CEN/TS 15747:2008
(Main)Solid recovered fuels - 14C-based methods for the determination of the biomass content
Solid recovered fuels - 14C-based methods for the determination of the biomass content
This Technical Specification specifies the test methods for the determination of the biomass carbon content in solid recovered fuels based on the 14C content. The biomass fraction by weight and by energy are calculated from the biomass carbon content.
Feste Sekundärbrennstoffe - 14C-Verfahren zur Bestimmung des Gehaltes an Biomasse
Diese Technische Spezifikation legt die Prüfverfahren zur Bestimmung des Kohlenstoffgehaltes von Biomasse
in festen Sekundärbrennstoffen auf der Grundlage des 14C-Gehaltes fest. Der Massenanteil an Biomasse und
der Biomasse-Energieanteil werden aus dem Massenanteil an Kohlenstoff der Biomasse berechnet.
Combustibles solides de récupération - Méthodes basées sur le 14C pour la détermination de la teneur en biomasse
Trdno alternativno gorivo - Metode za določevanje vsebnosti biomase na osnovi izotopa ogljika 14C
General Information
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Standards Content (Sample)
SLOVENSKI STANDARD
01-januar-2009
7UGQRDOWHUQDWLYQRJRULYR0HWRGH]DGRORþHYDQMHYVHEQRVWLELRPDVHQDRVQRYL
L]RWRSDRJOMLND&
Solid recovered fuels - 14C-based methods for the determination of the biomass content
Feste Sekundärbrennstoffe - 14C-Verfahren zur Bestimmung des Gehaltes an Biomasse
Combustibles solides de récupération - Méthodes basées sur le 14C pour la
détermination de la teneur en biomasse
Ta slovenski standard je istoveten z: CEN/TS 15747:2008
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 15747
SPÉCIFICATION TECHNIQUE
TECHNISCHE SPEZIFIKATION
October 2008
ICS 75.160.10
English Version
Solid recovered fuels - C-based methods for the determination
of the biomass content
Combustibles solides de récupération - Méthodes basées Feste Sekundärbrennstoffe - C-Verfahren zur
sur le C pour la détermination de la teneur en biomasse Bestimmung des Gehaltes an Biomasse
This Technical Specification (CEN/TS) was approved by CEN on 11 May 2008 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, Bulgaria, 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
© 2008 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TS 15747:2008: 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 Symbols and abbreviations .5
5 Equipment and reagents.6
6 Principle.7
7 Procedure .7
8 Measurements.8
9 Calculation.9
10 Test report .11
Annex A (normative) C Determination by Proportional Scintillation-counter Method (PSM).12
Annex B (normative) C Determination by Beta-ionisation (BI) .16
Annex C (normative) C Determination by Accelerator Mass Spectrometry (AMS) .20
Annex D (informative) Exclusions, mentioned in CEN/TS 15440, which can be resolved using the
C method.25
Bibliography .26
Foreword
This document (CEN/TS 15747:2008) has been prepared by Technical Committee CEN/TC 343 “Solid
Recovered Fuels”, the secretariat of which is held by SFS.
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.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to announce this 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, Slovakia, Slovenia, Spain, Sweden, Switzerland
and the United Kingdom.
Introduction
The determination of the biomass carbon content using the C method is based on the well established
analytical procedures that are used for the determination of the age of carbon containing objects. It can be
used for normal sample types, sample types that cannot be analysed accurately with the methods described
in CEN/TS 15440 (1) (see Annex D), samples with a biomass carbon content below 5%, and for reference
measurements.
For the determination of the biomass carbon content based on the C method a general sample preparation
and the three common used methods for the determination of the C content are described. With this modular
approach it will be possible for normally equipped laboratories to prepare samples for the C content, and to
14 14
determine the C content with their own equipment or to outsource the determination of the C content to
laboratories that specialize in this matter.
For the collection from the sample of the C content, generally accepted methods for the conversion of the
carbon present in the sample to CO are described. For the measurement of the C content, methods are
selected that are already generally accepted as methods for the determination of the age of objects.
1 Scope
This Technical Specification specifies the test methods for the determination of the biomass carbon content in
solid recovered fuels based on the C content. The biomass fraction by weight and by energy are calculated
from the biomass carbon content.
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 15400, Solid recovered fuels — Methods for the determination of calorific value
CEN/TS 15413, Solid recovered fuels — Methods for the preparation of the test sample from the laboratory
sample
CEN/TS 15442, Solid recovered fuels — Methods for sampling
CEN/TS 15443, Solid recovered fuels — Methods for laboratory sample preparation
3 Terms and definitions
For the purposes of this document, the following terms and definitions apply.
3.1
biogenic carbon
mass fraction of total carbon that was produced in natural processes by living organisms but not fossilized or
derived from fossil resources
3.2
biomass carbon
equivalent to biogenic carbon
3.3
biomass content
mass fraction of biomass material present in the sample
3.4
isotope abundance
fraction of atoms of a particular isotope of an element
3.5
percentage modern Carbon (pmC)
percent modern carbon relative to the NIST Oxalic acid standard reference material SRM4990B. The
internationally accepted radiocarbon dating reference value is 95 percent of the activity, in AD 1950, of this
NBS oxalic acid SRM4990B. In 2006 the value of 100% biogenic carbon was set at 107 pmC.
4 Symbols and abbreviations
C Carbon isotope with an atomic mass of 14
AMS Accelerator Mass Spectrometry
β Beta particle, electron emitted during radioactive decay
BI Βeta Ionisation
Bq Bequerel, desintegrations per second
daf dry ash free
DPM Disintegrations per minute
CPM Counts per minute
GM Geiger Müller
LLD Lower Limit of Detection
MOP 3-Methoxy 1-propyl amine
LSC Liquid Scintillation Counter or Liquid Scintillation Counting
REF Reference value of 100% biogenic carbon
PSM Proportional Scintillation-counter Method
pmC percentage modern Carbon, carbon mass fraction from biogenic origin
RSD Relative Standard Deviation
SRF Solid Recovered Fuel
UHV Upper Heating Value
5 Equipment and reagents
Carbamate solution (e.g. Carbasorb® E)
Scintillation cocktail (e.g. Permafluor® E+)
Glass bottle (standard glass sample bottles with plastic screw caps that are resistant to 4M NaOH)
4 M NaOH absorption liquid
For the preparation of a carbonate free absorption liquid, preparation using freshly opened NaOH pellet
containers is sufficient. Dissolve the NaOH pellets in a small amount of water (the heat produced during the
dissolution process will enhance the dissolution process. Small amounts of precipitation are an indication of
the presence of Na CO . By decanting the clear phase the almost carbonate free solution can be diluted to the
2 3
desired volume. As the dissolution of NaOH is an exothermic process extra care should be taken as boiling of
the concentrated solution during dilution can occur.
For high precision measurements the following procedure can be used to produce a carbonate free NaOH
solution.
6700 ml demineralised water
1120 g NaOH pellets
300 ml saturated Ba(OH) solution. (± 25 g Ba(OH) in 300 ml demineralised water)
2 2
Dissolve the NaOH pellets in the demineralised water (use magnetic stirrer)
Heat the solution and the saturated Ba(OH) solution to 80 °C, and mix the two solutions. Cool down
the solution to -8 °C, stop the stirring and leave the solution overnight at -8 °C. After filtration the
solution is ready for use. Keep stored in a well-sealed container.
A list of equipment and reagents necessary for conversion and for the different measurements is presented in
the Annexes.
6 Principle
The methods for the determination of the biomass carbon content specified in this Technical Specification are
based on the determination of the C content. The amount of biomass carbon in solid recovered fuel is
proportional to this C content.
Complete combustion is carried out in a way to comply with the requirements of the subsequent measurement
of the C content. This measurement is carried out according to one of the three methods, Proportional
Scintillation Method (PSM), Beta Ionisation (BI) or Accelerated Mass Spectrometry (AMS). These methods are
considered equivalent, giving the same results within the scope of this Technical Specification. The results are
expressed as the percentage biomass carbon in the total carbon content. The fraction of biomass content by
weight and the fraction of biomass by energy content are calculated from the biomass carbon content, using
the biomass carbon content and the energy content of the biomass fraction that is present in the sample.
7 Procedure
7.1 Sampling
Sampling, transport, storage of the solid recovered fuel shall be conducted according CEN/TS 15442 and
CEN/TS 15443. Preparation of the test sample shall be conducted according to CEN/TS 15413.
7.2 Conversion of the carbon present in the sample to a suitable sample for C
determination
For the conversion of the sample to a form that can be used for the determination of the C content, three
methods are allowed: combustion in a calorimetric bomb (see 7.3), combustion in a tube furnace (see 7.5) and
combustion in a laboratory scale combustion apparatus (see 7.6). The carbon dioxide formed is then
absorbed in a suitable solution, which depends on the combustion method and the selected method for the
subsequent C measurement. For the PSM detection method two absorption solutions are possible. However
when substantial chemical or optical quenching is foreseen (high NO values, formation of coloured
x
substances) collection of the CO shall be done in the NaOH solution. The use of pure oxygen or a mix of
oxygen and argon during combustion will reduce the formation of nitrous oxides to an acceptable level.
7.3 Combustion of the sample in a calorimetric bomb
For the determination of the calorific value of the sample, CEN/TS 15400 shall be used. After the complete
combustion in the oxygen bomb the combustion gases are collected in a gas bag as described in 7.4. For the
determination of the C content by PSM the carbon dioxide shall be collected in a cooled mixture of
carbamate solution and a suitable scintillation liquid. For the determination of the C content by AMS or BI the
carbon dioxide shall be collected in a 4 M NaOH solution. For AMS, alternatively ca. 2 ml of the CO gas can
be taken from the bag using a glass syringe and the gas can be transferred to the AMS target preparations
system. A
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