Waste - State-of-the-art document - Halogens and sulfur by oxidative pyrohydrolytic combustion followed by ion chromatography detection

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.

Abfall - Dokument zum Stand der Technik - Bestimmung von Halogenen und Schwefel mittels oxidativer pyro-hydrolytischer Verbrennung mit Ionenchromatographie Detektion

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

Status
Published
Publication Date
12-Feb-2019
Current Stage
6060 - Definitive text made available (DAV) - Publishing
Due Date
13-Feb-2019
Completion Date
13-Feb-2019

Buy Standard

Technical report
-TP CEN/TR 17345:2019
English language
25 pages
sale 10% off
Preview
sale 10% off
Preview

e-Library read for
1 day

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.

---------------------- Page: 1 ----------------------
SIST-TP CEN/TR 17345:2019
---------------------- Page: 2 ----------------------
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.
---------------------- Page: 3 ----------------------
SIST-TP CEN/TR 17345:2019
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

---------------------- Page: 4 ----------------------
SIST-TP CEN/TR 17345:2019
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.

---------------------- Page: 5 ----------------------
SIST-TP CEN/TR 17345:2019
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.
---------------------- Page: 6 ----------------------
SIST-TP CEN/TR 17345:2019
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

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
---------------------- Page: 7 ----------------------
SIST-TP CEN/TR 17345:2019
CEN/TR 17345:2019 (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

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

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 ).

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.
---------------------- Page: 8 ----------------------
SIST-TP CEN/TR 17345:2019
CEN/TR 17345:2019 (E)

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
---------------------- Page: 9 ----------------------
SIST-TP CEN/TR 17345:2019
CEN/TR 17345:2019 (E)
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 -
---------------------- Page: 10 ----------------------
SIST-TP CEN/TR 17345:2019
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
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

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

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

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.
---------------------- Page: 11 ----------------------
SIST-TP CEN/TR 17345:2019
CEN/TR 17345:2019 (E)

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

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
...

Questions, Comments and Discussion

Ask us and Technical Secretary will try to provide an answer. You can facilitate discussion about the standard in here.