EN 13649:2001

SLOVENSKI STANDARD
01-maj-2002
(PLVLMHQHSUHPLþQLKYLURY'RORþHYDQMHPDVQHNRQFHQWUDFLMHSRVDPH]QLK
RUJDQVNLKVSRMLQYSOLQDVWLID]L0HWRGD]DNWLYQLPRJOMHPLQGHVRUSFLMHVWRSLORP
Stationary source emissions - Determination of the mass concentration of individual
gaseous organic compounds - Activated carbon and solvent desorption method
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
einzelnen gasförmigen organischen Verbindungen - Aktivkohleadsorptions- und
Lösemitteldesorptionsverfahren
Emissions de sources fixes - Détermination de la concentration massique en composés
organiques gazeux individuels - Méthode par charbon actif et description des solvants
Ta slovenski standard je istoveten z: EN 13649:2001
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

EUROPEAN STANDARD
EN 13649
NORME EUROPÉENNE
EUROPÄISCHE NORM
November 2001
ICS 13.040.40
English version
Stationary source emissions - Determination of the mass
concentration of individual gaseous organic compounds -
Activated carbon and solvent desorption method
Emissions de sources fixes - Détermination de la Emissionen aus stationären Quellen - Bestimmung der
concentration massique en composés organiques gazeux Massenkonzentration von einzelnen gasförmigen
individuels - Méthode par charbon actif et désorption des organischen Verbindungen - Aktivkohleadsorptions- und
solvants Lösemitteldesorptionsverfahren
This European Standard was approved by CEN on 29 September 2001.
CEN members are bound to comply with the CEN/CENELEC Internal Regulations which stipulate the conditions for giving this European
Standard the status of a national standard without any alteration. Up-to-date lists and bibliographical references concerning such national
standards may be obtained on application to the Management Centre or to any CEN member.
This European Standard exists in three official versions (English, French, German). A version in any other language made by translation
under the responsibility of a CEN member into its own language and notified to the Management Centre has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, Czech Republic, Denmark, Finland, France, Germany, Greece,
Iceland, Ireland, Italy, Luxembourg, Netherlands, Norway, Portugal, 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
© 2001 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 13649:2001 E
worldwide for CEN national Members.

Contents
page
Foreword 3
1 Scope 3
2 Normative references 3
3 Terms and definitions 4
4 Principle 4
5 Apparatus and materials 5
6 Sampling procedure 9
7 Analytical procedure 11
8 Calculation 13
9 Report 13
Annex A (informative) Measurement uncertainty and associated statistics 15
Annex B (informative) Typical desorption efficiencies of selected organic components on
activated carbon 17
Annex C (informative) Procedure for control of leakage 19
Annex D (informative) Procedure for dilution sampling 20
Annex E (informative) Safety measures 21
Foreword
This European Standard has been prepared by Technical Committee CEN/TC 264 "Air
Quality", the secretariat of which is held by DIN.
This European Standard shall be given the status of a national standard, either by publication
of an identical text or by endorsement, at the latest by May 2002, and conflicting national
standards shall be withdrawn at the latest by May 2002.
This European Standard has been prepared under a mandate given to CEN by the European
Commission and European Free Trade Association.
The annexes A, B, C, D and E are informative.
According to the CEN/CENELEC Internal Regulations, the national standards organizations
of the following countries are bound to implement this European Standard: Austria, Belgium,
Czech Republic, Denmark, Finland, France, Germany, Greece, Iceland, Ireland, Italy,
Luxembourg, Netherlands, Norway, Portugal, Spain, Sweden, Switzerland and the United
Kingdom.
1Scope
This European Standard specifies procedures for the sampling onto activated carbon, the
preparation and the analysis of samples of volatile organic components such as those arising
from solvent using processes. It can be used as a reference method.
NOTE  See Council Directive 1999/13/EEC.
The results obtained using this Standard are expressed as the mass concentration (mg/m ) of
the individual gaseous organic components. This Standard is suitable for use in the range of
3 3
about 0,5 mg/m to 2000 mg/m .
For the measurement of the mass concentration of total organic carbon arising from solvent
using processes then EN 13526 should be used.
2 Normative references
This European Standard incorporates, by dated or undated reference, provisions from other
publications. These normative references are cited at the appropriate places in the text, and
the publications are listed hereafter. For dated references, subsequent amendments to or
revisions of any of these publications apply to this European Standard only when incorporated
in it by amendment or revision. For undated references the latest edition of the publication
referred to applies (including amendments).
EN 13526:2001, Stationary source emissions - Determination of the mass concentration of
total gaseous organic carbon in flue gases from solvent using processes - Continuous flame
ionisation detector method.
ISO 5725-1, Accuracy (trueness and precision) of measurement methods and results Part 1:
General principles and definitions.
ISO 9169, Air Quality – Determination of performance characteristics of measurement
methods.
3 Terms and definitions
For the purposes of this European Standard the following terms and definitions apply.
3.1
desorption efficiency
ratio of the mass of the recovered organic material to the mass of organic material added to
the carbon adsorbent expressed as a percentage
3.2
detection limit
minimum concentration of a substance which produces an observable response, as referred to
in ISO 9169
3.3
dilution gas
gas used to dilute sampled flue gas to prevent water condensation
3.4
flue gas
gaseous waste product from a solvent using process
4 Principle
4.1 General
There are three steps in the measurement of individual gaseous organic components. They are
flue gas sampling, the treatment of sampled material, and the chemical analysis by gas
chromatography.
4.2 Flue gas sampling
The principles of sampling are as follows:
- Organic components from a measured volume of gas shall be adsorbable onto the
activated carbon.
- Particulate material which might interfere with the measurement should be removed.
- Water condensation should be prevented.
4.3 Treatment of sampled material
The collected organic material shall be desorbed using an extraction solvent.
4.4 Chemical analysis
An aliquot of the sample is injected into a gas chromatography system equipped with a
capillary column and an appropriate detector (e.g. flame ionisation detector, mass selective
detector etc.). The components are separated by gas chromatography. The detector signals are
evaluated using the calibration function.
4.5 Desorption efficiency determination
At the sample preparation stage a known amount of a reference material is introduced on to a
blank carbon tube to determine component desorption efficiency.
The desorption efficiency can be determined as shown in annex B.
NOTE  The desorption efficiency should be better than 80 %.
5 Apparatus and materials
5.1 Sampling system – general aspects
The sampling system shall be designed to take account of the flue gas characteristics:
- it shall be made of a material that is chemically and physically inert to the constituents
of the flue gas;
NOTE 1  Stainless steel, glass, polytetrafluoroethylene and polypropylenefluoride are well proven
construction materials.
- the sampling line shall be as short as possible;
- the sampling line shall include a filtering device directly after the probe to trap
particles;
- it shall be designed to prevent condensation.
NOTE 2  Many of the solvent using processes covered by the Council Directive 1999/13/EEC
produce flue gases which do not have a high water content. Where high solvent concentrations or the
condensation of water vapour is expected this CEN Standard recommends the use of dilution
sampling systems.
Examples of systems suitable for sampling both dry and wet flue gases are described in this
standard.
5.1.1 Sampling without dilution
An example of a suitable sampling system is shown in Figure 1.
4 7
3 56 8


1 Prefilter/sampling probe unit
2Sample line
3 Sorbent tube
4Drying unit
5Adjustment Valve
6Pump
7 Flow meter
8Gas meter
Figure 1 - Example of a flue gas sampling system
5.1.2 Sampling using dynamic dilution
An example of a dynamic dilution system is shown in Figure 2.
The dilution should be adjustable and shall be constant to within 5 % during operation.
4 7
3 56 8


5 9 2 6


1 Prefilter/sampling probe unit
2Sample line
3 Sorbent tube
4Drying unit
5Adjustment Valve
6Pump
7 Flow meter
8 Gas meter (total volume)
9 Carbon
10 Gas meter (dilution volume)
Figure 2 - Example of a dynamic dilution sampling system
5.1.3 Sampling using static dilution
Static dilution sampling can be carried out by part filling a sample bag, fabricated from an
inert material, with a known volume of dry dilution gas, a known volume of flue gas is then
added. A heated sampling probe can be used to ensure that no condensation occurs before the
sample enters the bag. Following sampling the bag is emptied through the sorbent tube.
NOTE 1  A suitable procedure is the ‘lung principle’ in which a sample bag is placed in a rigid, leak
proof container, the air is removed from the container using a vacuum pump, the reduced pressure in
the container causes the bag to fill with a volume of sample equal to that which has been removed
from the container. A pressure control device operating at not greater than 250 Pa should be used to
prevent the bag bursting.
NOTE 2  A suitable bag material include polyvinyl fluoride.
NOTE 3  A suitable procedure for collecting diluted gas samples is given in annex D.


Key
1 PTFE tube
2 Pump
3 Bag (partially filled with dilution gas)
4 Rigid container
5 PTFE valve
6 Pressure control device
Figure 3 - Example of a static dilution sampling system
5.1.4 Sorbent tube
The sorbent tube, filled with activated carbon as the adsorbent, shall have the following
characteristics:
- a main adsorbent layer containing not less than 100 mg of activated carbon;
NOTE 1  A suitable material is activated carbon prepared from coconut shell.
- a security adsorbent layer to detect breakthrough;
- the sorbent tube construction material shall be inert;
NOTE 2  A suitable material is glass.
- the sorbent tubes shall be free from contamination.
Open or used sorbent tubes shall not be reused. Sorbent tubes shall be used in accordance
with the manufacturers instructions to avoid leakage and sample loss.
NOTE 3  Typical desorption efficiencies of common solvents from tubes of this type are given in
annex B.
5.1.5 Dilution gas
Dilution gas should be nitrogen or dry air containing less than 0.1 % of the emission limit
value of any of the principal components under investigation.
NOTE  Nitrogen of purity 99,999 % or ambient air, purified by passage through activated carbon,
normally meets these requirements.
5.2 Analytical reagents
5.2.1 General
Only reagents of recognised analytical grade or better quality shall be used.
5.2.2 Extraction Solvent
Extraction solvents shall be of chromatographic quality and free from components co-eluting
with the components of interest.
NOTE 1  Carbon disulphide (CS ) is a suitable extraction solvent for most of the components likely
to be encountered in solvent using processes.
NOTE 2  For polar substances other extraction solvents can be used (see annex B).
5.2.3 Reference materials for calibration of the analytical procedure
The chromatograph shall be calibrated with those reference materials which correspond to the
components likely to arise in the process under investigation.
For the purpose of calibration the reference materials shall be prepared in a solution of the
extraction solvent to be used. The extraction solvents are highly volatile and fresh reference
standards should be prepared regularly.
5.3 Analytical apparatus
Laboratory apparatus suitable for capillary column chromatography shall be used.
6 Sampling procedure
6.1 General Aspects
The sample shall be representative of both the process emission and the local distribution of
the measured constituents in the sampling plane.
The following points should be considered when sampling:
- the nature of the plant process e.g. steady state or cyclic. If possible the sampling
programme should be carried out under steady operating conditions of the plant;
- the expected concentration to be measured and any required averaging period, both of
which can influence the sampling time.
6.2 Choice of sampling procedure
The choice of sampling procedure shall be governed by the characteristics of the gas.
Sampling directly onto the sorbent material can be used when the flue gas does not have a
high water content and the mass concentration of (organic) material is such that break through
is unlikely to occur.
o
The temperature of the flue gas should not exceed 40 C during adsorption. Provided that no
condensation occurs hotter flue gas can be cooled down using a cooling section (inert
sampling line). Sampling using dilution or equivalent methods shall be used if the exhaust gas
is so moist that condensation occurs or the mass concentration of organic components is such
that there is a risk of exceeding the capacity of the sorbent tubes. Dilution can be either static
or dynamic.
NOTE  A suitable procedure for dilution sampling is given in annex D.
6.3 Minimum sampling time and flow rate
The sampling time shall be chosen taking into consideration any required averaging period,
process conditions, sampling and analytical equipment, and the lower detection limit of the
analysis. A typical time for an individual periodic measurement for most applications is 10-30
minutes. When sampling processes which are not steady state it may be necessary to reduce
the sampling time. The sampling time should not be shorter than 5 minutes.
NOTE 1  Using activated carbon tubes with 100 mg activated carbon in the main adsorbent layer, 1
ml extraction solvent and a capillary column gas chromatograph with a flame ionisation detector,
(absolute detection limit is <1 μg). A sampling time of 30 min and a sample gas flow of 0,5 l/min
gives a sample gas volume of 15 l and a relative detection limit of approximately 0,1 mg/ m³.
NOTE 2  Using activated carbon tubes with 1000 mg activated carbon, 10 ml extraction solvent and
the same analytical equipment as above (Note 1). A sampling time of 30 min and a sample gas flow
of 1 l/min gives a sample gas volume of 30 l and a relative detection limit of about 0,5 mg/m .
NOTE 3  Using a gas chromatograph with a mass selective detector in single ion monitoring-modus
the detection limit can be a factor of 100 lower.
NOTE 4  For other times and conditions the detection limit can be estimated from the figures above.
NOTE 5  The typical volume flow rate is 0,3 l/min to 1,0 l/min.
6.4 Measurement of flue gas sample volume
The volume of the gas sampled shall be measured using a gas meter or other suitable device
calibrated in the range used. The sample temperature at the gas meter and atmospheric
pressure shall be measured.
6.5 Control of leakage
Leakage contributes significantly to the errors when sampling and shall be controlled by
appropriate check procedures before each sampling run. A suitable procedure for control of
leakage is given in annex C.
NOTE  A leak check after the sampling run is recommended where leak-sensitive devices such as
gas bags are used, and in sampling conditions where the
...