1、BSI Standards PublicationPD CEN/TS 13649:2014Stationary source emissions Determination of the massconcentration of individualgaseous organic compounds Sorptive sampling methodfollowed by solvent extractionor thermal desorptionPD CEN/TS 13649:2014 PUBLISHED DOCUMENTNational forewordThis Published Doc
2、ument is the UK implementation of CEN/TS13649:2014. It supersedes BS EN 13649:2002 which is withdrawn.The UK participation in its preparation was entrusted to TechnicalCommittee EH/2/1, Stationary source emission.A list of organizations represented on this committee can beobtained on request to its
3、secretary.This publication does not purport to include all the necessaryprovisions of a contract. Users are responsible for its correctapplication. The British Standards Institution 2014. Published by BSI StandardsLimited 2014ISBN 978 0 580 74710 6ICS 13.040.40Compliance with a British Standard cann
4、ot confer immunity fromlegal obligations.This Published Document was published under the authority of theStandards Policy and Strategy Committee on 31 December 2014.Amendments issued since publicationDate Text affectedPD CEN/TS 13649:2014TECHNICAL SPECIFICATION SPCIFICATION TECHNIQUE TECHNISCHE SPEZ
5、IFIKATION CEN/TS 13649 December 2014 ICS 13.040.40 Supersedes EN 13649:2001English Version Stationary source emissions - Determination of the mass concentration of individual gaseous organic compounds - Sorptive sampling method followed by solvent extraction or thermal desorption Emissions de source
6、s fixes - Dtermination de la concentration massique en composs organiques gazeux individuels - chantillonnage par adsorption et extraction par solvant ou thermodsorption Emissionen aus stationren Quellen - Bestimmung der Massenkonzentration von gasfrmigen organischen Einzelverbindungen - Sorptive Pr
7、obenahme und Lsemittelextraktion oder thermische Desorption This Technical Specification (CEN/TS) was approved by CEN on 25 August 2014 for provisional application. The period of validity of this CEN/TS is limited initially to three years. After two years the members of CEN will be requested to subm
8、it their comments, particularly on the question whether the CEN/TS can be converted into a European Standard. CEN members are required to announce the existence of this CEN/TS in the same way as for an EN and to make the CEN/TS available promptly at national level in an appropriate form. It is permi
9、ssible to keep conflicting national standards in force (in parallel to the CEN/TS) until the final decision about the possible conversion of the CEN/TS into an EN is reached. CEN members are the national standards bodies of Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estoni
10、a, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and United Kingdom. EUROPEAN COMMITTEE FOR STANDA
11、RDIZATION COMIT EUROPEN DE NORMALISATION EUROPISCHES KOMITEE FR NORMUNG CEN-CENELEC Management Centre: Avenue Marnix 17, B-1000 Brussels 2014 CEN All rights of exploitation in any form and by any means reserved worldwide for CEN national Members. Ref. No. CEN/TS 13649:2014 EPD CEN/TS 13649:2014CEN/T
12、S 13649:2014 (E) 2 Contents Page Foreword 4 1 Scope 5 2 Normative references 5 3 Terms and definitions .5 4 Principle 6 5 Apparatus and materials .6 5.1 Method of measurement .6 5.2 Sampling system .8 5.3 Sampling tubes 8 5.3.1 Sampling tubes for solvent extraction 8 5.3.2 Sampling tubes for thermal
13、 desorption.8 5.4 Pumps and other devices for sampling 8 5.5 Gas volume meter 9 5.6 Analytical reagents 9 5.6.1 General 9 5.6.2 Extraction solvent (for solvent extraction) .9 5.6.3 Reference materials for calibration of the analytical procedure 9 5.7 Analytical apparatus . 10 5.7.1 Capillary gas chr
14、omatograph (GC) . 10 5.7.2 Thermal desorber (for thermal desorption) . 10 6 Sampling procedure . 10 6.1 General . 10 6.2 Sampling conditions 10 6.3 Measurement of waste gas sample volume . 11 6.4 Control of leakage. 11 6.5 Handling, storage, transport of sampled tubes . 11 6.5.1 General . 11 6.5.2 A
15、ctivated carbon (charcoal) tubes 11 6.5.3 Thermal desorption tubes 12 6.6 Blanks 12 6.6.1 Field blanks . 12 6.6.2 Analytical (laboratory) blanks . 12 6.6.3 Solvent blank . 12 7 Analytical procedure 12 7.1 Calibration of the GC analysis . 12 7.1.1 GC calibration for analysis of solvent extracts . 12
16、7.1.2 Calibration for thermal desorption analysis 13 7.2 Sample preparation (desorption/extraction) 13 7.2.1 Solvent desorption . 13 7.2.2 Thermal desorption 14 7.3 Analysis . 14 7.3.1 GC analysis of extract from activated carbon tubes. 14 7.3.2 Thermal desorption / GC analysis of sorbent tubes . 14
17、 7.4 Quantification of individual organic compound concentrations . 15 8 Calculation of results . 16 8.1 Concentration 16 8.2 Uncertainty 16 PD CEN/TS 13649:2014CEN/TS 13649:2014 (E) 3 9 Quality control . 16 9.1 General . 16 9.2 Performance requirements . 17 9.2.1 Sampling. 17 9.2.2 Analytical 17 10
18、 Report . 18 Annex A (normative) Sample trains 19 Annex B (informative) Solvent extraction of activated charcoal tubes . 23 Annex C (informative) Additional information on flue gas sampling using thermal desorption tubes . 24 Annex D (informative) Validation of monitoring methods for speciated organ
19、ic substances in stack gas 27 Annex E (informative) Safety measures . 45 Bibliography 46 PD CEN/TS 13649:2014CEN/TS 13649:2014 (E) 4 Foreword This document (CEN/TS 13649:2014) has been prepared by Technical Committee CEN/TC 264 “Air quality”, the secretariat of which is held by DIN. Attention is dra
20、wn 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 13649:2001. Significant technical changes between this Technical Specifica
21、tion and the previous edition of EN 13649 are: a) the status of the document has been changed from European Standard (EN) to Technical Specification (TS); b) the scope has been clarified regarding the use of the TS and its applicability; c) a decision tree for the determination of the sampling proce
22、dure has been included; d) the sampling strategy has been aligned with EN 15259; e) the thermal desorption technique has been added; f) comprehensive information on the validation of monitoring methods for speciated organic substances in stack gas is given. According to the CEN-CENELEC Internal Regu
23、lations, the national standards organizations of the following countries are bound to announce this Technical Specification: Austria, Belgium, Bulgaria, Croatia, Cyprus, Czech Republic, Denmark, Estonia, Finland, Former Yugoslav Republic of Macedonia, France, Germany, Greece, Hungary, Iceland, Irela
24、nd, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland, Turkey and the United Kingdom. PD CEN/TS 13649:2014CEN/TS 13649:2014 (E) 5 1 Scope This Technical Specification specifies procedures for the sampling, prep
25、aration and analysis of individual volatile organic compounds (VOCs) in waste gas, such as those arising from solvent using processes. Sampling occurs by adsorption on sorbents, preparation by solvent extraction or thermodesorption and analysis by gas chromatography. Examples of individual VOC are g
26、iven in relevant industry sector BAT Reference documents (BREFs). The results obtained are expressed as the mass concentration (mg/m3) of the individual gaseous organic compounds. This document is suitable for measuring individual VOCs whose ranges vary depending on compound and test method, refer t
27、o Annex B and C. This Technical Specification may be used to meet the monitoring requirements of the Industrial Emission Directive (IED) and associated supporting documents. This Technical Specification is not suitable for measuring total organic carbon (TOC). For the measurement of the mass concent
28、ration of total organic carbon then EN 12619 3 is applicable. 2 Normative references The following documents, in whole or in part, are normatively referenced in this document and are indispensable for its application. For dated references, only the edition cited applies. For undated references, the
29、latest edition of the referenced document (including any amendments) applies. EN 15259, Air quality - Measurement of stationary source emissions - Requirements for measurement sections and sites and for the measurement objective, plan and report EN ISO 14956, Air quality - Evaluation of the suitabil
30、ity of a measurement procedure by comparison with a required measurement uncertainty (ISO 14956) EN ISO 16017-1, Indoor, ambient and workplace air - Sampling and analysis of volatile organic compounds by sorbent tube/thermal desorption/capillary gas chromatography - Part 1: Pumped sampling (ISO 1601
31、7-1) 3 Terms and definitions For the purposes of this document, 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 collected by the adsorbent expressed as a percentage 3.2 sampling tube for solvent
32、extraction glass tube filled with activated carbon as the adsorbent 3.3 sampling tubes for thermal desorption stainless steel, inert-coated steel or glass tube-form samplers supplied capped and packed with one or more conditioned, thermal desorption compatible sorbents PD CEN/TS 13649:2014CEN/TS 136
33、49:2014 (E) 6 3.4 uncertainty parameter associated with the result of a measurement, that characterizes the dispersion of the values that could reasonably be attributed to the measurand SOURCE: ISO/IEC Guide 98-3:2008 2 3.5 volatile organic compound VOC any organic compound having at 293,15 K a vapo
34、ur pressure of 0,01 kPa or more, or having a corresponding volatility under the particular conditions of use 3.6 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 a
35、chieve a quantification level adapted to the task 4 Principle There are three steps in the measurement of individual gaseous organic compounds: sampling, desorption and analysis. Sampling approaches vary depending on waste gas conditions. Suitable sorbent shall be selected. This document specifies s
36、olvent extraction or thermal desorption. Analysis is by gas chromatography. Other methods may also be applicable e.g. canister, as an alternative to sorbent sampling for very volatile compounds, or condensate trap (catchpot) sampling systems, as an alternative to dilution sampling, providing their s
37、uitability can be demonstrated, e.g. according to CEN/TS 14793 1. Figure 1 shows the decision tree for determining the sampling procedure. 5 Apparatus and materials 5.1 Method of measurement The sample gas is extracted from the waste gas exhaust duct via a sampling system and onto a solid sorbent tu
38、be using a pump. The solid sorbent tube is then solvent extracted or thermally desorbed and the compounds are determined by gas chromatography. Many of the solvent using processes covered by the Industrial Emissions Directive produce waste gases which do not have a high water content. This document
39、requires the use of a dilution sampling system when the concentration of water or solvent is high enough to cause the risk of condensation. NOTE The limit values of EU Directives are expressed in mg/m3, on a wet basis, for non-combustion process and on a dry basis, for combustion processes, at the r
40、eference conditions of 273 K and 101,3 kPa. PD CEN/TS 13649:2014CEN/TS 13649:2014 (E) 7 Figure 1 Decision tree for determination of sampling procedure Liquid water interferes with the sorption process and shall not be allowed to reach the sorbent material (activated carbon or thermal desorption comp
41、atible sorbents). There shall be no visible condensation within the tube. Drying tubes, e.g. sodium sulfate, shall not be used upstream of the sorbent because of the risk of VOC losses. Sorbent sampling methods (activated carbon or thermal desorption-compatible) are only compatible with the vapour-p
42、hase fraction of semi-volatile compounds. Any particulates in the sample gas shall be entrained on filters before the sample is allowed to reach the sorbent bed. PD CEN/TS 13649:2014CEN/TS 13649:2014 (E) 8 5.2 Sampling system The set-up of a suitable sampling system is shown in Annex A. The sampling
43、 system shall be made of materials which are chemically and physically inert to the constituents of the gaseous effluent. Glass, PTFE and polypropylene fluoride or any other material for which it has been shown that they do not absorb or react with compounds present in the sample gas at the temperat
44、ure considered, are suitable. To avoid contamination from particulate, a dust filter shall be used. This should be heated if necessary, depending on application. 5.3 Sampling tubes 5.3.1 Sampling tubes for solvent extraction The sorbent tube, filled with activated carbon as the adsorbent, shall have
45、 the following characteristics: a main adsorbent layer containing 100 mg of activated carbon with a glass wool plug at the front of the tube; a security adsorbent layer to detect breakthrough, containing 50 mg of activated carbon separated from the front layer. Sorbent tubes shall be used in accorda
46、nce with the manufacturers instructions to avoid leakage and sample loss. Open or used carbon tubes shall not be reused. NOTE A suitable type of tubes is NIOSH type B with closed melted ends. 5.3.2 Sampling tubes for thermal desorption Stainless steel, inert-coated steel or glass samplers supplied c
47、apped and packed with one or more conditioned, thermal desorption compatible sorbents shall be used for organic vapour sampling and subsequent thermal desorption analysis. See Annex C and EN ISO 16017-1 for more details. The sampling end of an identical, secondary (back-up) tube can be connected to
48、the outlet of the primary sampling tube as a check on breakthrough. See 6.3 and Annex C for more information. Unions for connecting the two tubes in series shall comprise inert materials such as stainless steel, coated stainless steel or PTFE and shall not damage tube ends. NOTE Stainless steel (or
49、inert-coated steel) compression couplings fitted with combined PTFE ferrules have been found to be effective for connecting sample tubes together in series. Thermal desorption sampling tubes can be re-used many times (typically 100 thermal cycles). Conditioned tubes shall be considered sufficiently clean if individual artefact masses do not exceed 10 % of the mass retained when sampling flue gases at the lowest concentration of interest. See also 6.6. 5.4 Pumps and other devices for sampling A sampling pump or some alternative means of pulling a controlled flo
