SIST EN 14792:2006

Stationary source emissions - Determination of mass concentration of nitrogen oxides (NOx) - Reference method: Chemiluminescence

This European Standard describes the chemiluminescence method, including the sampling and the gas conditioning system, to determine the NO/NO2/NOX concentrations in flue gases emitted from ducts and stacks to atmosphere. This European Standard is the Standard Reference Method (SRM) for periodic monitoring and for calibration or control of Automatic Measuring Systems (AMS) permanently installed on a stack, for regulatory or other purposes such as calibration. To be used as the SRM, the user shall demonstrate that the performance characteristics of the method are better than the performance criteria defined in this European Standard and that the overall uncertainty of the method is less than ± 10 percent relative at the daily Emission Limit Value (ELV).
NOTE   When the chemiluminescence method is the measurement principle used for AMS, reference should be made to EN 14181 and other relevant standards provided by CEN TC 264.
An Alternative Method to this SRM may be used provided that the user can demonstrate equivalence according to the Technical Specification CEN TS 14793, to the satisfaction of his national accreditation body or law.
This SRM has been evaluated during field tests on waste incineration, co-incineration and large combustion installations. It has been validated for sampling periods of 30 min in the range of 0 mgNO2/m3 to 1 300 mgNO2/m3 for large combustion plants and 0 mgNO2/m3 to 400 mgNO2/m3 for waste incineration, according to emission limit values (ELVs) laid down in the following Council Directives:
   Council Directive 2001/80/EC on the limitation of emissions of certain pollutants into the air from large combustion plants;
   Council Directive 2000/76/EC on waste incineration plants.
The ELVs for NOx (NO + NO2) in EU directives are expressed in mgNO2/m3, on dry basis, at a reference value for O2 and at the reference conditions (273 K and 101,3 kPa).

Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von Stickstoffoxiden (NOx) - Referenzverfahren : Chemilumineszenz

Diese Europäische Norm beschreibt das Chemilumineszenz-Verfahren, einschließlich Probenahmeeinrichtung und Gasaufbereitungssystem, von Abgaskonzentrationen an NO/NO2/NOx in Abgaskanälen, die ins Freie emittieren. Diese Europäische Norm ist das Standardreferenzverfahren (SRM) für die periodische Überwachung und für die Kalibrierung oder Überprüfung von automatischen Messsystemen (AMS), die permanent an einem Abgaskanal installiert sind. Wenn dieses Verfahren als Standardreferenzverfahren angewandt wird, muss nachgewiesen werden, dass die Verfahrenskenngrößen besser sind als die in dieser Europäischen Norm festgelegten Leistungskriterien und dass die Gesamtmessunsicherheit des Verfahrens kleiner ist als 10 %, bezogen auf den Tages-Emissionsgrenzwert (ELV).
ANMERKUNG   Wenn das Chemilumineszenz-Verfahren das Messprinzip der automatischen Messeinrichtung darstellt, sollte auf EN 14181 oder eine andere geeignete Norm des CEN/TC 264 Bezug genommen werden.
Ein Alternativverfahren zu diesem Standardreferenzverfahren darf angewendet werden, wenn der Anwender vor der nationalen Akkreditierungsstelle oder dem Gesetz die Äquivalenz nach der Technischen Spezifikation CEN/TS 14793 nachweisen kann.
Dieses Standardreferenzverfahren wurde in Feldversuchen an Abfallverbrennungsanlagen und Mitverbrennungsanlagen sowie an Großfeuerungsanlagen beurteilt. Es wurde validiert mit Probenahmedauern von 30 min für NO2-Konzentrationen im Bereich von 0 mg/m3 bis 1 300 mg/m3 an Großfeuerungsanlagen und im Bereich von 0 mg/m3 bis 400 mg/m3 an Abfallverbrennungsanlagen, entsprechend den in den folgenden Europäischen Richtlinien festgelegten Emissionsgrenzwerten:
-   Richtlinie 2001/80/EG des Europäischen Parlaments und des Rates vom 23. Oktober 2001 zur Begrenzung von Schadstoffemissionen von Großfeuerungsanlagen in die Luft;
-   Richtlinie 2000/76/EG des Europäischen Parlaments und des Rates vom 4. Dezember 2000 über die Verbrennung von Abfällen.

Emissions de sources fixes - Détermination de la concentration massique en oxides d'azote (NOx) - Méthode de référence: Chimuluminescence

Emisije nepremičnih virov – Določevanje masne koncentracije dušikovih oksidov (NOx) – Referenčna metoda: kemiluminiscenca

General Information

• Status: Withdrawn
• Publication Date: 31-Jan-2006
• Withdrawal Date: 31-Jan-2017
• ICS: 13.040.40 - Stationary source emissions
• Technical Committee: KAZ - Air quality
• Current Stage: 9900 - Withdrawal (Adopted Project)
• Start Date: 27-Jan-2017
• Due Date: 19-Feb-2017
• Completion Date: 01-Feb-2017
• Directive: 88/609/EEC - Limitation of emissions of certain pollutants into the air from large combustion plants
• Directive: 89/369/EEC - Prevention of air pollution from new municipal waste incineration plants
• Directive: 89/429/EEC - Reduction of air pollution from existing municipal waste incineration plants
• Directive: 94/67/EC - Incineration of hazardous waste
• Mandate: M/278 - Standardization mandate to CEN for manual reference methods for the calibration of automated measurement systems for sulphur dioxide (S02) and nitrogen oxides (NOx) emissions in stack
• Ref Project: EN 14792:2005 - Stationary source emissions - Determination of mass concentration of nitrogen oxides (NOx) - Reference method: Chemiluminescence

Relations

• Replaced By: SIST EN 14792:2017 - Stationary source emissions - Determination of mass concentration of nitrogen oxides - Standard reference method: chemiluminescence
• Effective Date: 01-Mar-2017

Standards Content (Sample)

SLOVENSKI STANDARD
SIST EN 14792:2006
01-februar-2006
(PLVLMHQHSUHPLþQLKYLURY±'RORþHYDQMHPDVQHNRQFHQWUDFLMHGXãLNRYLKRNVLGRY
12[±5HIHUHQþQDPHWRGDNHPLOXPLQLVFHQFD
Stationary source emissions - Determination of mass concentration of nitrogen oxides
(NOx) - Reference method: Chemiluminescence
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
Stickstoffoxiden (NOx) - Referenzverfahren : Chemilumineszenz
Emissions de sources fixes - Détermination de la concentration massique en oxides
d'azote (NOx) - Méthode de référence: Chimuluminescence
Ta slovenski standard je istoveten z: EN 14792:2005
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
SIST EN 14792:2006 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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SIST EN 14792:2006

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SIST EN 14792:2006
EUROPEAN STANDARD
EN 14792
NORME EUROPÉENNE
EUROPÄISCHE NORM
November 2005
ICS 13.040.40

English Version
Stationary source emissions - Determination of mass
concentration of nitrogen oxides (NOx) - Reference method:
Chemiluminescence
missions de sources fixes - Détermination de la Emissionen aus stationären Quellen - Bestimmung der
concentration massique en oxides d'azote (NOx) - Méthode Massenkonzentration von Stickstoffoxiden (NOx) -
de référence: Chimuluminescence Referenzverfahren : Chemilumineszenz
This European Standard was approved by CEN on 30 September 2005.
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 Central Secretariat 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 Central Secretariat has the same status as the official
versions.
CEN members are the national standards bodies of Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,
Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, 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
© 2005 CEN All rights of exploitation in any form and by any means reserved Ref. No. EN 14792:2005: E
worldwide for CEN national Members.

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SIST EN 14792:2006
EN 14792:2005 (E)
Contents Page
Foreword .4
1 Scope.5
2 Normative references.5
3 Terms and definitions.6
4 Principle.10
4.1 General.10
4.2 Measuring principle.10
5 Description of measuring equipment - Sampling and sample gas conditioning systems.11
5.1 General.11
5.2 Sampling line components.12
5.2.1 Sampling line.12
5.2.2 Filter.12
5.2.3 Sample cooler (configuration 1) .12
5.2.4 Permeation drier (configuration 2).12
5.2.5 Dilution system (configuration 3) .13
5.2.6 Heated line and heated analyser (configuration 4).13
5.2.7 Sample pump.13
5.2.8 Secondary filter.13
5.2.9 Flow controller and flow meter .13
6 Analyser equipment.14
6.1 General.14
6.2 Converter.14
6.3 Ozone generator.14
6.4 Reaction chamber.15
6.5 Optical filter.15
6.6 Photomultiplier tube.15
6.7 Ozone removal.15
7 Determination of the characteristics of the SRM: analyser, sampling and conditioning line.15
7.1 General.15
7.2 Relevant performance characteristics of the SRM and performance criteria .16
7.3 Establishment of the uncertainty budget.17
8 Field operation.18
8.1 Sampling location.18
8.2 Sampling point(s).18
8.3 Choice of the measuring system .19
8.4 Setting of the SRM on site.19
8.4.1 General.19
8.4.2 Preliminary zero and span check, and adjustments .20
8.4.3 Zero and span checks after measurement.20
9 Ongoing quality control.21
9.1 General.21
9.2 Frequency of checks .21
10 Expression of results.22
11 Evaluation of the method in the field.23
12 Equivalence with an alternative method .23
13 Test report.24
2

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SIST EN 14792:2006
EN 14792:2005 (E)

Annex A (informative) Four different sampling and conditioning configurations.25
Annex B (normative) Determination of converter efficiency .26
B.1 General.26
B.2 First method : cylinder gases for calibration.26
B.3 Second method : gaseous phase titration .26
Annex C (informative) Examples of different types of converters.28
C.1 Quartz converter.28
C.2 Low temperature converter (molybdenum).28
C.3 Stainless steel converter.28
Annex D (informative) Example of assessment of compliance of chemiluminescence method for
NO with requirements on emission measurements.29
x
D.1 General.29
D.2 Process of uncertainty estimation.29
D.2.1 Determination of the model equation.29
D.2.2 Quantification of uncertainty components .29
D.2.3 Calculation of the combined uncertainty.29
D.3 Specific conditions in the field .30
D.4 Performance characteristics of the method .31
D.4.1 NO measurement.32
D.4.2 NOx measurement .38
D.4.3 Results of standard uncertainties calculation.40
D.4.4 Calculation of combined uncertainties .42
3

D.5 Conversion of the concentrations in mg/m .42
D.5.1 No measurement.43
D.5.2 NO measurement.43
2
D.5.3 NO measurement .43
x
D.5.4 Combined uncertainty.43
D.5.5 Overall uncertainty.43
D.6 Evaluation of the compliance with the required measurement quality.43
Annex E (informative) Procedure of correction of data from drift effect.45
Annex F (informative) Evaluation of the method in the field.46
F.1 General.46

F.2 Characteristics of installations.46
F.3 Repeatability and reproducibility in the field.47
F.3.1 General.47
F.3.2 Repeatability.48
F.3.3 Reproducibility.49
Annex ZA (informative) Relationship with EU Directives.50
Bibliography.51

3

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SIST EN 14792:2006
EN 14792:2005 (E)
Foreword
This European Standard (EN 14792:2005) 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 2006, and conflicting national standards shall be withdrawn at the
latest by May 2006.
This European Standard has been prepared under a mandate given to CEN by the European Commission
and the European Free Trade Association, and supports essential requirements of EU Directive(s).
For relationship with EU Directive(s), see informative Annex ZA, which is an integral part of this European
Standard.
According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following
countries are bound to implement this European Standard: 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 United Kingdom.
4

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SIST EN 14792:2006
EN 14792:2005 (E)
1 Scope
This European Standard describes the chemiluminescence method, including the sampling and the gas
conditioning system, to determine the NO/NO /NO concentrations in flue gases emitted from ducts and
2 x
stacks to atmosphere. This European Standard is the Standard Reference Method (SRM) for periodic
monitoring and for calibration or control of Automatic Measuring Systems (AMS) permanently installed on a
stack, for regulatory or other purposes such as calibration. To be used as the SRM, the user shall
demonstrate that the performance characteristics of the method are better than the performance criteria
defined in this European Standard and that the overall uncertainty of the method is less than ± 10 % relative at
the daily Emission Limit Value (ELV).
NOTE When the chemiluminescence method is the measurement principle used for AMS, reference should be made
to EN 14181 and other relevant standards provided by CEN TC 264.
An Alternative Method to this SRM may be used provided that the user can demonstrate equivalence
according to the Technical Specification CEN TS 14793, to the satisfaction of his national accreditation body
or law.
This SRM has been evaluated during field tests on waste incineration, co-incineration and large combustion
3
installations. It has been validated for sampling periods of 30 min in the range of 0 mg NO /m to
2
3 3 3
1 300 mg NO /m for large combustion plants and 0 mg NO /m to 400 mg NO /m for waste incineration,
2 2 2
according to emission limit values (ELVs) laid down in the following Council Directives:
 Council Directive 2001/80/EC on the limitation of emissions of certain pollutants into the air from large
combustion plants;
 Council Directive 2000/76/EC on waste incineration plants.
3
The ELVs for NO (NO + NO ) in EU directives are expressed in mg NO /m , on dry basis, at a reference
x 2 2
value for O and at the reference conditions (273 K and 101,3 kPa).
2
2 Normative references
The following referenced documents are indispensable for the application of this European Standard. For
dated references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
ENV 13005, Guide to the expression of uncertainty in measurement.
EN 14790:2003, Stationary source emissions - Determination of the water vapour in ducts.
CEN/TS 14793, Stationary source emissions - Intralaboratory validation procedure for an alternative method
compared to a reference method.
EN ISO 14956, Air quality - Evaluation of the suitability of a measurement procedure by comparison with a
required measurement uncertainty (ISO 14956:2002).
5

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EN 14792:2005 (E)
3 Terms and definitions
For the purposes of this European Standard, the following terms and definitions apply.
NOTE In this European Standard, NO is defined as the sum of NO and NO . The mass concentration of NO is
x 2 x
expressed as the equivalent NO concentration in milligrams per cubic metre at normal conditions.
2
3.1
adjustment (of a measuring system)
operation of bringing a measuring system into a state of performance suitable for its use
[VIM 4.30]
3.2
ambient temperature
temperature of the air around the measuring system
3.3
automatic measuring system (AMS)
measuring system permanently installed on site for continuous monitoring of emissions
NOTE 1 An AM is a method which is traceable to a reference method.
NOTE 2 Apart from the analyser, an AMS includes facilities for taking samples (e.g. probe, sample gas lines, flow
meters, regulators, delivery pumps) and for sample conditioning (e.g. dust filter, moisture removal devices, converters,
diluters). This definition also includes testing and adjusting devices, that are required for regular functional checks.
[EN 14181]
3.4
calibration
statistical relationship between values of the measurand indicated by the measuring system (AMS) and the
corresponding values given by the standard reference method (SRM) used during the same period of time
and giving a representative measurement on the same sampling plane
NOTE The result of calibration permits to establish the relationship between the values of the SRM and the AMS
(calibration function).
3.5
converter efficiency
percentage of NO present in the sample gas converted to NO by the converter
2
3.6
drift
difference between two zero (zero drift) or span readings (span drift) at the beginning and at the end of a
measuring period
3.7
emission limit value (ELV)
emission limit value according to EU Directives on the basis of 30 min, 1 hour or 1 day
6

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EN 14792:2005 (E)
3.8
influence quantity
quantity that is not the measurand but that affects the result of the measurement
[adapted VIM 2.7]
NOTE Examples:
 ambient temperature;
 atmospheric pressure;
 presence of interfering gases in the flue gas matrix;
 pressure of the gas sample.
3.9
interference
negative or positive effect upon the response of the measuring system, due to a component of the sample that
is not the measurand
3.10
lack of fit
systematic deviation within the range of application between the measurement result obtained by applying the
calibration function to the observed response of the measuring system measuring test gases and the
corresponding accepted value of such test gases
NOTE 1 Lack of fit may be a function of the measurement result.
NOTE 2 The expression “lack of fit” is often replaced in everyday language by "linearity" or "deviation from linearity".
3.11
measurand
particular quantity subject to measurement
[VIM 2.6]
3.12
measuring system
complete set of measuring instruments and other equipment assembled to carry out specified measurements
[VIM 4.5]
3.13
performance characteristic
one of the quantities (described by values, tolerances, range…) assigned to equipment in order to define its
performance
3.14
repeatability in the laboratory
closeness of the agreement between the results of successive measurements of the same measurand carried
out under the same conditions of measurement
NOTE 1 Repeatability conditions include:
 same measurement procedure;
 same laboratory;
 same measuring instrument, used under the same conditions;
7

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EN 14792:2005 (E)
 same location;
 repetition over a short period of time.
NOTE 2 Repeatability may be expressed quantitatively in terms of the dispersion characteristics of the results.
In this European Standard the repeatability is expressed as a value with a level of confidence of 95 %.
[VIM 3.6]
3.15
repeatability in the field
closeness of the agreement between the results of simultaneous measurements of the same measurand
carried out with two sets of equipment under the same conditions of measurement
NOTE 1 These conditions include:
 same measurement procedure;
 two sets of equipment, the performance of which fulfils the requirements of the reference method, used under the
same conditions;
 same location;
 implemented by the same laboratory;
 typically calculated on short periods of time in order to avoid the effect of changes of influence parameters (e.g.
30 min).
NOTE 2 Repeatability may be expressed quantitatively in terms of the dispersion characteristics of the results.
In this European Standard the repeatability under field conditions is expressed as a value with a level of
confidence of 95 %.
3.16
reproducibility in the field
closeness of the agreement between the results of simultaneous measurements of the same measurand
carried out using several sets of equipment under the same conditions of measurement
NOTE 1 These conditions are called field reproducibility conditions and include:
 same measurement procedure;
 several sets of equipment, the performance of which fulfils the requirements of the reference method, used under the
same conditions;
 same location;
 implemented by several laboratories.
NOTE 2 Reproducibility may be expressed quantitatively in terms of the dispersion characteristics of the results.
In this European Standard the reproducibility under field conditions is expressed as a value with a level of
confidence of 95 %.
3.17
residence time in the measuring system
time period for the sampled gas to be transported from the inlet of the probe to the inlet of the measurement
cell
8

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EN 14792:2005 (E)
3.18
response time
time interval between the instant when a stimulus is subjected to a specified abrupt change and the instant
when the response reaches and remains within specified limits around its final steady value
NOTE By convention, time taken for the output signal to pass from 0 % to 90 % of the final change
[VIM 5.17]
3.19
sampling location
specific area close to the sampling plane where the measurement devices are set up
3.20
sampling plane
plane normal to the centreline of the duct at the sampling position
[EN 13284-1]
3.21
sampling point
specific position on a sampling line at which a sample is extracted
[EN 13284-1]
3.22
span gas
test gas used to adjust and check a specific point on the response line of the measuring system
NOTE This concentration is often chosen around 80 % of the upper limit of the range or around the ELV.
3.23
standard reference method (SRM)
measurement method recognised by experts and taken as a reference by convention, which gives, or is
presumed to give, the accepted reference value of the concentration of the measurand (3.11) to be measured
3.24
uncertainty
parameter associated with the result of a measurement, that characterises the dispersion of the values that
could reasonably be attributed to the measurand
3.24.1
standard uncertainty u
uncertainty of the result of a measurement expressed as a standard deviation u
3.24.2
combined uncertainty u
c
standard uncertainty u attached to the measurement result calculated by combination of several standard
c
uncertainties according to GUM
3.24.3
expanded uncertainty U
quantity defining a level of confidence about the result of a measurement that may be expected to encompass
a specific fraction of the distribution of values that could reasonably be attributed to a measurand
U = k × u
NOTE In this European Standard, the expanded uncertainty is calculated with a coverage factor of k = 2, and with a
level of confidence of 95 %.
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EN 14792:2005 (E)
3.24.4
overall uncertainty U
c
expanded combined standard uncertainty attached to the measurement result calculated according to GUM
U = k × u
c c
3.25
uncertainty budget
calculation table combining all the sources of uncertainty according to EN ISO 14956 or ENV 13005 in order
to calculate the overall uncertainty of the method at a specified value
4 Principle
4.1 General
This European Standard describes the SRM, based on the chemiluminescence principle for sampling and
determining NO , NO and NO concentrations in flue gases emitted to atmosphere from ducts and stacks. The
x
2
specific components and the requirements for the sampling system and the chemiluminescence analyser are
described. A number of performance characteristics, together with associated minimum performance criteria
are specified for the analyser. These performance characteristics and the overall uncertainty of the method
shall meet the performance criteria given in this European Standard. Requirements and recommendations for
quality assurance and quality control are given for measurements in the field (see table 1 in 7.2).
4.2 Measuring principle
The principle of chemiluminescence to measure NO is based on the following reaction between nitrogen
x
monoxide and ozone:
2 NO + 2 O ⇒ NO + NO * +2 O
3 2 2 2
NO *⇒ NO + hν
2 2
Some of the NO created during the reaction of NO and O is in an excited state. When returning to the basic
2 3
state, these NO molecules can radiate light, the intensity of which depends on the NO content and is
2
influenced by the pressure and presence of other gases.
In a chemiluminescence analyser, gas is sampled through a sampling line and fed at a constant flow rate into
the reaction chamber of the analyser, where it is mixed with an excess of ozone for the determination of
nitrogen oxide only. The emitted radiation (chemiluminescence) is proportional to the amount of NO present in
the sampled gas. The emitted radiation is filtered by means of a selective optical filter and converted into an
electric signal by means of a photomultiplier tube.
For the determination of the amount of nitrogen dioxide, the sampled gas is fed through a converter where the
nitrogen dioxide is reduced to nitrogen monoxide and analysed in the same way as previously described. The
electric signal obtained from the photomultiplier tube is proportional to the sum of concentrations of nitrogen
dioxides and nitrogen monoxides. The amount of nitrogen dioxide is calculated from the difference between
this concentration and that obtained for nitrogen monoxide only (wh
...