C). 2 Normative references The following r
25、eferenced documents are indispensable for the application of this European Standard. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 13656, Characterization of waste Microwave assisted
26、digestion with hydrofluoric (HF), nitric (HNO3) and hydrochloric (HCI) acid mixture for subsequent determination of elements EN 15357:2011, Solid recovered fuels Terminology, definitions and descriptions EN 15403, Solid recovered fuels Determination of ash content EN 15413, Solid recovered fuels Met
27、hods for the preparation of the test sample from the laboratory sample EN 15414-3, Solid recovered 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 3
28、696:1987) 3 Terms and definitions For the purpose of this document, the terms and definitions given in EN 15357:2011 and the following apply. EN 15411:2011 (E) 6 3.1 digestion mineralization of the organic matter of a sample and dissolution of its mineral part, more or less completely, when reacted
29、with a reagent mixture 3.2 microwave unit whole microwave digestion system (oven and associated equipment) 4 Safety remarks The safety in handling of potentially hazardous materials is dealt with by the relevant national and European regulations, which every laboratory should refer to. In addition t
30、he following information is given: Only experienced personnel can use the microwave apparatus, following the operating instructions described in the manufacturer manual; Most of the reagents used within this European Standard are strongly corrosive and toxic. Safety precautions are absolutely necess
31、ary due to strong corrosive reagents, high temperature and high pressure; All procedures have to be performed in a hood or in closed force-ventilated equipment. By the use of strong oxidising reagents the formation of explosive organic intermediates is possible, especially when dealing with samples
32、with a high organic content. Do not open pressurised vessels before they have cooled down. Avoid contact with the chemicals and the gaseous reaction products. 5 Principle The test portion is digested using one of the proposed methods with a suitable acid mixture. The digested sample is then analysed
33、 by the most appropriate spectrometric technique, such as atomic absorption or emission spectroscopy. 6 Apparatus 6.1 Microwave unit Intended for laboratory use and preferably equipped with temperature control. 6.2 Resistance heating oven A resistance heated oven or heating block that can be used at
34、 a temperature of at least 220 C and an accuracy of 10 C. 6.3 Digestion vessels The vessels used in the microwave unit shall be equipped with a pressure relieve valve or another technical equipment which avoids the bursting of the vessels at suddenly occurring excess pressure. The material of the ve
35、ssels has to be inert to the acids used for digestion. The digestion vessel shall withstand the pressure of at least 8 bar. If the amount of organic carbon exceeds 100 mg, it has to be ensured that the digestion vessel is capable of withstanding higher pressures. 6.4 Inductively coupled plasma EN 15
36、411:2011 (E) 7 Normal commercial instrumentation with optical or mass spectrometric detector (ICP-OES, ICP-MS). 6.5 Atomic absorption spectrophotometer Normal commercial instrumentation, equipped with graphite furnace or hydride generation systems or cold vapour (GF-AAS, HG-AAS, CV-AAS). 6.6 X-ray f
37、luorescence spectrometer Energy or wavelength dispersion system suitable for qualitative analysis of the elements listed in this European Standard (with the exception of beryllium). 6.7 Balances Analytical balance resolution 0,1 mg. 6.8 General equipment General laboratory equipment, including volum
38、etric graduated flasks and pipettes of adequate size. Filter equipment of adequate chemical resistance and purity or centrifuge. The use of glassware shall be excluded when free hydrofluoric acid is present. The glassware used in the digestion procedure should be carefully pre-cleaned with for examp
39、le 10 % nitric acid solution. 7 Reagents All reagents shall be at least of analytical grade and suitable for their specific purposes. Other specific reagents are listed and described in the reference methods for digestion or instrumental determination listed in Clause 2. NOTE Acids used in the prepa
40、ration of standards and for sample processing are of high purity. Redistilled acids are recommended because of the high sensitivity of ICP-MS. Nitric acid at less than 2 % (v/v) is recommended for ICP-MS to minimize damage to the interface and to minimize isobaric molecular-ion interferences with th
41、e analytes. Many more molecular-ion interferences are observed when hydrochloric and sulphuric acids are used. 7.1 Water of grade 1 as specified by EN ISO 3696:1995. 7.2 Nitric acid (HNO3), 65 % (w/w), 1,40 g/ml. 7.3 Hydrofluoric acid (HF), 40 % (w/w), 1,14 g/ml. 7.4 Perchloric acid (HClO4), 70 % (w
42、/w), 1,62 g/ml. 7.5 Hydrochloric acid (HCl), 65 % (w/w), 1,40 g/ml. 8 Procedure 8.1 Sample conservation and pre-treatment The laboratory samples shall be stored according to guidelines defined in Annex A. EN 15411:2011 (E) 8 It is advisable to contact the people performing the sampling in order to a
43、gree a procedure for the laboratory sample preparation and storage before delivering to the laboratory. In particular, any treatment procedure which can increase the temperature of the material above 40 C should be avoided, in order to avoid significant loss of mercury or other volatile compounds. F
44、urthermore, any possible source of contamination during the laboratory sample preparation (e.g. grinding with metallic apparatus) shall be avoided or reduced as much as possible. The laboratory sample should be stored and delivered in sealed high-density plastic containers. 8.2 Sample preparation Th
45、e test portion shall be prepared from the laboratory sample according to EN 15413. In addition, for the purposes of this method, the target size should be 1 mm or below. Depending on the used digestion method, the amount of test portion ranges between 0,2 g and 0,5 g. Whereas the determination is ca
46、rried out on a dry basis, the moisture content shall be determined according to EN 15414-3. 9 Digestion procedure 9.1 Method A Weigh between 0,2 g to 0,5 g of the sample, to the nearest 0,1 mg, prepared according to Clause 8 and transfer it into the vessel. If necessary, the sample may be moistened
47、with a minimum amount of water. Proceed according to the general principle of EN 13656. After cooling, the solutions are transferred to volumetric flasks of suitable volume (e.g. 50 ml). Any residue shall be separated by filtration or centrifugation and the composition is controlled by XRF or any ot
48、her suitable technique: if a significant amount of the elements of interested is detected, an alternative digestion method for the dissolution of the residual material is necessary. The control on the residue can be avoided if its composition is known from previous analysis of the same kind of mater
49、ials or on the basis of experience. 9.2 Method B (informative) Weigh 0,2 g of ashed sample according to EN 15403 in a low pressure teflon bomb with relief valve and proceed according to the general principle of method reported in EN 13656. 4 ml aqua regia and 1 ml concentrated HF are added. After closing, the bombs are placed in a water bath at 90 C for 3 h. After cooling, the solutions are transferred to volumetric flasks of suitable vol
