Stationary source emissions - Determination of mass concentration of gaseous chlorides expressed as HCl - Standard reference method

The method described in this European Standard determines the concentration of chlorinated compounds in a flue gas that - after passage of the sampling system including a particle filter - give Cl- ions in the absorption solution. This Standard Reference Method has been evaluated during field tests on waste incineration. The method applies to waste gases in which chlorides concentration expressed as HCl may vary between 1 mg-m-3 and 5 000 mg-m-3 under normal pressure and temperature conditions (see Note 1), and according to emission limit values laid down, for example, in the Council Directive 2000/76/EC on waste incineration plants.
NOTE 1 The limit values of this European Standard are expressed in mg HCl/m3, on dry basis, at the reference conditions of 273 K and 101,3 kPa and at the reference O2 concentration.

Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von gasförmigen Chloriden, angegeben als HCl - Standardreferenzverfahren

Mit dem in dieser Europäischen Norm beschriebenen Verfahren wird die Konzentration von Chlorverbindungen in einem Abgas, die – nach Passage der Probenahmeeinrichtung einschließlich eines Partikelfilters – in der Absorptionslösung Cl–-Ionen bilden, bestimmt. Das Verfahren wurde durch Felduntersuchungen an Müllverbrennungsanlagen validiert. Es ist anwendbar für Abgase, in denen die Chloridkonzentration, angegeben als HCl, bei normalen Druck- und Temperaturbedingungen (siehe Anmerkung 1) zwischen 1 mg⋅m–3 und 5 000 mg⋅m–3 liegt, sowie in Bezug auf einen Emissionsgrenzwert, wie er z. B. in der Richtlinie 2000/76/EG über die Verbrennung von Abfällen festgelegt ist.
ANMERKUNG 1 Die mit dieser Europäischen Norm ermittelten Werte werden in mg/m3 (trocken) bei Normbedingungen (273 K, 101,3 kPa) und dem O2-Bezugsgehalt angegeben.

Emissions de sources fixes - Détermination de la concentration massique en chlorures gazeux, exprimée en HCl - Méthode de référence normalisée

La présente Norme européenne décrit la méthode de référence normalisée (SRM) avec trois techniques analytiques alternatives pouvant être utilisées pour déterminer la teneur en chlorures gazeux émise dans l’atmosphère par les conduits et les cheminées. Elle décrit les composants spécifiques et les exigences
concernant le système de mesurage. Un certain nombre de caractéristiques de performance ainsi que les critères de performance minimums correspondants sont fournis pour le système de mesurage (voir les Tableaux 1 et 2 en 7.2). La présente Norme européenne peut être utilisée comme SRM à condition que
l’incertitude globale de la méthode soit inférieure à ± 30,0 % de la valeur limite d’émission (VLE) journalière pour les incinérateurs et les grandes installations de combustion, ou à la VLE prescrite par les règlements correspondants pour les autres installations. Une méthode alternative à cette SRM peut être employée si l’utilisateur peut démontrer son équivalence conformément à la Spécification technique TS 14793.
La présente méthode détermine la concentration en composés chlorés donnant des ions Cl– dans la solution
d’absorption. La présente méthode de référence normalisée a été évaluée lors d’essais sur site d’incinération
des déchets. La méthode s’applique aux gaz résiduaires dont la concentration en chlorures, exprimée sous
forme de HCl, peut varier entre 1 mg⋅m–3 et 5 000 mg⋅m–3 dans des conditions normales de pression et de
température (voir la Note), et conformément aux valeurs limites d’émission établies dans les Directives du
Conseil suivantes :
- Directive du Conseil 2001/80/CE relative à la limitation des émissions de certains polluants dans
l-atmosphère en provenance des grandes installations de combustion ;
- Directive du Conseil 2000/76/CE sur l’incinération des déchets.

Emisije nepremičnih virov - Določevanje masne koncentracije plinastih kloridov, izraženih kot HCl - Standardna referenčna metoda

Metoda, ki je opisana v tem evropskem standardu, določa koncentracijo kloriranih spojin v odpadnih (dimnih) plinih, iz katerih se - po prehodu skozi sistem vzorčenja, vključno s filtriranjem delcev, v absorpcijski raztopini absorbirajo Cl- ioni. Ta standardna referenčna metoda je bila ovrednotena med terenskimi preskusi pri sežiganju odpadkov. Metoda velja za odpadne pline, v katerih se lahko koncentracija kloridov, izražena kot HCl, giblje od 1 mg-m3 do 5000 mg-m3 pri normalnih pogojih (tlak, temperatura)(glej opombo 1) ter v skladu z mejnimi vrednostmi emisij, določenih na primer v Direktivi Sveta 2000/76/ES o sežigalnicah odpadkov.
OPOMBA 1 Mejne vrednosti so v tem evropskem standardu izražene v mg HCl/m3 (suhe snovi) pri normalnih pogojih (273 K,101,3 kPa) in referenčni koncentraciji O2.

General Information

Status
Published
Public Enquiry End Date
19-Feb-2009
Publication Date
13-Jan-2011
Technical Committee
Current Stage
6060 - National Implementation/Publication (Adopted Project)
Start Date
13-Jan-2011
Due Date
20-Mar-2011
Completion Date
14-Jan-2011

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2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von gasförmigen Chloriden, angegeben als HCl - StandardreferenzverfahrenEmissions de sources fixes - Détermination de la concentration massique en chlorures gazeux, exprimée en HCl - Méthode de référence normaliséeStationary source emissions - Determination of mass concentration of gaseous chlorides expressed as HCl - Standard reference method13.040.40Stationary source emissionsICS:Ta slovenski standard je istoveten z:EN 1911:2010SIST EN 1911:2011en,fr,de01-februar-2011SIST EN 1911:2011SLOVENSKI
STANDARDSIST EN 1911-3:1999SIST EN 1911-2:1999SIST EN 1911-1:19991DGRPHãþD



SIST EN 1911:2011



EUROPEAN STANDARD NORME EUROPÉENNE EUROPÄISCHE NORM
EN 1911
August 2010 ICS 13.040.40 Supersedes EN 1911-1:1998, EN 1911-2:1998, EN 1911-3:1998English Version
Stationary source emissions - Determination of mass concentration of gaseous chlorides expressed as HCl - Standard reference method
Emissions de sources fixes - Détermination de la concentration massique en chlorures gazeux, exprimée en HCl - Méthode de référence normalisée
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von gasförmigen Chloriden, angegeben als HCl - Standardreferenzverfahren This European Standard was approved by CEN on 26 June 2010.
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 CEN 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 CEN Management Centre has the same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre:
Avenue Marnix 17,
B-1000 Brussels © 2010 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. EN 1911:2010: ESIST EN 1911:2011



EN 1911:2010 (E) 2 Contents Page Foreword .4Introduction .51Scope .62Normative references .63Terms, definitions and abbreviations .63.1Terms and definitions .63.2Abbreviations .94Principle . 115Sampling . 115.1Sampling strategy . 115.1.1General . 115.1.2Non isokinetic sampling . 125.1.3Isokinetic sampling. 135.1.4Losses of gaseous chlorides and side reactions during sampling . 145.2Sampling equipment . 145.3Sampling procedure . 185.3.1Preparation and installation of equipment . 185.3.2Sampling procedure . 195.3.3Validation of results . 206Analysis . 216.1Introduction . 216.2Reagents and samples to be analysed . 226.2.1Reagents for analysis . 226.2.2Samples to be analysed . 226.3Silver titration: potentiometric method . 226.3.1Apparatus . 226.3.2Reagents and solutions . 236.3.3Procedure . 236.3.4Interferences . 236.3.5Calculations . 246.4Mercuric-thiocyanate spectrophotometry . 246.4.1Warning . 246.4.2Apparatus . 246.4.3Reagents . 246.4.4Procedure . 256.4.5Interferences . 256.4.6Calculations . 266.5Ion-exchange chromatography . 267Expression of results . 278Determination of the characteristics of the method: sampling and analysis. 288.1General . 288.2Relevant performance characteristics of the method and performance criteria . 288.2.1General . 288.2.2Sampling procedure . 288.2.3Analyse procedure. 298.3Establishment of the uncertainty budget . 309Measurement report . 31SIST EN 1911:2011



EN 1911:2010 (E) 3 Annex A (informative)
Examples of absorbers . 32Annex B (informative)
Comparison between mercuric-thiocyanate spectrophotometry and ion exchange chromatography method (methods B and C) . 34Annex C (informative)
Example of assessment of compliance of the reference method for chlorides . 35C.1General . 35C.2Process of uncertainty estimation . 35C.3Specific conditions in the field . 36C.4Performance characteristics of the method . 37C.5Calculation of standard uncertainty of concentration measured. 38C.6Calculation of the overall (or expanded) uncertainty . 41C.7Uncertainty associated to the mass concentration of gaseous chlorides at O2 reference concentration . 41Annex D (informative)
Performance characteristics of the whole measurement method . 43D.1Analytical detection limit of the method . 43D.2Repeatability and reproducibility of the method in the field . 43Annex E (informative)
Significant technical changes . 45Bibliography . 46 SIST EN 1911:2011



EN 1911:2010 (E) 4 Foreword This document (EN 1911:2010) 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 February 2011, and conflicting national standards shall be withdrawn at the latest by February 2011. Attention is drawn to the possibility that some of the elements of this document may be the subject of patent rights. CEN [and/or CENELEC] shall not be held responsible for identifying any or all such patent rights. This document supersedes EN 1911-1:1998, EN 1911-2:1998 and EN 1911-3:1998. Annex E provides details of significant technical changes between this European Standard and the previous edition. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to implement this European Standard: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and the United Kingdom. SIST EN 1911:2011



EN 1911:2010 (E) 5 Introduction This European Standard describes the Standard Reference Method (SRM) with three alternative analytical techniques for determining gaseous chlorides content emitting to atmosphere from ducts and stacks. The specific components and the requirements for the measuring system are described. A number of performance characteristics with associated minimum performance criteria are specified for the measuring system (see Tables 1 and 2 in 8.2). This European Standard can be used as an SRM provided the overall uncertainty of the method is less than 30,0 % relative at the daily Emission Limit Value (ELV) for incineration and large combustion plants or at the ELV prescribed by the specific regulations for other plants. An Alternative Method to this SRM may be used provided that the user can demonstrate equivalence according to CEN/TS 14793. SIST EN 1911:2011



EN 1911:2010 (E) 6 1 Scope The method described in this European Standard determines the concentration of chlorinated compounds in a flue gas that – after passage of the sampling system including a particle filter – give Cl- ions in the absorption solution. This Standard Reference Method has been evaluated during field tests on waste incineration. The method applies to waste gases in which chlorides concentration expressed as HCl may vary between 1 mg⋅m-3 and 5 000 mg⋅m-3 under normal pressure and temperature conditions (see Note 1), and according to emission limit values laid down, for example, in the Council Directive 2000/76/EC on waste incineration plants. NOTE 1 The limit values of this European Standard are expressed in mg HCl/m3, on dry basis, at the reference conditions of 273 K and 101,3 kPa and at the reference O2 concentration.
NOTE 2 The required uncertainty results from the capacity of the method tested in the field (Annex D) and in the laboratory (see performance characteristics in Tables 1 and 2 and Annex C). 2 Normative references The following referenced documents are indispensable for the application of this document. For dated references, only the edition cited applies. For undated references, the latest edition of the referenced document (including any amendments) applies. EN 13284-1:2001, Stationary source emissions — Determination of low range mass concentration of dust — Part 1: Manual gravimetric method ENV 13005, Guide to the expression of uncertainly in measurement EN 15259:2007, Air quality — Measurement of stationary source emissions — Requirements for measurement sections and sites and for the measurement objective, plan and report EN ISO 3696:1995, Water for analytical laboratory use — Specification and test methods (ISO 3696:1987) EN ISO 10304-1, Water quality — Determination of dissolved anions by liquid chromatography of ions — Part 1: Determination of bromide, chloride, fluoride, nitrate, nitrite, phosphate and sulfate (ISO 10304-1:2007) EN ISO 14956, Air quality — Evaluation of the suitability of a measurement procedure by comparison with a required measurement uncertainty (ISO 14956:2002) 3 Terms, definitions and abbreviations 3.1 Terms and definitions For the purposes of this document, the following terms and definitions apply. 3.1.1 absorber device in which gaseous chloride is absorbed into an absorption solution 3.1.2 chemical blank chloride ion content of an unexposed sample of the absorption solution, plus reagents that are added to the solution before analysis if necessary SIST EN 1911:2011



EN 1911:2010 (E) 7 3.1.3 analytical detection limit
DL concentration value of the measurand below which there is at least 95 % level of confidence that the measured value corresponds to a sample free of that measurand 3.1.4 field blank value determined by a specific procedure used to ensure that no significant contamination has occurred during all steps of the measurement and to check that the operator can achieve a quantification level adapted to the task 3.1.5 isokinetic sampling sampling at a rate such that the velocity and direction of the gas entering the sampling nozzle is the same as that of the gas in the duct at the sampling point [EN 13284-1:2001] 3.1.6 measurand particular quantity subject to measurement [ISO/IEC Guide 99:2007, 2.6] 3.1.7 measurement series several successive measurements carried out on the same sampling plane and at the same process operating conditions [EN 13284-1:2001] 3.1.8 performance characteristic one of the quantities (described by values, tolerances, range, etc.) assigned to equipment in order to define its performance 3.1.9 analytical repeatability closeness of the agreement between the results of successive measurements of the same measurand carried out under the same conditions of measurement NOTE 1 Analytical repeatability conditions include:  the same measurement procedure;  the same laboratory;  the same sampling equipment, used under the same conditions and at the same location;  repetition over a short period of time. NOTE 2 Analytical repeatability may be expressed quantitatively in terms of the dispersion characteristics of the results.
[ISO/IEC Guide 99:2007, 3.6] NOTE 3 In this European Standard the analytical repeatability is expressed as a value with a level of confidence of 95 %. SIST EN 1911:2011



EN 1911:2010 (E) 8 3.1.10 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:  the same measurement procedure;  two sets of equipment, the performances of which are fulfilling the requirements of the reference method, used under the same conditions;  the same location;  implemented by the same laboratory;  typically calculated over 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. NOTE 3 In this European Standard the repeatability under field conditions is expressed as a value with a level of confidence of 95 %. 3.1.11 reproducibility in the field closeness of the agreement between the results of simultaneous measurements of the same measurand carried out with several sets of equipment under the same conditions of measurement NOTE 1 These conditions are called field reproducibility conditions and include:  the same measurement procedure;  several sets of equipment, the performance of which fulfils the requirements of the reference method, used under the same conditions;  the same location;  implemented by several laboratories. NOTE 2 Reproducibility may be expressed quantitatively in terms of the dispersion characteristics of the results. NOTE 3 In this European Standard the reproducibility under field conditions is expressed as a value with a level of confidence of 95 %. 3.1.12 sampling location specific area close to the sampling plane where the measurement devices are set up 3.1.13 sampling plane plane normal to the centreline of the duct at the sampling position [EN 13284-1:2001] 3.1.14 sampling point specific position on a sampling plane at which a sample is extracted SIST EN 1911:2011



EN 1911:2010 (E) 9 [EN 13284-1:2001] 3.1.15 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 to be measured 3.1.16 uncertainty parameter associated with the result of a measurement, that characterises the dispersion of the values that could reasonably be attributed to the measurand 3.1.17 standard uncertainty
u uncertainty of the result of a measurement expressed as a standard deviation
3.1.18 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 NOTE 1 ukU.= NOTE 2 In this European Standard, the expanded uncertainty is calculated with a coverage factor of k = 2, and with a level of confidence of 95 %. 3.1.19 combined uncertainty
uc standard uncertainty uattached to the measurement result calculated by combination of several standard uncertainties according to GUM
NOTE ∑==Niicuu12 3.1.20 overall uncertainty
cU expanded combined standard uncertainty attached to the measurement result calculated according to GUM NOTE ccukU×= 3.2 Abbreviations AgC
concentration of silver nitrate solution, in moles per litre (mol/l) rCI repeatability confidence interval RCI reproducibility confidence interval SIST EN 1911:2011



EN 1911:2010 (E) 10 corrC corrected concentration of measurand actualC concentration of measurand at actual O2 concentration )(ClchloridesC chlorides content expressed in milligrams Cl- per cubic metre )(HClchloridesC chlorides content expressed in milligrams HCl per cubic metre DL analytical detection limit MCl molar mass of chloride MHCl molar mass of hydrogen chloride chloridesm quantity of gaseous chlorides collected in the sampling device, , in milligrams Cl measO,2 dry oxygen content refO,2 oxygen reference concentration P absolute pressure in kilopascals (kPa) at the gas volume meter; P is equal to the sum of relative pressure measured at the gas volume meter relP plus atmospheric pressure atmP relP relative pressure measured at the gas volume meter in kilopascals (kPa) atmP atmospheric pressure in kilopascals (kPa) )(2OHpS saturated vapour pressure at the temperature of the gas meter, in kilopascals (kPa) resp residual vapour pressure, in kilopascals (kPa) rs repeatability standard deviation Rs reproducibility standard deviation t0,95;np-1 student factor for a level of confidence of 95 % and a degree of freedom of np-1 T actual temperature, in Kelvins (K) u standard uncertainty cu combined uncertainty U expanded uncertainty cU overall uncertainty Vstd volume of gas sampled under standard conditions and dry basis, in cubic metres (m³) SIST EN 1911:2011



EN 1911:2010 (E) 11 sv volume of absorption solution Se, in millilitres (ml) asv, aliquot portion of Se used for analysis, in millilitres (ml) 3AgNOV volume of the Ag NO3 solution used for dosing the solution Se , in millilitres (ml) 3,AgNOoV volume of the Ag NO3 solution used for taking into account the chemical blank value, in millilitres (ml) pTV, volume under actual conditions of temperature and pressure, on dry basis with "dry" gas meter or wet basis with "wet" gas meter, in cubic metres (m³) 4 Principle This European Standard describes the Standard Reference Method (SRM) for determining chloride ions content, expressed as HCl, emitting to atmosphere from ducts and stacks. The specific components and the requirements for the measuring system are described. A number of performance characteristics with associated minimum performance criteria are specified for the measuring system (see Tables 1 and 2 in 8.2). These performance characteristics and the overall uncertainty of the method shall meet the specifications given in this European Standard.
A known volume of flue gas is extracted representatively from a duct or a chimney during a certain period of time at a controlled flow rate with a heated probe. A heated filter removes the dust in the sampled volume, thereafter the gas stream containing gaseous chlorides is passed through a series of absorbers containing an absorption solution (chloride-free water). All compounds which are volatile at the temperature of filtration and produce chloride ions upon dissolution during sampling are measured by this method, which gives therefore the volatile inorganic chlorides content of the waste gas. The results shall be expressed as HCI. After sampling the solutions are analysed by one of the following methods:  silver titration: potentiometric method (Method A);  mercuric-thiocyanate spectrophotometry (Method B);  ion-exchange chromatography (Method C). 5 Sampling 5.1 Sampling strategy 5.1.1 General The test programme shall be established following the advice and requirements described in EN 15259:2007 (5.4, Clauses 6, 7 and 8). a) Quantification of several compounds simultaneously, if relevant. NOTE 1 Compounds such as gaseous chlorides, HF, SO2, NH3 and water vapour, can be sampled simultaneously in parallel side stream lines. NOTE 2 When performing isokinetic sampling the presence of water droplets means water vapour cannot be measured simultaneously in the same equipment. SIST EN 1911:2011



EN 1911:2010 (E) 12 NOTE 3 Gaseous chlorides and dust can be sampled simultaneously and require an isokinetic sampling with a probe equipped with a nozzle. b) Representativeness of the emission of the process. The following points shall be considered when preparing the sampling programme: 1) the nature of the plant process, e.g. steady state or discontinuous; 2) the homogeneity of the gas effluents at the sampling sections can be performed either by using an automatic HCl analyser or any other relevant surrogates gases (e.g. O2, CO2, etc.). When droplets are present, it is not necessary to perform the homogeneity test because a grid sampling is performed; 3) the expected concentration to be measured and any required averaging period, both of which can influence the measuring and sampling time. When a grid measurement is required, sampling time shall be in accordance with EN 13284-1 requirements related to the representativeness of the sample; 4) In some cases where flue gases are treated by a wet scrubber, they may be vapour saturated or slightly supersaturated, thus containing droplets which may have a high chloride content (dissolved HCl and/or dissolved chlorides). For example, this may occur when sampling gases downstream a humid scrubber without subsequent reheating. These droplets, sampled with the gas to some extent influence the results. It has been shown that, in such cases, the reproducibility and the accuracy of the measurement is better by using an isokinetic sampling than by using classical gas sampling by a straight probe. Therefore, when the occurrence of droplets is suspected or known in the gas to be analysed, isokinetic sampling is required. 5.1.2 Non isokinetic sampling Sampling shall be carried out at one or several points in the sampling section, in accordance with the result of the test of homogeneity carried out according to EN 15259. Sampling may be carried out using a straight heated probe, without nozzle. Dust is removed by a high efficiency heated filter, and then gaseous chlorides are collected in absorbers (see Figure 1).
Key 1 heated sampling probe
5 cartridge with desiccant (optional) 2 heated particle filter (alternatives)
6 pump 3 absorber(s)
7 flow meter behind the filter (e.g. diaphragm) or before the gas meter 4 guard bottle (optional)
8 gas meter Figure 1 — Example of non-isokinetic sampling equipment SIST EN 1911:2011



EN 1911:2010 (E) 13 5.1.3 Isokinetic sampling 5.1.3.1 Isokinetic sampling with a side stream Because probe nozzle diameters shall comply with EN 13284-1, isokinetic sampling often requires volume flow rates much higher than those which can be admitted by the absorbers used for gaseous chlorides collection. Therefore, downstream of the filter, only a part of the gases is drawn through the absorber(s) through a secondary line, the main line and the secondary line having their own gas metering systems and suction devices. The measurement of the flow in the main line can be measured either by a diaphragm or any other appropriate device, placed behind the filter and before the T piece or before the volume meter (see Figure 2).
Key 1 heated sampling probe
5 cartridge with desiccant (optional) 2 heated particle filter (alternatives)
6 pump 3 absorber(s)
7 flow meter behind the filter (e.g. diaphragm) or before the gas meter 4 guard bottle (optional)
8 gas meter Figure 2 — Example of isokinetic sampling equipment with a side stream For practical reasons it is difficult to adjust the secondary line volume flow rate quickly at each sampling point. Therefore, in the cases where the concentration is homogeneous in the sampling section, the flow rate can be kept constant. However, if the concentrations across the sampling section are not homogeneous, then the laboratory shall decide, depending on the measuring quality objectives to be reached, to fulfil or not the requirement EN 15259 of a flow rate proportional to the local veloc
...

SLOVENSKI STANDARD
oSIST prEN 1911:2009
01-januar-2009
(PLVLMHQHSUHPLþQLKYLURY'RORþHYDQMHPDVQHNRQFHQWUDFLMHSOLQDVWLKNORULGRY
L]UDåHQLKNRW+&O6WDQGDUGQDUHIHUHQþQDPHWRGD
Stationary source emissions - Determination of mass concentration of gaseous chlorides
expressed as HCl - Standard reference method
Emissionen aus stationären Quellen - Bestimmung der Massenkonzentration von
gasförmigen Chloriden, angegeben als HCl - Standardreferenzverfahren
Emissions de sources fixes - Détermination de la concentration massique en chlorures
gazeux, exprimée en HCl - Méthode de référence normalisée
Ta slovenski standard je istoveten z: prEN 1911
ICS:
13.040.40 (PLVLMHQHSUHPLþQLKYLURY Stationary source emissions
oSIST prEN 1911:2009 en,fr,de
2003-01.Slovenski inštitut za standardizacijo. Razmnoževanje celote ali delov tega standarda ni dovoljeno.

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oSIST prEN 1911:2009

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oSIST prEN 1911:2009
EUROPEAN STANDARD
DRAFT
prEN 1911
NORME EUROPÉENNE
EUROPÄISCHE NORM
October 2008
ICS 13.040.40 Will supersede EN 1911-1:1998, EN 1911-2:1998, EN
1911-3:1998
English Version
Stationary source emissions - Determination of mass
concentration of gaseous chlorides expressed as HCl - Standard
reference method
Emissions de sources fixes - Détermination de la Emissionen aus stationären Quellen - Bestimmung der
concentration massique en chlorures gazeux, exprimée en Massenkonzentration von gasförmigen Chloriden,
HCl - Méthode de référence normalisée angegeben als HCl - Standardreferenzverfahren
This draft European Standard is submitted to CEN members for enquiry. It has been drawn up by the Technical Committee CEN/TC 264.
If this draft becomes a European Standard, 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.
This draft European Standard was established by CEN 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 CEN Management Centre has the
same status as the official versions.
CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Cyprus, Czech Republic, Denmark, Estonia, Finland,
France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal,
Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom.
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 European Standard. It is distributed for review and comments. It is subject to change without notice and
shall not be referred to as a European Standard.
EUROPEAN COMMITTEE FOR STANDARDIZATION
COMITÉ EUROPÉEN DE NORMALISATION
EUROPÄISCHES KOMITEE FÜR NORMUNG
Management Centre: rue de Stassart, 36  B-1050 Brussels
© 2008 CEN All rights of exploitation in any form and by any means reserved Ref. No. prEN 1911:2008: E
worldwide for CEN national Members.

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oSIST prEN 1911:2009
prEN 1911:2008 (E)
Contents Page
Foreword.3
1 Scope .4
2 Normative references .4
3 Definitions .5
4 Sampling.8
4.1 Sampling principle.8
4.2 Sampling strategy.8
4.3 Sampling equipment .11
4.4 Sampling procedure .16
5 Analysis .19
5.1 Introduction.19
5.2 Reagents and samples to be analysed.20
5.3 Silver titration: potentiometric method .20
5.4 Mercuric-thiocyanate spectrophotometry.22
5.5 Ion-exchange chromatography .24
6 Expression of results .24
7 Determination of the characteristics of the method: sampling and analysis.25
7.1 General.25
7.2 Relevant performance characteristics of the method and performance criteria .26
7.3 Establishment of the uncertainty budget.28
8 Measurement report .29
Annex A (informative) Examples of absorbers .30
Annex B (informative) Comparison between mercuric-thiocyanate spectrophotometry and ion
exchange chromatography method (methods B and C).32
Annex C (informative) Example of assessment of compliance or reference method for chlorides
with requirements on emission measurements .33
Annex D (informative) Performance characteristics of the whole measurement method.40
Bibliography .42

2

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oSIST prEN 1911:2009
prEN 1911:2008 (E)
Foreword
This document (prEN 1911:2008) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the
secretariat of which is held by DIN.
This document is currently submitted to the CEN Enquiry.
This document will supersede EN 1911-1:1998, EN 1911-2:1998, EN 1911-3:1998.
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1 Scope
This European Standard describes the Standard Reference Method (SRM) with three alternative analytical
techniques for determining gaseous chlorides content emitting to atmosphere from ducts and stacks. The
specific components and the requirements for the measuring system are described. A number of performance
characteristics with associated minimum performance criteria are specified for the measuring system (see
tables 1 and 2 in 7.2). This European standard can be used as a SRM provided the overall uncertainty of the
method is less than ± 30,0 % relative at the daily Emission Limit Value (ELV) for incineration and large
combustion plants or at the ELV prescribed by the specific regulations for other plants.
An Alternative Method to this SRM may be used provided that the user can demonstrate equivalence
according to the Technical Specification TS 14793.

This method determines the concentration of chlorinated compounds that give Cl ions in the absorption
solution. This Standard Reference Method has been evaluated during field tests on waste incineration. The
method applies to waste gases in which chlorides concentration expressed as HCl may vary between
–3 –3

1 mg⋅m and 5 000 mg⋅m under normal pressure and temperature conditions (see Note), and according to
emission limit values 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.
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NOTE The limit values of EU directives are expressed in mg HCl/m , on dry basis, at the reference conditions of

273 K and 101,3 kPa and at the reference O concentration.
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2 Normative references
The following referenced documents are indispensable for the application of this document. For dated
references, only the edition cited applies. For undated references, the latest edition of the referenced
document (including any amendments) applies.
EN 13284-1:2001, Stationary source emissions – Determination of low range mass concentrations of dust –
Part 1: Manual gravimetric method
TS 14793:2004, Stationary source emission - Intra-laboratory validation procedure for an alternative method
compared to a reference method
EN ISO 14956:2002, Air Quality – Evaluation of the suitability of a measurement method by comparison with a
stated measurement uncertainty
ENV 13005:1999, Guide to the expression of uncertainly in measurement (GUM)
EN ISO 3696:1995, Water for analytical laboratory use – Specification and test methods (ISO 3696:1987)
EN ISO 10304-1:1995, Water quality – Determination of dissolved fluoride, chloride, nitrite, orthophosphate,
bromide, nitrate and sulphate ions, using liquid chromatography of ions – Part 1: Method for water with low
contamination (ISO 10304-1:1992)
EN ISO 20988:2007, Air quality – Guidelines for estimating measurement uncertainty
EN 15259:2007, Air quality – Measurement of stationary source emissions – Requirements for measurement
sections and sites and for the measurement objective, plan and report
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3 Definitions
For the purposes of this European Standard, the following terms and definitions apply:
3.1
absorber
device in which gaseous chloride is absorbed into an absorption liquid
3.2
absorption efficiency (є)
ratio є of quantity of the analyte q collected in the first absorber divided by the quantity of the analyte
1
collected in the first and the second absorber (q +q )
1 2
є = q / (q + q )
1 1 2
3.3
automatic measuring system (AMS)
measuring system permanently installed on site for continuous monitoring of emissions
NOTE 1 An AMS is traceable to a standard reference method (SRM).
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.
3.4
calibration of an AMS
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
chemical blank value
chloride ion content of an unexposed sample of the absorption solution, plus reagents that are added to the
solution before analysis if necessary
3.6
analytical detection limit (D )
L
concentration value of the measurand below which there is at least 95 % level of confidence that the
measured value corresponds to a sample free of that measurand
3.7
emission limit value (ELV)
emission limit value according to EU Directives on the basis of 30 min, 1 hour or 1 day
3.8
field blank
value determined by a specific procedure used to ensure that no significant contamination has occurred
during all steps of the measurement and to check that the operator can achieve a quantification level adapted
to the task
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3.9
isokinetic sampling
sampling at a rate such that the velocity and direction of the gas entering the sampling nozzle is the same as
that of the gas in the duct at the sampling point
[EN 13284-1]
3.10
measurand
particular quantity subject to measurement
[VIM 2.6]
3.11
measurement series
several successive measurements carried out on the same sampling plane and at the same process
operating conditions
[EN 13284-1]
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:
 the same measurement procedure
 the same laboratory
 the same sampling equipment, used under the same conditions
 the 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 equipments under the same conditions of measurement
NOTE 1 These conditions include:
 the same measurement procedure
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 two equipments, the performances of which are fulfilling the requirements of the reference method, used under the
same conditions
 the 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 with several sets of equipment under the same conditions of measurement
NOTE 1 These conditions are called field reproducibility conditions and include:
 the same measurement procedure
 several sets of equipment, the performance of which fulfils the requirements of the reference method, used under the
same conditions
 the 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
sampling location
specific area close to the sampling plane where the measurement devices are set up
3.18
sampling plane
plane normal to the centreline of the duct at the sampling position
[EN 13284-1]
3.1.21
sampling point
specific position on a sampling plane at which a sample is extracted
[EN 13284-1]
3.19
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 (3.1.11) to be
measured
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3.20
uncertainty
parameter associated with the result of a measurement, that characterises the dispersion of the values that
could reasonably be attributed to the measurand
3.20.1
standard uncertainty u
uncertainty of the result of a measurement expressed as a standard deviation u
3.20.2
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 %.
3.21
combined uncertainty u
c
standard uncertainty u attached to the measurement result calculated by combination of several standard
c
uncertainties according to GUM
3.22
overall uncertainty U
c
expanded combined standard uncertainty attached to the measurement result calculated according to GUM
U = k ⋅ u
c c
3.23
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
Add a sub-clause with symbols and abbreviations
4 Sampling
4.1 Sampling principle
A known volume of flue gas is extracted representatively from a duct or a chimney during a certain period of
time at a controlled flow rate with a temperature regulated probe. A temperature regulated filter removes the
dust in the sampled volume, thereafter the gas stream containing gaseous chlorides is passed through a
series of absorbers containing an absorption solution (chloride-free water).
All compounds which are volatile at the temperature of filtration and produce chloride ions upon dissolution
during sampling are measured by this method, which gives therefore the volatile inorganic chlorides content of
gases expressed as HCI.
4.2 Sampling strategy
4.2.1 General
The test programme shall be established on a sampling strategy that shall integrate at the same time:
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 Quantification of several compounds simultaneously.
 The following compounds gaseous chlorides, HF, SO , NH and H O can be sampled simultaneously in
2 3 2
parallel side stream lines. If isokinetic sampling is required, because droplets are present, H O cannot be
2
included in the measurement. Gaseous chlorides and dust can be sampled simultaneously in parallel side
stream lines and require an isokinetic sampling with a probe equipped with a nozzle.
 Representativeness of the emission of the process. The following points should be considered when
preparing the sampling programme:
 the nature of the plant process e.g. steady state or discontinuous;
 the expected concentration to be measured and any required averaging period, both of which can
influence the measuring and sampling time. When a grid measurement is required, sampling time
shall be in accordance with EN 13284-1 requirements related to the representativeness of the
sample;
 in the case of combination of several compounds measurement, each relevant SRM may give
guidelines to get an acceptable sample;
 EN 15259 deals with problem of the homogeneity of the gas effluents at the sampling sections. The
test of homogeneity could be performed either by using an automatic HCl analyser or any other
surrogates gases (e.g. O , CO , …).
2 2
The diagram below describes the strategy of measuring to be followed according to the situation met.


In some cases, the waste gases to be analysed may be water vapour saturated or slightly supersaturated,
thus containing droplets which may have a high chloride content (dissolved HCl and/or dissolved chlorides).
For example, this may occur when sampling gases downstream a humid scrubber without subsequent
reheating.
These droplets, sampled with the gas to some extent influence the results. It has been shown that, in such
cases, the reproducibility of measurement is better by using an isokinetic sampling than by using classical gas
sampling by a straight probe. Therefore, when the occurrence of droplets is suspected or known in the gas to
be analysed, isokinetic sampling is required (see Note). When droplets are absent then non-isokinetic
sampling may be used.
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NOTE When droplets are present and when a high heterogeneity has been demonstrated, the absorption efficiency
may fail. In that case, instead of a isokinetic grid sampling the grid sampling is carried out with a sampling time at each
point that is proportional to the local velocity.
4.2.2 Isokinetic sampling
Because probe nozzle diameters shall comply with EN 13284-1 and EN 15259 requirements isokinetic
sampling requires usually volume flow rates much higher than those which can be admitted by the absorbers
used for Gaseous chlorides collection. Therefore, downstream of the filter, only a part of the gases is drawn
through the absorber(s) through a secondary line, the main line and the secondary line having their own gas
metering systems and suction devices. The ratio between the main and the secondary line volume flow rates
shall be kept constant. To make easier the control of this ratio, the measurement, by a diaphragm or any other
appropriate device, of the total flow passing through the main line may be useful (see Figure 1).
NOTE A sampling system without any secondary line (side stream) can be used provided that the absorption
efficiency requirements in 4.3.2.2.2 are fulfilled.

1 nozzle and heated sampling probe    7 guard bottle (optional)
2 regulated temperature particle filter    8 cartridge with desiccant (optional)
3 heated T piece     9 pump
4 main flow unit for suction and measuring volume flow rate 10 flow meter
5 regulated temperature connecting line (optional)    11 gas meter
6 absorber(s)     12 diaphragm for total flow rate measurement (optional)
Figure 1 — Example of isokinetic sampling equipment
4.2.3 Non isokinetic sampling
Sampling shall be carried out at one or several points in the sampling section, in accordance with the result of
the test of homogeneity carried out according to EN 15259.
Sampling may be carried out using a straight regulated temperature probe, without nozzle. Dust is removed by
a high efficiency heated filter, then gaseous chlorides are collected in absorbers.
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1 heated sampling probe    8 cartridge with desiccant (optional)
2 regulated temperature particle filter   9 pump
3 heated T piece     10 flow meter
5 regulated temperature connecting line (optional)  11 gas meter
6 absorber (s)     12 diaphragm for total flow rate measurement
7 guard bottle (optional)
Figure 2 — Example of non-isokinetic sampling equipment
4.2.4 Losses of gaseous chlorides and side reactions during sampling
Attention is drawn to the risks of losses of gaseous chlorides in the sampling system, due to its high reactivity
and solubility: All the parts of the sampling system upstream of the absorber shall be made of inert materials,
and shall be heated in order to avoid cold points, which can lead to large losses of gaseous chlorides. Any
parts that are not heated shall be rinsed.
Some kinds of waste gases (e.g. incinerator plants, etc.) may contain chemical species (e.g. calcium salts or
hydroxide, ammonium salts or free ammonia, etc.) which can react with gaseous chlorides.
There are some experimental evidences that these reactions are strongly enhanced by filtration of sampled
gases at temperature below 130 °C. Because most of these side reactions products are retained on the filter,
this can lead to large underestimation of waste gases gaseous chlorides concentrations: it is the reason why
this European standard requires a minimum filtration temperature of 160 °C, and 20 °C higher than the acid
dew point of gases. When ammonia and chloride salts are present, a temperature of 180 °C is required to
avoid formation of NH Cl on the filter.
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4.3 Sampling equipment
4.3.1 Isokinetic sampling equipment
4.3.1.1 Main line
An example of the whole isokinetic sampling equipment is shown in Figure 1.
4.3.1.1.1 Probe
The length of the probe shall be enough to preheat the gas before entering the filter.
In order to access the representative measurement point(s) of the sampling plane, probes of different lengths
and inner diameters may be used, but the residence time of the sample gas in the probe shall be minimised.
The probe may be marked before sampling in order to reach more easily the representative measurement
point(s) in the measurement plane.
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The heated probe and entry nozzle shall be designed in accordance with EN 13284-1. However, since these
parts are often made of borosilicate glass, which is difficult to manufacture too close tolerances, requirements
may be less stringent concerning the edge of the entry nozzle.
4.3.1.1.2 Filter housing
The filter housing is located directly behind the probe (out-stack filtration).
If condensation is liable to occur in the sampling probe or in the filter housing, then a heated out-stack filter
housing shall be used. For out-stack filtration, the filter housing shall be heated at the controlled temperature
(see 4.2.4). It shall be connected to the probe without any cold path between the two.
Filter housings of different designs may be used, but the residence time of the sample gas shall be minimised.
NOTE 1 The filter housing has the possibility to be jointed with the probe thereby avoiding leaks.
NOTE 2 A stop valve after the filter housing can be useful to prevent back flush of absorption solution into the probe or
into the filter when sampling in flue gases under unfavourable conditions (e.g. high depression in the duct).
NOTE 3 In special cases where the sample gas temperature is > 200 °C, the heating jacket around the sampling probe,
filter housing and connector line may be switched off. However the temperature in the sampled gas just after the
filter housing should not fall below 20 °C above the (acid) dew point temperature.
4.3.1.1.3 Particle filter
The efficiency of the filter material shall be better than 99,5 % on a test aerosol of 0,3 µm mean diameter (or
99,9 % on a test aerosol of 0,6 µm mean diameter), for the maximal actual volume flow rate of the filter, to
avoid measurement errors due to fine particles of chloride salts which could be collected in the absorbers and
analysed as gaseous chlorides.
Filters with the most suitable properties for this purpose are plane filters: convenient borosilicate glass and
quartz fibres filters of different diameters and certified efficiency are commercially available.
Diameters of about 40 mm to 160 mm are generally convenient.
4.3.1.1.4 Temperature controller
A temperature controller is required for the probe and for the filter housing. It shall be capable of controlling
temperature with an uncertainty of ± 2,5 K or better (uncertainty of calibration).
4.3.1.1.5 Suction and volume flow meter
The unit for suction and metering the volume flow rate in the main line shall have an adjustable volume flow
rate and flow meter, in order to comply with isokinetic criteria.
Various kinds of devices may be used, for instance:
 volume flow rate measurement on wet basis using an heated orifice plate followed by a compressed air
ejector acting as suction device;
 water vapour removing device (condenser, dryer, etc.), leak tight pump, dry gas;
 meter and rotameter.
Flow meters shall be calibrated (corrected temperature, pressure and humidity). The volume flow rate in the
secondary line shall be taken into account in order to calculate the required volume flow rate in the main line.
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4.3.1.2 Secondary line
4.3.1.2.1 Connection to the main line
A tee piece ensures the division of the sample between the secondary line which allows a gas volume flow
rate that fulfils the collection efficiency criteria and the main line,
-1 -1
NOTE A flow of about 2 l⋅min to 3 l⋅min is generally used.
Care shall be taken to design the sampling system in such a way that no condensation shall occur between
the filter and the tee connection.
A line connecting the heated separator to the absorber made of borosilicate glass or PTFE. Parts of the line
which will not be rinsed shall be heated
...

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