SIST-TP CEN/TR 17345:2019
(Main)Waste - State-of-the-art document - Halogens and sulfur by oxidative pyrohydrolytic combustion followed by ion chromatography detection
Waste - State-of-the-art document - Halogens and sulfur by oxidative pyrohydrolytic combustion followed by ion chromatography detection
This technical report provides a supplementary description of the oxidative pyrohydrolytic combustion technique followed by ion chromatography detection for the determination of halogens and sulfur in waste samples.
Abfall - Dokument zum Stand der Technik - Bestimmung von Halogenen und Schwefel mittels oxidativer pyro-hydrolytischer Verbrennung mit Ionenchromatographie Detektion
Caractérisation des déchets - État de l’art - Halogènes et soufre par combustion pyrohydrolytique oxydative suivie d’une détection par chromatographie ionique
Dans le cadre de la Directive UE 99/31/CE [1] et de la Directive UE 2000/76/CE [2], les halogènes et le soufre doivent être dosés dans des échantillons de déchets. La mise en oeuvre de la technique associant combustion et chromatographie ionique (IC) permet de réaliser en un seul cycle la combustion de l’échantillon puis le dosage des halogènes et du soufre par chromatographie ionique. De plus, cet instrument peut être équipé d’un carrousel pour échantillons solides et liquides permettant d’automatiser ce type d’analyses.
Les récents développements de la technique C-IC l’ont rendue intéressante pour le dosage des halogènes et du soufre dans des échantillons de déchets. Un document sur les progrès actuels de la technique C-IC a donc été élaboré ; il contient l’évaluation des performances de différents systèmes disponibles dans le commerce et la présentation des résultats d’analyse obtenus sur des matériaux de référence certifiés et des échantillons de déchets.
Odpadki - Dokument o stanju tehnike - Določevanje halogenov in žvepla z ionsko kromatografijo po pirohidrolitskem sežigu
To tehnično poročilo zagotavlja dodaten opis tehnike pirohidrolitskega sežiga, ki mu sledi ionska kromatografija za določevanje halogenov in žvepla v vzorcih odpadkov.
General Information
Standards Content (Sample)
SLOVENSKI STANDARD
SIST-TP CEN/TR 17345:2019
01-julij-2019
Odpadki - Dokument o stanju tehnike - Določevanje halogenov in žvepla z ionsko
kromatografijo po pirohidrolitskem sežigu
Waste - State-of-the-art document - Halogens and sulfur by oxidative pyrohydrolytic
combustion followed by ion chromatography detection
Abfall - Dokument zum Stand der Technik - Bestimmung von Halogenen und Schwefel
mittels oxidativer pyro-hydrolytischer Verbrennung mit Ionenchromatographie Detektion
Caractérisation des déchets - État de l’art - Halogènes et soufre par combustion
pyrohydrolytique oxydative suivie d’une détection par chromatographie ionique
Ta slovenski standard je istoveten z: CEN/TR 17345:2019
ICS:
13.030.01 Odpadki na splošno Wastes in general
71.040.50 Fizikalnokemijske analitske Physicochemical methods of
metode analysis
SIST-TP CEN/TR 17345:2019 en
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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SIST-TP CEN/TR 17345:2019
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SIST-TP CEN/TR 17345:2019
CEN/TR 17345
TECHNICAL REPORT
RAPPORT TECHNIQUE
February 2019
TECHNISCHER BERICHT
ICS 13.030.40
English Version
Waste - State-of-the-art document - Halogens and sulfur by
oxidative pyrohydrolytic combustion followed by ion
chromatography detection
Caractérisation des déchets - État de l'art - Halogènes Abfall - Dokument zum Stand der Technik -
et soufre par combustion pyrohydrolytique oxydative Bestimmung von Halogenen und Schwefel mittels
suivie d'une détection par chromatographie ionique oxidativer pyro-hydrolytischer Verbrennung mit
Ionenchromatographie Detektion
This Technical Report was approved by CEN on 4 February 2019. It has been drawn up by the Technical Committee CEN/TC 444.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2019 CEN All rights of exploitation in any form and by any means reserved Ref. No. CEN/TR 17345:2019 E
worldwide for CEN national Members.
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CEN/TR 17345:2019 (E)
Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative references . 5
3 Terms and definitions . 5
4 Description of the combustion-IC technique . 5
4.1 Principle . 5
4.2 Configuration of the system . 6
4.2.1 Sample introduction . 6
4.2.2 Combustion system . 6
4.2.3 Gas absorption unit . 6
4.2.4 Ion chromatography system . 6
5 Available standard methods . 7
6 Evaluation study of the C-IC technique . 8
6.1 General . 8
6.2 Description of the samples . 8
6.3 Description of the applied C-IC systems . 9
6.4 Results for certified reference materials (CRM) . 10
6.5 Results of the waste samples . 15
7 Conclusions . 22
Bibliography . 24
2
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CEN/TR 17345:2019 (E)
European foreword
This document (CEN/TR 17345:2019) has been prepared by Technical Committee CEN/TC 444 “Test
methods for environmental characterization of solid matrices”, the secretariat of which is held by NEN.
Attention is drawn to the possibility that some of the elements of this document may be the subject of
patent rights. CEN shall not be held responsible for identifying any or all such patent rights.
3
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CEN/TR 17345:2019 (E)
Introduction
The content of sulfur, chlorine, fluorine and/or bromine has to be determined in various waste streams
such as refuse derived fuel, rubber granulates, post-shredder residue and plastics from wastes of
electrical and electronic equipment (WEEE).
At the moment the determination of these elements is performed according to EN 14582. This
European standard specifies a combustion method for the determination of halogen and sulfur contents
in materials by combustion in a closed system containing oxygen (calorimetric bomb), and the
subsequent analysis of the combustion product using different analytical techniques. Because the
combustion has to be conducted for each sample separately and no automation is possible, this method
is time-consuming and labour- intensive compared to combustion ion chromatography (C-IC).
The use of the combustion ion chromatography (C-IC) instrument would allow in one single run the
combustion of the material and the simultaneous determination of fluorine, chlorine, bromine, and
sulfur by ion chromatography. Moreover, the combustion module enables the sample digestion of
different type of samples under pyrolysis and oxidation conditions. The instrument may also be
equipped with automatic sample introduction modules for solids and liquids, which will benefit the
automation and reduce significantly the labour-intensive process. The system is already offered
commercially by different manufacturers.
Many laboratories are using none coupled customized hydropyrolysis systems for different kind of
applications. Offline systems can be used as sample preparation systems for IC measurement, too.
Coupling is no requirement for using the C-IC technique.
This document provides a technical description of the C-IC technique, an overview of available
commercial instruments, the strengths and limitations of this technique, and analytical results for
halogens and sulfur obtained on waste samples.
4
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CEN/TR 17345:2019 (E)
1 Scope
In the framework of EU Directive 99/31/EC [1] and EU Directive 2000/76/EC [2] halogens and sulfur
need to be determined on waste samples. The implementation of the combustion-IC technique would
allow in one single run the combustion of the sample followed by the determination of the halogens and
sulfur with ion chromatography. Moreover, this instrument may be provided with a sample carrousel
for both solids and liquids, allowing an automation of these type of analyses.
Recent developments of the C-IC technology have made this technique interesting for the determination
of halogens and sulfur in waste samples. Therefore, a document on the current progress of the C-IC
technology was prepared, including the evaluation of the performance of different commercially
available systems and the presentation of analytical results obtained on certified reference materials
and waste samples.
2 Normative references
There are no normative references in this document.
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
4 Description of the combustion-IC technique
4.1 Principle
Samples are introduced in the combustion tube using an automatic boat control device. First samples
are thermally combusted under argon atmosphere, followed by a combustion at 800 °C to 1 100 °C with
oxygen under pyrohydrolytic conditions. Sulfur in the samples converts to SO and halogens to
x
hydrogen halide. These volatile compounds are trapped in an aqueous absorbing solution and
subsequently injected for ion chromatographic analysis. The basic equipment configuration is shown in
Figure 1.
Figure 1 — Basic configuration of a C-IC system
5
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4.2 Configuration of the system
4.2.1 Sample introduction
All the systems have the ability to measure both solids and liquids. Automation is available for boat
trays as well as liquids in vials. Solid analysis is performed by weighing the sample into a sample boat.
Alternative to sampling liquids from vials, they can also be injected into sample boats placed on the boat
tray. In this case there should be no volatile compounds present due to possible losses by evaporation.
The intake will depend on the sample type, density and concentration. Upper limits are approximately
100 mg for solids and 100 µl for liquids. The sample shall be homogeneous with respect to sample
amount.
4.2.2 Combustion system
The furnace is provided with a quartz or ceramic pyrolysis tube. Alkali metals such as sodium, calcium
and magnesium have a tendency to react with SiO . Same effect can be seen when measuring silicium
2
bearing samples. The reactions cause devitrification of the quartz pyrolysis tube, which will result in
cracking of the tube. This can be overcome by working with a ceramic tube. Using a combustion
improver (e.g. WO , Fe O ), which binds with calcium and magnesium [4] will increase lifetime of glass
4 3 4
parts. Analogously the sample boat consists of quartz or ceramic material.
To achieve complete combustion of the sample and full recovery of analytes, choosing suitable
combustion temperatures, timings of boat movement, addition of water to the combustion gases
(hydropoyrolysis) and possibly addition of combustion improver is required. Special attention is
needed if organic matrices are analysed to prevent soot formation.
Combustion process
The sample boat is introduced under inert gas atmosphere. Samples are pyrolysed following the
temperature gradient at the inlet of the furnace. To prevent soot formation, this pyrolysis shall be
controlled by suitable means to ensure complete transformation of organic matter to CO . After
2
complete pyrolysis, the inner tube is flushed with oxygen to mobilize remaining analytes.
Hydropyrolysis
To ensure complete mobilization of fluorine during pyrolysis, addition of water to the inert gas is
required. The amount added depends on sample type and analyte concentrations.
4.2.3 Gas absorption unit
The combustion gases are fed into an absorption vessel and passed through an aqueous absorption
solution. Hydrogen halides absorbed as halide anions, SOx is converted to sulfite and sulfate. To unify
analytes for quantification, H O (or a suitable oxidant) is added to the absorption solution to oxidize all
2 2
species to SO . H O also acts as reducing agent if halogens, especially bromine, are combusted to
4 2 2
halogen gas (Br ).
2
The absorption unit is equipped with measures to quantify total absorption solution volume after
combustion, accounting for water addition by hydropyrolysis. Such measures can be automatic or
manual adjustment to a known volume, calculation of volume changes or addition of an internal
standard.
Sample transfer and loading to ion chromatography sample loop can be fully automatic or manual.
4.2.4 Ion chromatography system
The ion chromatography system uses chromatographic columns based on ion exchange materials to
achieve separation of anionic analytes. To achieve good signal to noise ratio, peak separation and peak
resolution, different setups may be used.
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Elution from the column may be performed by isocratic or gradient elution. As H O is creating an
2 2
interference with fluoride detection, additional measures are necessary if very low contents of fluorine
are analysed. Suitable measures may be gradient elution to achieve better separation or physical
separation of H O by a matrix elimination/preconcentration column.
2 2
5 Available standard methods
A range of standard methods are available describing the determination of halogens and sulfur in a
variety of matrices. In Table 1 a non-limited list is given of relevant standard methods containing a
particular section on C-IC. For each standard method information on the analysed matrix, the element
determined and the measuring range, if available, is presented. Table 2 shows a non-limited list of
relevant standard methods allowing analysis by C-IC without a particular section on this technique.
Table 1 — Non-limited list of standard methods containing a particular section on C-IC
Elements and measuring range
Standard method Matrix mg/kg Ref.
Fluorine Chlorine Bromine Sulfur
EN 62321-3-2 Polymers and electronics - - 96 to 976 - 11
ASTM D 7359–14 Aromatics hydrocarbons 0,1 to 10 0,1 −10 - 0,1 −10 12
ASTM D 7994–17 Liquified petroleum gases 1 to 300 5 to 300 - 1 - 300 13
ASTM D 8150 Crude oil (naphta fraction) - 1 to 50 - - 14
ASTM UOP 991-13 Liquid organics 0,1 to 100 0,1 to 100 0.2 to 100 - 15
ASTM UOP 1001-14 Liquified petroleum gases 1 to 1 500 1 to 1 500 - - 16
JIS K 7392 Waste plastic - - 100 to 20 000 - 17
Halogen free soldering
JEITA ET-7304A < 1 000 < 1 000 < 1 000 - 18
material
KS M01080-2009 Electronic equipment X X X - 19
Table 2 — Non-limited list of standard methods allowing analysis by C-IC without a particular
section on C-IC
Elements and measuring range
Standard method Matrix mg/kg Ref.
Fluorine Chlorine Bromine Sulfur
60 to 90 to
EN ISO 16994 Solid biofuels - - 20
2 000 1 200
ISO 11724 Coal, cole and fly ash X - - - 21
7
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Elements and measuring range
Standard method Matrix mg/kg Ref.
Fluorine Chlorine Bromine Sulfur
ISO 17947 Nitride X X X X 22
ASTM D 5987–07 Coal and coke 20 to 500 - - - 23
DIN 51723 Solid fuels X - - - 24
DIN 51724 Coal and coke - - - X 25
JIS R 1616 Silicon carbide X - - - 26
JIS R 9301–3-11 Alumina powder X - - - 27
JIS Z 7302–6/7 Refuse derived fuel - X - X 28
6 Evaluation study of the C-IC technique
6.1 General
A study was conducted by the Flemish Institute for Technological Research (VITO, Flanders, Belgium) in
commission of the Public Waste Agency of Flanders (OVAM, Belgium) to evaluate the C-IC technique for
the determination of halogens and sulfur in waste samples [3]. The main results of this study are
incorporated in this document.
The evaluation of the C-IC technique was performed by conducting comparative tests on C-IC systems
from 2 suppliers (Mitsubishi Chemical, Japan in combination with ion chromatography from Thermo
Fisher Scientific, USA and Metrohm, Belgium). These two different C-IC units were used to analyse
about 9 certified reference materials, as well as 10 waste samples. The analyses on the Mitsubishi
system were performed by Mitsubishi itself, while the analyses on the Metrohm C-IC system were
performed by VITO in the application laboratory of Metrohm in Antwerp, Belgium.
6.2 Description of the samples
For this study, the reference samples considered were oil, clay, coal, fly ash, polymer, phosphate rock.
Table 3 lists the certified values for these reference materials.
Table 3 — Overview certified values of the reference materials
Identification Matrix x x x x
ass ass ass ass
Fluorine Chlorine Bromine Sulfur
mg/kg mg/kg mg/kg mg/kg
AOD 1.11 Oil - 9 500 ±50 - 6 500 ±40
AOD 1.12 Oil 4 300 ±40 - 9 500 ±50 -
BCR 461 Clay 568 ±10 119 ±25 - -
BCR 460 Coal 225 59 - -
BCR 182 Coal - 3 700 ±70 36,5 -
8
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CEN/TR 17345:2019 (E)
Identification Matrix x x x x
ass ass ass ass
Fluorine Chlorine Bromine Sulfur
mg/kg mg/kg mg/kg mg/kg
BCR 038 Fly ash 538 ±13 323 ±22 - -
N1633b Fly ash - - 2,9 2 075 ±11
BCR 681 Polymer - 93 ±2,8 98 ±2,8 78 ±17
BCR 032 PO rock 40 400 ±600 - - 7 360 ±320
4
Where
x is the assigned value
ass
italic: indicative values
In consultation with OVAM, a number of waste samples were selected for analysis with C-IC as
presented in Table 4. All waste samples were dried at 105 °C and fine grinded down to < 0,5 mm using
an universal cutting mill.
Table 4 — Overview of analysed waste samples
Sample number Type of sample
CIC1 Fine shredder
CIC2 SRF fraction(industrial waste)
CIC3 SRF fraction (household waste)
CIC4 Sewage sludge
CIC5 Post shredder residue (electrical equipment)-SRF
CIC6 Post shredder residue (electrical equipment)
CIC7 Post shredder residue (electrical equipment)-fluff
shredder
CIC8 Rubber granulates
CIC9 Plastics from WEEE (containing bromine)
CIC10 Rubber fraction
6.3 Description of the applied C-IC systems
The C-IC unit 1 (C-IC 1) is a double furnace system which was equipped with a ceramic pyrolysis tube
and ceramic boats. Furnace 1 was set at 900 °C and furnace 2 at 1 000 °C for organic samples and at
1 100 °C for both furnaces for inorganic samples and mixtures. The samples were pyrolysed under
humidified inert atmosphere and combusted in oxidising atmosphere. The resultant vapors were
absorbed in an aqueous solution (H O added), gas lines were washed, the absorption volume adjusted
2 2
to a defined volume by liquid level sensor and afterwards injected directly into the IC system for
2-
analysis. H O was added into the absorbing solution to oxidize SO to form SO .
2 2 2 4
In some cases, especially for the determination of sulfur, a combustion improver (WO ) was added. The
3
IC measurements were conducted using a separation column at 35 °C and 2,7 mM Na CO and
2 3
0,3 mM NaHCO as eluent with a flow rate of 1 ml/min. The ion chromatograph was calibrated for
3
fluorine, chlorine and sulfate (for this study the element bromine was not calibrated, although it is
feasible). There was no need for usage of a pre-concentration column or variable injection volumes for
the IC.
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The C-IC unit 2 (C-IC 2) consists of a combustion module including a flame sensor to control the speed
at which the boat sample holder is introduced into the furnace. Quartz boat sample holders and a quartz
pyrolysis tube were used for the measurements. The combustion takes place at 1 100 °C. Argon gas
(100 ml/min) is initially supplied to prevent excessive combustion. Afterwards O gas is supplied to
2
achieve complete post- combustion (no more soot present). In the incinerator the sample is incinerated
for 600 s. The resultant vapors are absorbed in an aqueous solution, and introduced directly into the IC
system for analysis. Some experiments were conducted using a pre-concentration column to remove
the excess of H O required for the oxidation of all the sulfur compounds to SO . The ion chromatograph
2 2 4
has a separation column at 30 °C. As eluent 3,2 mmol/l Na CO , 1,0 mmol/l NaHCO was used with a
2 3 3
flow rate of 0,7 ml/min. The ion chromatograph was calibrated for fluorine, chlorine, bromine and
sulfate, where fo
...
SLOVENSKI STANDARD
kSIST-TP FprCEN/TR 17345:2018
01-november-2018
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Waste - State-of-the-art document - Halogens and sulfur by oxidative pyrohydrolytic
combustion followed by ion chromatography detection
Abfall - Dokument zum Stand der Technik - Bestimmung von Halogenen und Schwefel
mittels oxidativer pyro-hydrolytischer Verbrennung mit Ionenchromatographie Detektion
Caractérisation des déchets - État de l’art - Halogènes et soufre par combustion
pyrohydrolytique oxydative suivie d’une détection par chromatographie ionique
Ta slovenski standard je istoveten z: FprCEN/TR 17345
ICS:
13.030.01 Odpadki na splošno Wastes in general
kSIST-TP FprCEN/TR 17345:2018 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.
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kSIST-TP FprCEN/TR 17345:2018
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kSIST-TP FprCEN/TR 17345:2018
FINAL DRAFT
TECHNICAL REPORT
FprCEN/TR 17345
RAPPORT TECHNIQUE
TECHNISCHER BERICHT
October 2018
ICS
English Version
Waste - State-of-the-art document - Halogens and sulfur by
oxidative pyrohydrolytic combustion followed by ion
chromatography detection
Abfall - Dokument zum Stand der Technik -
Bestimmung von Halogenen und Schwefel mittels
oxidativer pyro-hydrolytischer Verbrennung mit
Ionenchromatographie Detektion
This draft Technical Report is submitted to CEN members for Vote. It has been drawn up by the Technical Committee CEN/TC
444.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia,
Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania,
Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Serbia, Slovakia, Slovenia, Spain, Sweden, Switzerland,
Turkey and United Kingdom.
Recipients of this draft are invited to submit, with their comments, notification of any relevant patent rights of which they are
aware and to provide supporting documentation.
Warning : This document is not a Technical Report. It is distributed for review and comments. It is subject to change without
notice and shall not be referred to as a Technical Report.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
CEN-CENELEC Management Centre: Rue de la Science 23, B-1040 Brussels
© 2018 CEN All rights of exploitation in any form and by any means reserved Ref. No. FprCEN/TR 17345:2018 E
worldwide for CEN national Members.
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kSIST-TP FprCEN/TR 17345:2018
FprCEN/TR 17345:2018 (E)
Contents Page
European foreword . 3
Introduction . 4
1 Scope . 5
2 Normative References . 5
3 Terms and definitions . 5
4 Description of the combustion-IC technique . 5
4.1 Principle . 5
4.2 Configuration of the system . 6
4.2.1 Sample introduction . 6
4.2.2 Combustion system . 6
4.2.3 Gas absorption unit . 6
4.2.4 Ion chromatography system . 6
5 Available standard methods . 7
6 Evaluation study of the C-IC technique . 8
6.1 General . 8
6.2 Description of the samples . 8
6.3 Description of the applied C-IC systems . 9
6.4 Results for certified reference materials (CRM) . 10
6.5 Results of the waste samples . 15
7 Conclusions . 22
Bibliography . 24
2
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kSIST-TP FprCEN/TR 17345:2018
FprCEN/TR 17345:2018 (E)
European foreword
This document (FprCEN/TR 17345:2018) has been prepared by Technical Committee CEN/TC 444
“Test methods for environmental characterization of solid matrices”, the secretariat of which is held by
NEN.
This document is currently submitted to the Vote on TR.
3
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kSIST-TP FprCEN/TR 17345:2018
FprCEN/TR 17345:2018 (E)
Introduction
The content of sulfur, chlorine, fluorine and/or bromine has to be determined in various waste streams
such as refuse derived fuel, rubber granulates, post-shredder residue and plastics from wastes of
electrical and electronic equipment (WEEE).
At the moment the determination of these elements is performed according to EN 14582. This
European standard specifies a combustion method for the determination of halogen and sulfur contents
in materials by combustion in a closed system containing oxygen (calorimetric bomb), and the
subsequent analysis of the combustion product using different analytical techniques. Because the
combustion has to be conducted for each sample separately and no automation is possible, this method
is time-consuming and labour- intensive compared to combustion ion chromatography (C-IC).
The use of the combustion ion chromatography (C-IC) instrument would allow in one single run the
combustion of the material and the simultaneous determination of fluorine, chlorine, bromine, and
sulfur by ion chromatography. Moreover, the combustion module enables the sample digestion of
different type of samples under pyrolysis and oxidation conditions. The instrument may also be
equipped with automatic sample introduction modules for solids and liquids, which will benefit the
automation and reduce significantly the labour-intensive process. The system is already offered
commercially by different manufacturers.
Many laboratories are using none coupled customized hydropyrolysis systems for different kind of
applications. Offline systems can be used as sample preparation systems for IC measurement, too.
Coupling is no requirement for using the C-IC technique.
This document provides a technical description of the C-IC technique, an overview of available
commercial instruments, the strengths and limitations of this technique, and analytical results for
halogens and sulfur obtained on waste samples.
4
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kSIST-TP FprCEN/TR 17345:2018
FprCEN/TR 17345:2018 (E)
1 Scope
In the framework of EU Directive 99/31/EC [1] and EU Directive 2000/76/EC [2] halogens and sulfur
need to be determined on waste samples. The implementation of the combustion-IC technique would
allow in one single run the combustion of the sample followed by the determination of the halogens and
sulfur with ion chromatography. Moreover, this instrument may be provided with a sample carrousel
for both solids and liquids, allowing an automation of these type of analyses.
Recent developments of the C-IC technology have made this technique interesting for the determination
of halogens and sulfur in waste samples. Therefore, a document on the current progress of the C-IC
technology was prepared, including the evaluation of the performance of different commercially
available systems and the presentation of analytical results obtained on certified reference materials
and waste samples.
2 Normative References
There are no normative references in this document.
3 Terms and definitions
No terms and definitions are listed in this document.
ISO and IEC maintain terminological databases for use in standardization at the following addresses:
• IEC Electropedia: available at http://www.electropedia.org/
• ISO Online browsing platform: available at http://www.iso.org/obp
4 Description of the combustion-IC technique
4.1 Principle
Samples are introduced in the combustion tube using an automatic boat control device. First samples
are thermally combusted under argon atmosphere, followed by a combustion at 800 °C to 1 100 °C with
oxygen under pyrohydrolytic conditions. Sulfur in the samples converts to SO and halogens to
x
hydrogen halide. These volatile compounds are trapped in an aqueous absorbing solution and
subsequently injected for ion chromatographic analysis. The basic equipment configuration is shown in
Figure 1.
Figure 1 — Basic configuration of a C-IC system
5
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FprCEN/TR 17345:2018 (E)
4.2 Configuration of the system
4.2.1 Sample introduction
All the systems have the ability to measure both solids and liquids. Automation is available for boat
trays as well as liquids in vials. Solid analysis is performed by weighing the sample into a sample boat.
Alternative to sampling liquids from vials, they can also be injected into sample boats placed on the boat
tray. In this case there should be no volatile compounds present due to possible losses by evaporation.
The intake will depend on the sample type, density and concentration. Upper limits are approximately
100 mg for solids and 100 µl for liquids. The sample shall be homogeneous with respect to sample
amount.
4.2.2 Combustion system
The furnace is provided with a quartz or ceramic pyrolysis tube. Alkali metals such as sodium, calcium
and magnesium have a tendency to react with SiO . Same effect can be seen when measuring silicium
2
bearing samples. The reactions cause devitrification of the quartz pyrolysis tube, which will result in
cracking of the tube. This can be overcome by working with a ceramic tube. Using a combustion
improver (e.g. WO , Fe O ), which binds with calcium and magnesium [4] will increase lifetime of glass
4 3 4
parts. Analogously the sample boat consists of quartz or ceramic material.
To achieve complete combustion of the sample and full recovery of analytes, choosing suitable
combustion temperatures, timings of boat movement, addition of water to the combustion gases
(hydropoyrolysis) and possibly addition of combustion improver is required. Special attention is
needed if organic matrices are analysed to prevent soot formation.
Combustion process
The sample boat is introduced under inert gas atmosphere. Samples are pyrolysed following the
temperature gradient at the inlet of the furnace. To prevent soot formation, this pyrolysis shall be
controlled by suitable means to ensure complete transformation of organic matter to CO . After
2
complete pyrolysis, the inner tube is flushed with oxygen to mobilize remaining analytes.
Hydropyrolysis
To ensure complete mobilization of fluorine during pyrolysis, addition of water to the inert gas is
required. The amount added depends on sample type and analyte concentrations.
4.2.3 Gas absorption unit
The combustion gases are fed into an absorption vessel and passed through an aqueous absorption
solution. Hydrogen halides absorbed as halide anions, SOx is converted to sulfite and sulfate. To unify
analytes for quantification, H O (or a suitable oxidant) is added to the absorption solution to oxidize all
2 2
species to SO . H O also acts as reducing agent if halogens, especially bromine, are combusted to
4 2 2
halogen gas (Br ).
2
The absorption unit is equipped with measures to quantify total absorption solution volume after
combustion, accounting for water addition by hydropyrolysis. Such measures can be automatic or
manual adjustment to a known volume, calculation of volume changes or addition of an internal
standard.
Sample transfer and loading to ion chromatography sample loop can be fully automatic or manual.
4.2.4 Ion chromatography system
The ion chromatography system uses chromatographic columns based on ion exchange materials to
achieve separation of anionic analytes. To achieve good signal to noise ratio, peak separation and peak
resolution, different setups may be used.
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Elution from the column may be performed by isocratic or gradient elution. As H O is creating an
2 2
interference with fluoride detection, additional measures are necessary if very low contents of fluorine
are analysed. Suitable measures may be gradient elution to achieve better separation or physical
separation of H O by a matrix elimination/preconcentration column.
2 2
5 Available standard methods
A range of standard methods are available describing the determination of halogens and sulfur in a
variety of matrices. In Table 1 a non-limited list is given of relevant standard methods containing a
particular section on C-IC. For each standard method information on the analysed matrix, the element
determined and the measuring range, if available, is presented. Table 2 shows a non-limited list of
relevant standard methods allowing analysis by C-IC without a particular section on this technique.
Table 1 — Non-limited list of standard methods containing a particular section on C-IC
Elements and measuring range
Standard method Matrix mg/kg Ref.
Fluorine Chlorine Bromine Sulfur
IEC 62321-3-2 Polymers and electronics - - 96 to 976 - 11
ASTM D 7359–14 Aromatics hydrocarbons 0,1 to 10 0,1 −10 - 0,1 −10 12
ASTM D 7994–17 Liquified petroleum gases 1 to 300 5 to 300 - 1 - 300 13
ASTM D 8150 Crude oil (naphta fraction) - 1 to 50 - - 14
ASTM UOP 991-13 Liquid organics 0,1 to 100 0,1 to 100 0.2 to 100 - 15
ASTM UOP 1001-14 Liquified petroleum gases 1 to 1 500 1 to 1 500 - - 16
JIS K 7392 Waste plastic - - 100 to 20 000 - 17
Halogen free soldering
JEITA ET-7304A < 1 000 < 1 000 < 1 000 - 18
material
KS M01080-2009 Electronic equipment X X X - 19
Table 2 — Non-limited list of standard methods allowing analysis by C-IC without a particular
section on C-IC
Elements and measuring range
Standard method Matrix mg/kg Ref.
Fluorine Chlorine Bromine Sulfur
60 to 90 to
EN ISO 16994 Solid biofuels - - 20
2 000 1 200
ISO 11724 Coal, cole and fly ash X - - - 21
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Elements and measuring range
Standard method Matrix mg/kg Ref.
Fluorine Chlorine Bromine Sulfur
ISO 17947 Nitride X X X X 22
ASTM D 5987–07 Coal and coke 20 to 500 - - - 23
DIN 51723 Solid fuels X - - - 24
DIN 51724 Coal and coke - - - X 25
JIS R 1616 Silicon carbide X - - - 26
JIS R 9301–3-11 Alumina powder X - - - 27
JIS Z 7302–6/7 Refuse derived fuel - X - X 28
6 Evaluation study of the C-IC technique
6.1 General
A study was conducted by the Flemish Institute for Technological Research (VITO, Flanders, Belgium) in
commission of the Public Waste Agency of Flanders (OVAM, Belgium) to evaluate the C-IC technique for
the determination of halogens and sulfur in waste samples [3]. The main results of this study are
incorporated in this document.
The evaluation of the C-IC technique was performed by conducting comparative tests on C-IC systems
from 2 suppliers (Mitsubishi Chemical, Japan in combination with ion chromatography from Thermo
Fisher Scientific, USA and Metrohm, Belgium). These two different C-IC units were used to analyse
about 9 certified reference materials, as well as 10 waste samples. The analyses on the Mitsubishi
system were performed by Mitsubishi itself, while the analyses on the Metrohm C-IC system were
performed by VITO in the application laboratory of Metrohm in Antwerp, Belgium.
6.2 Description of the samples
For this study, the reference samples considered were oil, clay, coal, fly ash, polymer, phosphate rock.
Table 3 lists the certified values for these reference materials.
Table 3 — Overview certified values of the reference materials
Identification Matrix x x x x
ass ass ass ass
Fluorine Chlorine Bromine Sulfur
mg/kg mg/kg mg/kg mg/kg
AOD 1.11 Oil - 9 500 ±50 - 6 500 ±40
AOD 1.12 Oil 4 300 ±40 - 9 500 ±50 -
BCR 461 Clay 568 ±10 119 ±25 - -
BCR 460 Coal 225 59 - -
BCR 182 Coal - 3 700 ±70 36,5 -
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Identification Matrix x x x x
ass ass ass ass
Fluorine Chlorine Bromine Sulfur
mg/kg mg/kg mg/kg mg/kg
BCR 038 Fly ash 538 ±13 323 ±22 - -
N1633b Fly ash - - 2,9 2 075 ±11
BCR 681 Polymer - 93 ±2,8 98 ±2,8 78 ±17
BCR 032 PO rock 40 400 ±600 - - 7 360 ±320
4
Where
x is the assigned value
ass
italic: indicative values
In consultation with OVAM, a number of waste samples were selected for analysis with C-IC as
presented in Table 4. All waste samples were dried at 105 °C and fine grinded down to < 0,5 mm using
an universal cutting mill.
Table 4 — Overview of analysed waste samples
Sample number Type of sample
CIC1 Fine shredder
CIC2 SRF fraction(industrial waste)
CIC3 SRF fraction (household waste)
CIC4 Sewage sludge
CIC5 Post shredder residue (electrical equipment)-SRF
CIC6 Post shredder residue (electrical equipment)
CIC7 Post shredder residue (electrical equipment)-fluff
shredder
CIC8 Rubber granulates
CIC9 Plastics from WEEE (containing bromine)
CIC10 Rubber fraction
6.3 Description of the applied C-IC systems
The C-IC unit 1 (C-IC 1) is a double furnace system which was equipped with a ceramic pyrolysis tube
and ceramic boats. Furnace 1 was set at 900 °C and furnace 2 at 1 000 °C for organic samples and at
1 100 °C for both furnaces for inorganic samples and mixtures. The samples were pyrolysed under
humidified inert atmosphere and combusted in oxidising atmosphere. The resultant vapors were
absorbed in an aqueous solution (H O added), gas lines were washed, the absorption volume adjusted
2 2
to a defined volume by liquid level sensor and afterwards injected directly into the IC system for
2-
analysis. H O was added into the absorbing solution to oxidize SO to form SO .
2 2 2 4
In some cases, especially for the determination of sulfur, a combustion improver (WO ) was added. The
3
IC measurements were conducted using a separation column at 35 °C and 2,7 mM Na CO and
2 3
0,3 mM NaHCO as eluent with a flow rate of 1 ml/min. The ion chromatograph was calibrated for
3
fluorine, chlorine and sulfate (for this study the element bromine was not calibrated, although it is
feasible). There was no need for usage of a pre-concentration column or variable injection volumes for
the IC.
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The C-IC unit 2 (C-IC 2) consists of a combustion module including a flame sensor to control the speed
at which the boat sample holder is introduced into the furnace. Quartz boat sample holders and a quartz
pyrolysis tube were used for the measurements. The combustion takes place at 1 100 °C. Argon gas
(100 ml/min) is initially supplied to prevent excessive combustion. Afterwards O gas is supplied to
2
achieve complete post- combustion (no more soot present). In the incinerator the sample is incinerated
for 600 s. The resultant vapors are absorbed in an aqueous solution, and introduced directly into the IC
system for analysis. Some experiments were conducted using a pre-concentration column to remove
the excess of H O required for the oxidation of all the sulfur compounds to SO . The ion chromatograph
2 2 4
has a separation column at 30 °C. As eluent 3,2 mmol/l Na CO , 1,0 mmol/l NaHCO was used with a
2 3 3
flow rate of 0,7 ml/min. The ion chromatograph was calibrated for fluorine, chlorine, bromine and
sulfa
...
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