CEN/TS 15408:2006
(Main)Solid recovered fuels - Methods for the determination of sulphur (S), chlorine (Cl), fluorine (F) and bromine (Br) content
Solid recovered fuels - Methods for the determination of sulphur (S), chlorine (Cl), fluorine (F) and bromine (Br) content
This Technical Specification describes the determination of S, Cl, F and Br in solid recovered fuels of various origin and composition after combustion in oxygen atmosphere. S and Cl can be alternatively determined by direct automatic analysis (see Bibliography for examples of available methods). Other methods could also be used provided that it is demonstrated that they give the same results.
This method is applicable for concentrations over 0,025 g/kg, depending on the element and on the determination technique.
Insoluble halides and sulphate present in the original sample or produced during the combustion step are not completely determined by these methods.
This Technical Specification provides recommendations concerning standardised methods for determination of halides and sulphate in the solution obtained after combustion.
Feste Sekundärbrennstoffe - Verfahren zur Bestimmung des Gehaltes an Schwefel (S), Chlor (Cl), Fluor (F) und Brom (Br)
Combustibles solides de récupération - Méthodes pour la détermination de la teneur en soufre (S), en chlore (Cl), en fluor (F), et en brome (Br)
Trdno alternativno gorivo - Metode za določevanje žvepla (S), klora (Cl), fluora (F) in broma (Br)
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
01-marec-2007
7UGQRDOWHUQDWLYQRJRULYR0HWRGH]DGRORþHYDQMHåYHSOD 6 NORUD &O IOXRUD )
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Solid recovered fuels - Methods for the determination of sulphur (S), chlorine (Cl),
fluorine (F) and bromine (Br) content
Feste Sekundärbrennstoffe - Verfahren zur Bestimmung des Gehaltes an Schwefel (S),
Chlor (Cl), Fluor (F) und Brom (Br)
Combustibles solides de récupération - Méthodes pour la détermination de la teneur en
soufre (S), en chlore (Cl), en fluor (F), et en brome (Br)
Ta slovenski standard je istoveten z: CEN/TS 15408:2006
ICS:
75.160.10 Trda goriva Solid fuels
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
TECHNICAL SPECIFICATION
CEN/TS 15408
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
September 2006
ICS 75.160.10
English Version
Solid recovered fuels - Methods for the determination of sulphur
(S), chlorine (Cl), fluorine (F) and bromine (Br) content
Combustibles solides de récupération - Méthodes pour la Feste Sekundärbrennstoffe - Verfahren zur Bestimmung
détermination de la teneur en soufre (S), en chlore (Cl), en des Gehaltes an Schwefel (S), Chlor (Cl), Fluor (F) und
fluor (F), et en brome (Br) Brom (Br)
This Technical Specification (CEN/TS) was approved by CEN on 25 March 2006 for provisional application.
The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to submit their
comments, particularly on the question whether the CEN/TS can be converted into a European Standard.
CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available
promptly at national level in an appropriate form. It is permissible to keep conflicting national standards in force (in parallel to the CEN/TS)
until the final decision about the possible conversion of the CEN/TS into an EN is reached.
CEN members are the national standards bodies of Austria, Belgium, 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, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36 B-1050 Brussels
© 2006 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 15408:2006: E
worldwide for CEN national Members.
Contents Page
Foreword.3
Introduction .4
1 Scope .5
2 Normative references .5
3 Terms and definitions .5
4 Safety remarks .6
5 Principle.6
6 Apparatus .6
7 Reagents.7
8 Interferences and sources of error .8
9 Procedure .8
10 Calculation and evaluation .9
11 Quality control.10
12 Performance characteristics .10
13 Test report .10
Annex A (normative) Guidelines - Characteristics of the laboratory sample for chemical analysis
of SRF .11
Bibliography .13
Foreword
This document (CEN/TS 15408:2006) has been prepared by Technical Committee CEN/TC 343 “Solid
Recovered Fuels”, the secretariat of which is held by SFS.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to announce this CEN Technical Specification: Austria, Belgium, 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, Sweden,
Switzerland and United Kingdom.
Introduction
Determination of total sulphur, chlorine, fluorine and bromine content of solid recovered fuels is necessary for
environmental and technical reasons both in the production and combustion stage.
During the combustion process they are usually converted to sulphur oxides 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, fluoride
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.
1 Scope
This Technical Specification describes the determination of S, Cl, F and Br in solid recovered fuels of various
origin and composition after combustion in oxygen atmosphere. S and Cl can be alternatively determined by
direct automatic analysis (see Bibliography for examples of available methods). Other methods could also be
used provided that it is demonstrated that they give the same results.
This method is applicable for concentrations over 0,025 g/kg, depending on the element and on the
determination technique.
Insoluble halides and sulphate present in the original sample or produced during the combustion step are not
completely determined by these methods.
This Technical Specification provides recommendations concerning 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 Technical Specification. For
dated references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
CEN/TS 15357:2006, Solid recovered fuels — Terminology, definitions and descriptions
CEN/TS 15413, Solid recovered fuels — Methods for the preparation of the test sample from the laboratory
sample
prCEN/TS 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 3696:1987)
EN ISO 10304-1:1995, Water quality — Determination of dissolved fluoride, chloride, nitrite, orthophosphate,
bromide, nitrate and sulfate ions, using liquid chromatography of ions — Part 1: Method for water with low
contamination (ISO 10304-1:1992)
EN ISO 10304-2:1996, Water quality — Determination of dissolved anions by liquid chromatography of ions —
Part 2: Determination of bromide, chloride, nitrate, nitrite, orthophosphate and sulfate in waste water (ISO
10304-2:1995)
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 quality — Determination of chloride — Silver nitrate titration with chromate indicator (Mohr’s
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 Technical Specification, the terms and definitions given in CEN/TS 15357:2006 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 solution
NOTE Be aware that the above definition is valid for this empirical Technical Specification 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 handling of potentially hazardous materials is dealt with in 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 described 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 containing oxygen under pressure. Halogenated and
sulphur compounds are converted respectively to fluoride, chloride, bromide and sulfate which are
absorbed and/or dissolved in an absorption solution (water or KOH 0,2 M solution);
- analysis of Cl, F and S and Br by ion chromatography or other suitable technique, reported in the
reference documents listed in Clause 2. Br is preferably determined by ICP-MS since several oxidation
states of Br occur after oxygen combustion.
6 Apparatus
Ordinary laboratory apparatus, and:
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 adsorb 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 bomb 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 bomb are commercially
available).
The combustion apparatus is equipped with automatic ignition system and oxygen gas supply.
6.2 Balances
- Analytical balance resolution ± 0,1 mg.
- Balance resolution ± 0,1 g.
6.3 Ion chromatograph
An ion chromatograph with suitable anion separator column, pre-column, 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 introduction 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 3696:1995.
7.2 Oxygen
Free of combustion material, minimum 99,99 purity.
7.3 Nitrogen
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 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 M solution is more efficient for trapping the gases. As a preliminary 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.
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 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 of the control
...
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