CEN/TS 15289:2006
(Main)Solid Biofuels - Determination of total content of sulphur and chlorine
Solid Biofuels - Determination of total content of sulphur and chlorine
This Technical Specification describes methods for the determination of the total sulphur and total chlorine content in solid biofuels. The method describes a procedure for the digestion and different analytical techniques for the quantification of the elements in the digestion solution.
The method is applicable for all biofuel samples containing more than 50 mg/kg of chlorine and/or sulphur.
Feste Biobrennstoffe - Bestimmung des Gesamtgehaltes an Schwefel und Chlor
Diese Technische Spezifikation legt Verfahren zur Bestimmung des Gesamtgehaltes an Schwefel und an
Chlor in festen Biobrennstoffen fest. Das Verfahren umfasst die Durchführung eines Aufschlusses und ver-schiedene
Analysenverfahren für die quantitative Bestimmung der Elemente in der Aufschlusslösung.
Das Verfahren gilt für alle Biobrennstoffproben, die mehr als 50 mg/kg Chlor und/oder Schwefel enthalten.
Biocombustibles solides - Détermination de la teneur en chlore et en soufre
Trdna biogoriva – Določevanje celotnega žvepla in klora
General Information
Relations
Standards Content (Sample)
SLOVENSKI STANDARD
01-september-2006
7UGQDELRJRULYD±'RORþHYDQMHFHORWQHJDåYHSODLQNORUD
Solid Biofuels - Determination of total content of sulphur and chlorine
Feste Biobrennstoffe - Bestimmung des Gesamtgehaltes an Schwefel und Chlor
Biocombustibles solides - Détermination de la teneur en chlore et en soufre
Ta slovenski standard je istoveten z: CEN/TS 15289:2006
ICS:
75.160.10
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
TECHNICAL SPECIFICATION
CEN/TS 15289
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
April 2006
ICS 75.160.10
English Version
Solid Biofuels - Determination of total content of sulphur and
chlorine
Biocombustibles solides - Détermination de la teneur en Feste Biobrennstoffe - Bestimmung des Gesamtgehaltes
chlore et en soufre an Schwefel und Chlor
This Technical Specification (CEN/TS) was approved by CEN on 22 November 2005 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 15289:2006: 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 Principle.5
5 Reagents.6
6 Apparatus .7
7 Preparation of the test sample.7
8 Procedure .7
9 Calculation.9
10 Precision of the method .10
11 Test report .11
Bibliography.12
Foreword
This Technical Specification (CEN/TS 15289:2006) has been prepared by Technical Committee CEN/TC 335
“Solid biofuels”, the secretariat of which is held by SIS.
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
Sulphur and chlorine are present in solid biofuels in varying concentrations. During the combustion process
they are usually converted to sulphur-oxides and chlorides. The presence of these elements and their reaction
products may contribute significantly to corrosion and to environmentally harmful emissions.
Chlorine may be present in different organic and inorganic compounds and should exceed or equal the water
soluble amount that can be determined by CEN/TS 15105:2005.
Oxygen combustion in a closed oxygen bomb is the preferred method to digest biomass samples.
Decomposition in closed vessels is an appropriate alternative method. Other analytical techniques (e.g. high
temperature combustion in a tube furnace, Wickbold or Schöninger combustion, Eschka method) may also be
used. The determination of the resultant chlorine and sulphur 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 Clause 10.
A list with typical sulphur and chlorine contents of biofuels can be found in Annex C of CEN/TS 14961:2005.
1 Scope
This Technical Specification describes methods for the determination of the total sulphur and total chlorine
content in solid biofuels. The method describes a procedure for the digestion and different analytical
techniques for the quantification of the elements in the digestion solution.
The method is applicable for all biofuel samples containing more than 50 mg/kg of chlorine and/or sulphur.
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 references, the latest edition of the referenced
document (including any amendments) applies.
CEN/TS 14588:2003, Solid biofuels – Terminology, definitions and descriptions.
CEN/TS 14774-3, Solid Biofuels – Methods for the determination of moisture content – Oven dry method –
Part 3: Moisture in general analysis sample.
CEN/TS 14780, Solid biofuels – Methods for sample preparation.
CEN/TS 14918, Solid biofuels – Method for the determination of calorific value.
CEN/TS 15296, Solid biofuels – Calculation of analyses to different bases.
CEN/TS 15290, Solid biofuels – Determination of major elements.
EN ISO 10304-1, Water quality – Determination of dissolved fluoride, chloride, nitrite, orthophosphate,
bromide, nitrate and sulphate ions, using liquid chromatography of ions – Part 1: Method for water with low
contamination (ISO 10304-1:1992).
EN ISO 11885, Water quality – Determination of 33 elements by inductively coupled plasma atomic emission
spectroscopy (ISO 11885:1996).
ISO 587, Solid mineral fuels – Determination of chlorine using Eschka mixture
ASTM D516-02, Standard test method for sulphate ion in water.
DIN 38405-1, German standard methods for the examination of water, waste water and sludge; anions (group
D); determination of chloride ions.
DIN 51727, Testing of solid fuels – determination of chlorine content.
3 Terms and definitions
For the purposes of this Technical Specification, the terms and definitions given in CEN/TS 14588:2003 apply.
4 Principle
4.1 General
The determination of total sulphur and total chlorine content is performed in two steps (4.2 and 4.3) or by
using automatic equipment (4.4).
4.2 Digestion of the biofuel and transfer of acidic gaseous components into solution
Combustion in an oxygen bomb and absorption of the acidic gas components in an absorption solution
(method A);
Decomposition in closed vessels as described in CEN/TS 15290 (method B).
4.3 Determination of sulphate and chloride in the receiving solution
Ion chromatography applying the principles of EN ISO 10304-1;
ICP, applying the principles of EN ISO 11885 (determination as sulphur and chlorine);
Other suitable analytical methods.
NOTE A large number of applicable methods for the quantification of sulphate and chloride exists but detection limits
and precision vary significantly.
4.4 Automatic equipment
Automatic equipments may be used when the method is validated with biomass reference samples of an
adequate biomass type. If automatic equipment is used, sulphur and chlorine compounds may be detected as
gaseous components (e.g. by infrared methods). Examples for automatic analysers are e.g. elemental
analysers, AOX-analysers.
X-ray fluorescence may be used to determine sulphur and chlorine directly in the solid biofuel samples.
NOTE An equipment validated only with e.g. straw reference materials is not automatically suitable for the
determination of sulphur and chlorine in e.g. wood samples because of the usually significant lower concentrations of the
elements in wood and/or the unknown influences of the different matrix.
5 Reagents
The below listed reagents concern only the digestion method specified in 8.1.1 (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 General
All reagents shall be at least of analytical grade and suitable for their specific purpose. Particularly, they shall
contain negligible amounts of chlorine and sulphur, i.e. amounts that do not contribute significantly to the
determination.
5.2 Water
Deionised water will normally fulfil the requirements of 5.1.
5.3 Oxygen
Pure with an assay of at least 99,5 % (V/V)
5.4 Combustion aid/enhancer
Various substances may be used e.g. benzoic acid, paraffin oil, acetobutyratcapsules, polyethelene bags.
6 Apparatus
6.1 General
Analytical balance, with a resolution of at least 0,1 mg;
General laboratory equipment as volumetric flasks and measuring cylinders.
6.2 Method A
6.2.1 Pellet press, capable of applying a force of 0,1 MN equipped with a die to press a pellet with a
diameter of about 13 mm.
6.2.2 Combustion bomb, suitable for the determination of sulphur and chlorine. The combustion bomb
may be the same as used for the determination of the calorific value (see CEN/TS 14918).
The bomb shall not leak during the test and shall permit a quantitative recovery of the liquid. Its inner surface
may be made of stainless steel or any other material that will not be affected by the combustion process or
products.
Note that not all calorimeter bombs can be used because the principle of construction, the materials used for
construction, or the surfaces in the bombs, may adsorb or react with the acidic gases formed during
combustion or it may not be possible to clean the bomb completely.
6.3 Method B
Closed vessels for the decomposition, see CEN/TS 15290.
7 Preparation of the test sample
The test sample is the general analysis test sample with a nominal top size of 1 mm or less prepared in
accordance with CEN/TS 14780.
NOTE For some instrumental methods and/or solid biofuels it may be necessary to prepare a test sample with a
lower nominal top size than 1 mm (e.g. 0,25 mm) in order to keep the stated precision and repeatability limits.
As the results are to be calculated on “dry basis", the moisture content of the test sample shall be determined
concurrently by the method described in CEN/TS 14774-3, using another portion of the test sample.
8 Procedure
8.1 Digestion
8.1.1 Method A: Combustion in a closed bomb
Solid biofuel samples are usually tested in a pellet form due to the low density and their combustion behaviour.
Take a sample of approximately 1 g (unless the combustion bomb is designed for other sample amounts).
Press the sample with a suitable force to produce a compact unbreakable pellet that is weighed to 0,1 mg.
If the calorific value is determined simultaneously, the sample amount may eventually be adjusted
according to the specification in CEN/TS 14918.
Transfer the sample into a quartz glass or metal crucible.
The test may be carried out using a combustion aid:
a) Liquid combustion aid: after the mass of the sample pellet is determined, the auxiliary liquid material shall
be added dropwise on the pellet placed in the crucible (allowing the liquid to be adsorbed); the added
amount has to be determined exactly by weighing;
b) Solid combustion aid: the sample may be filled in powdered form into a combustion bag or capsule with
precisely known weight. The sample mass is calculated by weighing the sample in the combustion bag or
capsule and subtracting the mass of the combustion aid.
Add 1 ml water into the bomb as receiving solution (see also CEN/TS 14918 if the calorific value is
determined simultaneously). Alternatively, the water may be omitted or more water (up to 5 ml) may be
used. If the content of chlorine or sulphur exceeds 2 % (m/m) alkaline solutions may be used to neutralize
the acidic compounds produced. When ion chromatography is used for determination, the absorption
solution may be the mobile phase e.g. a carbonate/bicarbonate solution. In all cases, the calibration of the
method and the blank tests have to be done with the same amount and the same kind of receiving
solution.
Place
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