1、DRAFT FOR DEVELOPMENTDD CEN/TS 15439:2006Biomass gasification Tar and particles in product gases Sampling and analysisICS 13.040.40; 75.160.10g49g50g3g38g50g51g60g44g49g42g3g58g44g55g43g50g56g55g3g37g54g44g3g51g40g53g48g44g54g54g44g50g49g3g40g59g38g40g51g55g3g36g54g3g51g40g53g48g44g55g55g40g39g3g37g
2、60g3g38g50g51g60g53g44g42g43g55g3g47g36g58Licensed Copy: Wang Bin, na, Tue May 29 07:33:31 GMT+00:00 2007, Uncontrolled Copy, (c) BSIDD CEN/TS 15439:2006This Draft for Development was published under the authority of the Standards Policy and Strategy Committee on 30 March 2007 BSI 2007ISBN 978 0 580
3、 50444 0National forewordThis Draft for Development was published by BSI. It is the UK implementation of CEN/TS 15439:2006.This publication is not to be regarded as a British Standard.It is being issued in the Draft for Development series of publications and is of a provisional nature. It should be
4、applied on this provisional basis, so that information and experience of its practical application can be obtained.Comments arising from the use of this Draft for Development are requested so that UK experience can be reported to the European organization responsible for its conversion to a European
5、 standard. A review of this publication will be initiated not later than 3 years after its publication by the European organization so that a decision can be taken on its status. Notification of the start of the review period will be made in an announcement in the appropriate issue of Update Standar
6、ds.According to the replies received by the end of the review period, the responsible BSI Committee will decide whether to support the conversion into a European Standard, to extend the life of the Technical Specification or to withdraw it. Comments should be sent to the Secretary of the responsible
7、 BSI Technical Committee at British Standards House, 389 Chiswick High Road, London W4 4AL.The UK participation in its preparation was entrusted to Technical Committee PTI/17, Solid biofuels.A list of organizations represented on PTI/17 can be obtained on request to its secretary.This publication do
8、es not purport to include all the necessary provisions of a contract. Users are responsible for its correct application. Amendments issued since publicationAmd. No. Date CommentsLicensed Copy: Wang Bin, na, Tue May 29 07:33:31 GMT+00:00 2007, Uncontrolled Copy, (c) BSITECHNICAL SPECIFICATIONSPCIFICA
9、TION TECHNIQUETECHNISCHE SPEZIFIKATIONCEN/TS 15439May 2006ICS 13.040.40; 75.160.10English VersionBiomass gasification - Tar and particles in product gases -Sampling and analysisGazification de biomasse - Goudron et particules dans lesgaz produits - chantillonnage et analyseBiomassevergasung - Teer u
10、nd Staub in Produktgasen -Probenahme und analytische BestimmungThis Technical Specification (CEN/TS) was approved by CEN on 21 February 2006 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
11、submit theircomments, 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 availablepromptly at national level in an appropriate form. It is perm
12、issible 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, Cyprus, Czech Republic, Denmark, Estonia, Finland, France,G
13、ermany, 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 STANDARDIZATIONCOMIT EUROPEN DE NORMALISATIONEUROPISCHES KOMITEE FR NORMUNGM
14、anagement Centre: rue de Stassart, 36 B-1050 Brussels 2006 CEN All rights of exploitation in any form and by any means reservedworldwide for CEN national Members.Ref. No. CEN/TS 15439:2006: ELicensed Copy: Wang Bin, na, Tue May 29 07:33:31 GMT+00:00 2007, Uncontrolled Copy, (c) BSI2 Contents Page Fo
15、reword3 Introduction .4 1 Scope 5 2 Normative references 5 3 Terms and definitions .5 4 Symbols and abbreviations 8 5 Principle of the measurement method 8 5.1 Introduction8 5.2 Sampling.8 5.3 Analysis 8 6 Reagents.9 6.1 Solvent for tar collection and Soxhlet extraction.9 6.2 Carrier gas in gas chro
16、matography.9 6.3 Calibration standards9 7 Equipment 9 7.1 Equipment for sampling9 7.2 Equipment for sample pretreatment and analysis 13 8 Preparation of sampling equipment . 13 8.1 Preconditioning of filter thimbles . 13 8.2 Cleaning of equipment . 14 8.3 Preparation of impinger bottles or Petersen
17、column 14 8.4 Sampling train leak test . 14 9 Procedure for sampling . 15 9.1 Introduction. 15 9.2 Duration of sampling 15 9.3 Sampling procedure . 16 10 Storage of samples. 16 11 Preparation for analysis. 17 11.1 Introduction. 17 11.2 Requirements for GC calibration standards and internal standards
18、 (ISTD) 17 12 Analysis procedures 18 12.1 Soxhlet extraction procedure 18 12.2 Combination of solvents 19 12.3 Determination of particle mass . 19 12.4 Determination of gravimetric tar mass. 19 12.5 Determination of individual tar compounds by GCMS or GC-FID. 20 13 Calculation of GC results. 21 14 P
19、erformance characteristics . 21 14.1 Introduction. 21 14.2 Performance of the analysis methods (Round Robin tests) 22 14.3 Performance of the whole Technical Specification (parallel tests). 23 15 Test report . 24 Annex A (informative) List of most abundant individual organic compounds in biomass gas
20、ification product gases . 25 Annex B (normative) List of organic compounds for which precision data have been collected . 26 Annex C (normative) Dimensions of the Petersen column 27 Annex D (informative) Additional information on Round Robin analysis 28 Annex E (informative) Additional information o
21、n parallel tests 34 Bibliography. 41 CEN/TS 15439:2006Licensed Copy: Wang Bin, na, Tue May 29 07:33:31 GMT+00:00 2007, Uncontrolled Copy, (c) BSI3 Foreword This Technical Specification (CEN/TS 15439:2006) has been prepared by Working Group CEN/BT/TF 143 “Measurement of organic contaminants (tar) in
22、biomass producer gases”, the secretariat of which is held by NEN. According to the CEN/CENELEC Internal Regulations, the national standards organizations of the following countries are bound to announce this CEN Technical Specification: Austria, Belgium, Cyprus, Czech Republic, Denmark, Estonia, Fin
23、land, France, Germany, Greece, Hungary, Iceland, Ireland, Italy, Latvia, Lithuania, Luxembourg, Malta, Netherlands, Norway, Poland, Portugal, Romania, Slovakia, Slovenia, Spain, Sweden, Switzerland and United Kingdom. CEN/TS 15439:2006Licensed Copy: Wang Bin, na, Tue May 29 07:33:31 GMT+00:00 2007,
24、Uncontrolled Copy, (c) BSI4Introduction The main contaminants in the product gases of biomass gasification are dust and soot particles, tars, alkali metals, acid gases and alkaline gases. Measuring techniques for these contaminants allow determination of the functioning of the gasifier itself, of th
25、e efficiency of the gas cleaning process and of the quality of the cleaned gas to be used in, for instance, a gas engine or gas turbine. The development of this Technical Specification started out of the need for a reliable method for the measurement of tars. For most contaminants in product gases o
26、f biomass gasification, well-developed measurement techniques exist that are similar to techniques used for related technologies, such as coal combustion and coal gasification. For tars, however, no well-developed and widely used measurement techniques existed in these related technology fields. As
27、some of the tars were (and are) seen as the major problem causing contaminants in biomass gasification, manufacturers and other workers in this field used a number of different sampling and analysis methods to determine the level of tars. As a result, comparison of data and definition of clear maxim
28、um allowable concentrations for tars was problematic. This formed an obstacle for market introduction of biomass gasification systems, as tars can cause damage or require an unacceptable level of maintenance. This Technical Specification gives methods for sampling and analysis of tars and particles
29、in product gases from biomass gasifiers operating under atmospheric or pressurised conditions. The sampling and analysis methods in this Technical Specification differ from most of the methods used for sampling organic compounds present in the gaseous emissions from various industrial processes such
30、 as flue gases or automobile exhaust gases. The differences are related to the fact that the levels of the organic compounds present in the gasification product gases exceed the levels found in flue gases generally by more than three orders of magnitude. Hence the methods described in this Technical
31、 Specification are not intended to be applicable for sampling organic compounds in trace concentrations (sub-ppm range). The tar-containing biomass gasification product gas is formed by thermal decomposition of biomass at sub stoichiometric conditions (pyrolysis, gasification) and is typically used
32、to produce electricity, heat, or gaseous or liquid biofuels. As tars from pyrolysis or gasification of coal are similar in nature compared to (high temperature) biomass gasification tars, coal tars can also be sampled and analysed with this Technical Specification. Biomass in this Technical Specific
33、ation is defined as material of biological origin excluding material embedded in geological formations and transformed to fossil1). The Technical Specification is developed for uncontaminated biomass, a term being defined in Clause 3 “Terms and definitions“. Tests on accuracy and repeatability of th
34、e Technical Specification have been performed with uncontaminated biomass. The Technical Specification may also be used for tars produced from gasification of contaminated biomass and for tars produced from gasification of fossil fuels, however, in this case it is up to the user to assess to what ex
35、tent the concentration and composition of the tars differ from gasification of uncontaminated biomass. Biomass gasifiers, as referred to in this Technical Specification, can be updraft fixed bed gasifiers, downdraft fixed bed gasifiers, stage divided gasifiers, fluidised bed gasifiers, entrained flo
36、w gasifiers and other types of gasifiers. Updraft and downdraft fixed bed, fluidised bed and entrained flow gasifiers are described in more detail in a background Technical Report 1. 1)This definition is the same as the definition of biomass in CEN TC 335 Solid Biofuels CEN/TS 15439:2006Licensed Cop
37、y: Wang Bin, na, Tue May 29 07:33:31 GMT+00:00 2007, Uncontrolled Copy, (c) BSI5 1 Scope This Technical Specification gives methods for sampling and analysis of tars and particles in order to determine the load of these contaminants in flowing biomass gasification product gases. The Technical Specif
38、ication is applicable to sampling and analysis of tars and particles in the concentration range typically from 1 mg/mn3to 300 g/mn3(tars) and from 20 mg/mn3to 30 g/mn3(particles) at all relevant sampling point conditions (0 C to 900C and 60 kPa to 6000 kPa (0,6 bar to 60 bar) )2), 3). Particle conce
39、ntrations lower than 20 mg/mn3are outside the scope of this Technical Specification and can be measured according to EN 13284-1. Application of this Technical Specification allows determination of five different parameters: A. The concentration of gravimetric tar in mg/mn3; B. The concentration of i
40、ndividual organic compounds in mg/mn3. This Technical Specification gives data on repeatability and reproducibility for the compounds listed in Annex B. The Technical Specification is also applicable for other organic compounds (e.g. those mentioned in Annex A), but repeatability and reproducibility
41、 have not been assessed for compounds other than those in Annex B; C. The sum of concentrations of identified GC-detectable compounds listed in Annex B; D. The sum of concentrations of all GC-detectable compounds with retention times in the range of benzene to coronene calculated as naphthalene (ben
42、zene excluded), given that this sum of concentrations can be determined. E. The concentration of particles in mg/mn3. 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 re
43、ferences, the latest edition of the referenced document (including any amendments) applies. ISO 9096 Stationary source emissions Manual determination of mass concentration of particulate matter 3 Terms and definitions For the purposes of this Technical Specification, the following terms and definiti
44、ons apply. 3.1 aerosol suspension of solid or liquid particles in a gas NOTE The term aerosol includes both the particles and the suspending gas. The particle size may range from about 0,002 m to more than 100 m. 3.2 biomass material of biological origin, excluding material embedded in geological fo
45、rmations and transformed to fossil NOTE This definition is the same as the definition of biomass in CEN TC 335 Solid Biofuels 7. 2)In fact it is not correct to give a concentration or to give concentration ranges for “tar” (see also its definition in Clause 3). This Technical Specification is design
46、ed and has been evaluated for measurement of tar and particles in the following concentration ranges: Gravimetric tar 500 mg/mn3to 300 g/mn3Sum of GC-detectable tars 1 mg/mn3to 300 g/mn3Particles 20 mg/mn3to 30 g/mn3The concentration range mentioned for gravimetric tar is a range based on a sampling
47、 time of 2 h. Lower concentration limits can be attained with proportionally longer sampling times (e.g. 100 mg/mn3with a sampling time of 10 h). Due to the determination method, it is recommended not to determine gravimetric tar below the concentration limit. 3)The performance characteristics in Cl
48、ause 14 are determined under atmospheric conditions. Under pressurised conditions, the Technical Specification as a whole has not been evaluated. However, sampling under pressurised conditions is based on relevant experience (relevant construction details of probes are mentioned in a background docu
49、ment 1) and the analysis of the liquid samples is identical for atmospheric and pressurised gasification. Therefore, pressurised conditions are included in this Technical Specification. CEN/TS 15439:2006Licensed Copy: Wang Bin, na, Tue May 29 07:33:31 GMT+00:00 2007, Uncontrolled Copy, (c) BSI63.3 contaminated biomass biomass not being uncontaminated biomass NOTE See 3.20. 3.4 downdraft gasification gasification process in which a bed of solid carbon-based material moves slowly downward under gravity as it is gasified, whilst the gasification agent (e.g. air) passes
