Dust and Gas Stack Emission Proficiency Tests

Transcription

1 page 1 of 12 Information Sheet Dust and Gas Stack Emission Proficiency Tests 1. Location 2. Contact 3. Participants Hessisches Landesamt für Naturschutz, Umwelt und Geologie Dezernat I3 Luftreinhaltung: Emissionen () HLNUG I3 Ludwig-Mond-Str. 33 D Kassel - GERMANY - emission@hlnug.hessen.de tel.: +49 (0) fax: +49 (0) Please note: The sampling takes place on the 1 st and 3 rd floor of the HLNUG building. A lift is not available. Dr Jens Cordes (Technical Supervisor Proficiency Testing) jens.cordes@hlnug.hessen.de tel.: +49 (0) Dr Dominik Wildanger (Head of Department) dominik.wildanger@hlnug.hessen.de tel.: +49 (0) HLNUG s stack emission proficiency tests were designed for laboratories authorized to perform measurements in accordance with 29b BImSchG (Federal Immission Control Act), as well as applicants for authorization in accordance with BImSchG. Nevertheless, other laboratories, manufacturers of equipment, industrial departments engaged in emission monitoring etc. are welcome to participate, too. Please note: Due to the limited space around the flue duct, without prior affirmation by the organizer for each laboratory only two people can participate in the sampling on site. The total number of participating laboratories is limited to 8.

2 page 2 of Task Objective of the dust proficiency test is the determination of mass concentrations of particulate flue gas components in the Emission Simulation Apparatus (ESA) and the determination of dust composition (heavy metals), as well as the measurement of the basic conditions of the flue gas. Objective of the gas proficiency test is the determination of mass concentrations of the inorganic components sulfur dioxide (SO 2), nitrogen oxides (NO + NO 2, to be specified as NO 2), and carbon monoxide (CO), the organic components ethyl benzene, toluene, and xylene (as sum of o-, m-, and p-isomers), along with propane as total organic carbon (TOC), and formaldehyde (HCHO) as well as the measurement of the basic conditions of the flue gas. 4.1 Operational state of the ESA during the proficiency test The ESA is operated using heated ambient air, which is cleaned by a particle filter EU 7 and usually operates in the medium performance range (which is between 2000 and 6500 m³/h). 4.2 Position of the sampling openings at the ESA The measurements take place on the 1 st and the 3 rd floor of the HLNUG building (room 130, and 371, respectively), approx. 5.0 and 12.5 m, respectively, above ground level and at the end of a 6.5/14 m long vertical flue duct. To carry out the proficiency test, sampling openings conforming to standard (DIN) ISO 228 are available in the following sizes: floor 3 internal thread (G3) 2 internal thread (G2) 1 st floor rd floor 6 7 For dust samplings, two G3 openings for grid measurements are allocated to each participant. For gas samplings, each participant can use at least one G3 and one G2 opening. The sampling equipment used during the proficiency test needs to fit the 40 cm diameter of the flue duct. The flow velocity of the flue gas is usually > 4 m/s. If automatic measurement devices within a monitoring vehicle are used during the proficiency test, a gas tube with a length of approx. 50 m from the measuring site to the monitoring vehicle is required. 5. Measurements 5.1 Determination of the basic conditions During the proficiency test, the following basic conditions are measured by all participants: measurement of the velocity profile in cross-section on two measurement axes (with 2 measurement points each) air pressure at the height of the measurement level static pressure temperature in the flue gas duct water vapour content in the flue gas calculation of the flue gas volume flow The measurement results for the flue gas basic conditions are re-checked daily by the participants and are handed in as part of the results submission.

3 page 3 of Sampling: Dust Every participant carries out the measurement of the dust load by means of isokinetic extraction of a partial volume conforming to standard EN (if applicable, in combination with guideline VDI 2066, Part 1) (half-hour mean values). For sampling procedures that do not conform to this standard, a proof of equivalence conforming to standard EN is required. A complete, appropriate set of equipment using a plane filter device for the determination of small amounts of dust is necessary, as well as the equipment for measurement of the basic emission conditions. All used equipment must be the property of the participant and must conform to the specifications of standard EN , and/or guideline VDI 2066 Part 1. Every individual measurement (sampling) takes exactly 30 minutes, interrupted by the time for the axis change. Ten individual measurements (nine samplings at different dust mass concentrations, plus an introductory measurement without dust dosing) are carried out. Concentrations within the following ranges are offered: level 1 1 to 4 mg/m 3 level 2 4 to 7 mg/m 3 level 3 7 to 12 mg/m 3 The gravimetric determination of the sampled dust must conform to standards and must be done in the laboratory of the participating measuring facility. Sampling is carried out simultaneously by all participants, conforming to the following standards: No. Component Compulsory method Concentration range P1 total dust EN ; VDI 2066, part 1 1 to 12 mg/m³ P2 P3 P4 P5 P6 * P7 P8 P9 * Cadmium Cobalt Chromium Copper Manganese Nickel Lead Vanadium EN 14385; VDI 2268, part 1-4 Please note: Due to the characteristics of the dust used in the proficiency test, impingers are not required during sampling. 1 to 120 µg/m³ (for each element) 5.3 Sampling: Gas Each individual measurement will take 30 min. If only continuous measurements are performed (no simultaneous discontinuous sampling), the measurement time is reduced to 15 min. Ten individual measurements (nine samplings at different concentrations, plus an introductory measurement without dosing for the determination of blinds) are carried out per component. * Voluntary component: Participation or passing are not required for a successful overall result in the proficiency test.

4 page 4 of 12 The determination of any discontinuously sampled components (sulfur dioxide, formaldehyde, ethyl benzene, toluene, and o-, m-, p-xylene) must conform to the respective standard. Any exchange of results with other participants is strictly forbidden. Sampling is carried out simultaneously by all participants, conforming to the following standards: No. Component Type of determination Compulsory method G1 SO2 discontinuous EN to 150 G2 SO2 continuous CEN/TS to 150 G3 NOx as NO2 continuous EN to 450 G4 G5 toluene ethyl benzene G6 o-, m-, and p-xylene discontinuous EN G7 formaldehyde discontinuous VDI 3862 part 2, 3, or 4 4 to 40 G8 TOC (ETX + propane) continuous EN to 100 G9 TOC (propane only) continuous EN to 100 G10 CO continuous EN to 100 Concentration range [mg/m³] 4 to 100 (sum of components G4-G6) HLNUG offers a verification of the participants span gases by comparison with its reference gases. For this verification, the following reference gas mixtures are used: C 3H 8 in synthetic air NO in N 2 CO in N 2 SO 2 in N 2 For further information, please see the Information Sheet Span Gas Verification. In addition to the determination of the mass concentrations of organic compounds in flue gas via sampling, the participants receive a standard containing ethyl benzene, toluene, and xylenes. This sample is handed out to the participants on the last day of the test. 5.4 Allocation of sampling openings The allocation of measurement levels and sampling openings is set by HLNUG staff on site. 6. Submission of results All measurement results must relate to normal conditions, dry ( K, hpa). The measurement results for the dust proficiency test and for the gas proficiency test are submitted and evaluated independently. Please submit measurement results for both proficiency tests via to: emission@hlnug.hessen.de using Excel-files provided by HLNUG. The necessary files can be downloaded at: Voluntary component: Participation or passing are not required for a successful overall result in the proficiency test. Recommended method. Compulsory requirement for component G2 is the use of a suitability tested measurement device. Sum of all three xylene isomers.

5 page 5 of 12 Please note the different deadlines for results submission for the two different proficiency tests. Each participant may only submit one result per measurement and component. Any exchange of results with other participants is strictly forbidden. If an authorization to perform measurements in the sense of 29b BImSchG exists or is aspired, any subcontraction of analyses connected with the proficiency test is forbidden as well. HLNUG s assessment of the participant s results will be sent by land mail within six weeks after the end of the result submission. 6.1 Dust proficiency test Total dust concentrations must be submitted in mg/m³ and heavy metal concentrations in µg/m³. All results need to be specified with one position after decimal point. The values must be rounded in accordance with DIN 1333 Presentation of numerical data. All results of the dust proficiency test must be submitted to HLNUG within six weeks after the conclusion of the dust proficiency test. Failure to do so results in the overall assessment failed for the proficiency test participation. 6.2 Gas proficiency test All concentrations of measurements at the ESA must be submitted in mg/m³. Results for components G1, G2, G3, G8, and G9 are to be specified with one position after decimal point, all other components are to be specified with two positions after decimal point. Results for the ETX reference standard are to be specified in µg/ml with two positions after decimal point. The concentration of xylenes is to be determined as sum of isomers. All results of the gas proficiency test must be submitted to HLNUG within four weeks after the conclusion of the gas proficiency test. Failure to do so results in the overall assessment failed for the proficiency test participation. 7. Evaluation of measurement results The evaluation of the proficiency test is carried out on the basis of the z-score procedure. For the measurement value x ijk, which is the result of measurement i of concentration level j of component k, a z-score value z ijk is determined: z ijk = x ijk X ijk σ k X ijk In this equation, X ijk is the assigned value of the measurement, and σ k is the precision criterion (criterion for proficiency assessment) for component k. The assigned value is calculated from measurement data of the dosing device and the volume flow. The z-scores can be interpreted using the following scheme: z ijk 2 result satisfactory 2 < z ijk < 3 result questionable z ijk 3 result unsatisfactory Generally, for each measurement resulting in a z-score of more than two, a causal research should be conducted.

6 page 6 of 12 In the next step of the evaluation, the mean value z jk of the absolute values of the n z-scores of one concentration level (unusually n = 3) is calculated: n z jk = z ijk n i=1 Based on z jk, to each concentration level a class number K jk is assigned according to the following scheme: z jk 2 K jk = 1 2 < z jk < 3 K jk = 2 z jk 3 K jk = 3 Finally, for each component k, the sum of class numbers K k for all three concentration levels is calculated: 3 K k = K jk j=1 For each component, at least six measurement values must be submitted, otherwise the component is automatically rated failed. The determination of the overall result for the different components, as well as the overall result for the participation in the proficiency test (evaluation result regarding 41. BImSchV) differs between dust and gas proficiency test. Successful determinations are labelled passed, unsuccessful determinations are labelled failed. 7.1 Dust emission proficiency test A component was determined successfully, if the respective sum of class numbers does not exceed 5. If in justified single cases only values for two concentration levels were submitted, the component was determined successfully if the sum of class numbers does not exceed 4 and the sum of absolute z-scores does not exceed the value 5.2. Successful determinations are labelled passed, unsuccessful determinations are labelled failed. The overall result (evaluation result regarding 41. BImSchV) is passed, if the component total dust (P1) and at least 5 out of the 6 mandatory heavy metal determinations (No. P2-P5, P7 and P8) are determined successfully. The criteria for proficiency assessment σ k are: Nr. Component σ k in % of true value P1 total dust 7 P2 Cd 8 P3 Co 8 P4 Cr 12 P5 Cu 8 P6 ** Mn 10 P7 Ni 8 P8 Pb 8 P9 ** V 10 ** Voluntary component: Participation or passing are not required for a successful overall result in the proficiency test.

7 page 7 of 12 If the result for total dust (component P1) is passed, but less than 5 of the mandatory heavy metal determinations were successful, the participant receives a dust sample for post-analysis. The evaluation of the post-analysis results replaces the previous evaluation results for heavy metal determinations via sampling in the final evaluation of the proficiency test. 7.2 Gas emission proficiency test A component was determined successfully, if the respective sum of class numbers does not exceed 6. If in justified single cases only values for two concentration levels were submitted, the component was determined successfully if the sum of class numbers does not exceed 4. The overall result of the proficiency test is passed, if all relevant components (No. G1 and G3-G8) are passed, otherwise the overall result is failed. No. Component Type of determination σ k in % of true value G1 SO2 discontinuous 3,1 G2 SO2 continuous 3,9 G3 NOx as NO2 continuous 3,1 G4 toluene discontinuous 5,6 G5 ethyl benzene discontinuous 5,8 G6 o-, m-, p-xylene discontinuous 5,3 G7 formaldehyde discontinuous 3,5 G8 TOC (ETX + propane) continuous 3,3 G9 TOC (propane only) continuous 3,3 G10 CO continuous 3,6 For the analytic part of the proficiency test (which does not include sampling), z-scores are calculated following the procedure shown above. In this case, the criterion for proficiency assessment is 4,5% of the true value. A component of the ETX-standard was determined successfully, if z k < 3 For the overall result passed in the analytic part of the test, all three components must be determined successfully, otherwise the result is failed. Voluntary component: Participation or passing are not required for a successful overall result in the proficiency test.

8 page 8 of 12 Operating Schedule for the Proficiency Tests Dust proficiency test (1 st day) (Monday) We recommend to arrive in Kassel one day early (on Sunday). Between 09:00 and 12:00 Arrival at HLNUG and set-up of equipment for dust measurements. Delivery of span gases for verification measurements in room 126/127. (Please make sure that labels and copies of certificates are prepared as described in the corresponding information sheet Span Gas Verification.) 12:00 Preliminary meeting dust and gas proficiency test (room 258, 2 nd floor) 12:30 13:15 1 st floor: Lunch break 3 rd floor: Measurement of basic conditions 13:15 14:00 1 st floor: Measurement of basic conditions 3 rd floor: Lunch break 14:00 17:00 Determination of flue gas dust load via isokinetic extraction of a partial volume conforming to standard EN , and/or conforming to guideline VDI 2066, Part 1. one introductory measurement (30 min plus interruption by axis change) three measurements conforming to above-mentioned standards (30 min plus interruption by axis change each) Participants that fail to arrive by this time are excluded from the proficiency test.

9 page 9 of 12 Dust proficiency test (2 nd day) (Tuesday) 08:00 08:45 1 st floor: Preparations 3 rd floor: Measurement/re-checking of basic conditions 08:45 09:30 1 st floor: Measurement/re-checking of basic conditions 3 rd floor: Preparations 09:30 11:45 Determination of flue gas dust load via isokinetic extraction of a partial volume conforming to standard EN , and/or conforming to guideline VDI 2066, Part 1. three measurements conforming to above-mentioned standards (30 min plus interruption by axis change each) 11:45 12:30 Lunch break 12:30 14:45 Determination of flue gas dust load via isokinetic extraction of a partial volume conforming to standard EN , and/or conforming to guideline VDI 2066, Part 1. three measurements conforming to above-mentioned standards (30 min plus interruption by axis change each) Removal of equipment for dust measurements 14:45 17:00 Set-up of equipment for gas measurements for the following day (formaldehyde). If possible: Pick-up of span gases from room 126/127. End of dust proficiency test: Final meeting for measuring institutes that only take part in the dust proficiency test (room 258, 2 nd floor). For measuring institutes that only take part in the gas proficiency test: until 15:30 Arrival and set-up of equipment for the measurement of basic conditions and for formaldehyde sampling. Delivery of span gases for verification measurements in room 126/127. (Please make sure that labels and copies of certificates are prepared as described in the corresponding information sheet Span Gas Verification.) 15:30 16:00 Preliminary meeting gas proficiency test (room 258, 2 nd floor) 16:00 17:00 Preparations for the following day.

10 page 10 of 12 Gas proficiency test (1 st day) (Wednesday) Please note: Participants that only take part in the gas proficiency test need to arrive the day before (see Tuesday). 07:30 08:00 1 st floor: Measurement of basic conditions 3 rd floor: Preparations 08:00 08:30 1 st floor: Preparations 3 rd floor: Measurement of basic conditions 08:30 12:15 Determination of the mass concentration of formaldehyde via discontinuous reference method conforming to guideline VDI 3862, Part 2 or 3 (DNPH-methods) or VDI 3862, Part 4 (AHMT-method) one introductory measurement (30 min) four measurements conforming to above-mentioned standards (30 min each) 12:15 13:00 Lunch break 13:00 16:45 Determination of the mass concentration of formaldehyde via discontinuous reference method conforming to guideline VDI 3862, Part 2 or 3 (DNPH-methods) or VDI 3862, Part 4 (AHMT-method) five measurements conforming to above-mentioned standards (30 min each) 16:45 17:30 Set-up of equipment for gas measurements for the following day (TOC continuously, ETX and SO 2 discontinuously). Pick-up of span gases from room 126/127.

11 page 11 of 12 Gas proficiency test (2 nd day) (Thursday) 07:30 08:00 1 st floor: Preparations 3 rd floor: Measurement/re-checking of basic conditions 08:00 08:30 1 st floor: Measurement/re-checking of basic conditions 3 rd floor: Preparations 08:30 12:15 Discontinuous determination of the mass concentration of SO 2 conforming to standard EN Simultaneously discontinuous determination of the mass concentrations of toluene, ethyl benzene, and o-, m-, p-xylene conforming to standard EN and continuous determination of the mass concentration of TOC conforming to standard EN 12619, using a continuous, suitability tested measuring device. one introductory measurement (30 min) four measurements (30 min each) 12:15 13:00 Lunch break 13:00 16:45 Discontinuous determination of the mass concentration of SO 2 conforming to standard EN Simultaneously discontinuous determination of the mass concentrations of toluene, ethyl benzene, and o-, m-, p-xylene conforming to standard EN and continuous determination of the mass concentration of TOC conforming to standard EN 12619, using a continuous, suitability tested measuring device. five measurements (30 min each) 16:45 17:30 Set-up of equipment for gas measurements for the following day (CO, propane, NO x and SO 2 continuously).

12 page 12 of 12 Gas proficiency test (3 rd day) (Friday) 07:30 08:15 1 st floor: Measurement/re-checking of basic conditions 3 rd floor: Preparations 08:15 09:00 1 st floor: Preparations 3 rd floor: Measurement/re-checking of basic conditions 09:00 13:00 Continuous determination of mass concentrations of CO, SO 2, NO x and propane (as TOC) conforming to standards EN (CO), EN (NO x) and EN (TOC), respectively, using suitability tested measuring devices. one introductory measurement (15 min) nine measurements (15 min each) ca. 12:00 12:30 around 13:00 Final meeting (room 258, 2 nd floor) (one person per participant needs to attend) Removal of equipment, departure of participants.