TÜV RHEINLAND ENERGIE UND UMWELT GMBH

Transcription

1 TÜV RHEINLAND ENERGIE UND UMWELT GMBH Report on the performance testing of the Emerson NGA 2000 MLT 2 measuring system manufactured by Emerson Process Management GmbH & Co. OHG for the component N2O TÜV- Cologne, 11 October luft@de.tuv.com The department of Environmental Protection of TÜV Rheinland Energie und Umwelt GmbH is accredited for the following work areas: - Determination of air quality and emissions of air pollution and odour substances; - Inspection of correct installation, function and calibration of continuously operating emission measuring instruments, including data evaluation and remote emission monitoring systems; - Performance testing of measuring systems for continuous monitoring of emissions and ambient air, and of electronic data evaluation and remote emission monitoring systems; according to EN ISO/IEC The accreditation is valid up to DAkkS-register number: D-PL Reproduction of extracts from this test report is subject to written consent. TÜV Rheinland Energie und Umwelt GmbH D Cologne, Am Grauen Stein, Tel: , Fax:

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3 Page 3 of 541 Overview Emerson Process Management GmbH & Co. OHG has commissioned TÜV Rheinland Energie und Umwelt GmbH to carry out a performance test of the Emerson NGA 2000 MLT 2 measuring system for the component N 2 O in accordance with the guidelines for continuous emission monitoring [1] and the EN standard [4]. The instrument was designed for measurement of emissions at plants requiring official approval (especially nitric acid plants). The Emerson NGA 2000 MLT 2 measuring system operates according to the principle of IR absorption. The following measuring ranges were tested: Component Certification range Supplementary range Unit N 2 O mg/m³ The minimum requirements of Standard EN [4] were fulfilled during performance testing. Hence, the measuring system also complies with the requirements QAL1 according to EN [6]. TÜV Rheinland Energie und Umwelt GmbH therefore suggests its publication as a suitabilitytested measuring system for continuous monitoring of emissions at plants requiring official approval.

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5 Page 5 of 541 MLT 2 measuring system manufactured by Emerson Process Management GmbH & Co. OHG for the component N2O Instrument tested: Emerson NGA 2000 MLT 2 Manufacturer: Emerson Process Management GmbH & Co. OHG Test period: 13 March September 2012 Date of report: 11 October 2012 Report number: 936/ /A Editor: Dipl.-Ing. Fritz Hausberg fritz.hausberg@de.tuv.com Technical supervisor: Dr. Peter Wilbring peter.wilbring@de.tuv.com Scope of report: Report: 103 pages Annex Page 104 ff. Manual Page 121 ff. Manual of 420 pages Total 541 pages

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7 Page 7 of 541 Contents 1. General Certification proposal Summary of test results Task Definition Nature of Test Objective Determination of the total uncertainty Description of the AMS tested Measuring principle AMS scope and set-up Test program Laboratory test Field test Standard reference measuring methods Method of measurement (discontinuous measurement) Determination of waste gas boundary conditions Test gases and test standards Test results a General Requirements a.1 [5.1 Application of performance criteria] a.2 [5.2 Ranges to be tested] a.3 [5.3 Manufacturing consistency and changes to AMS design] a.4 [5.4 Qualifications of test laboratories] b Performance criteria common to all AMS for laboratory testing b.1 [6.1 AMS for testing] b.2 [6.2 CE labelling] b.3 [6.3 Security] b.4 [6.4 Output ranges and zero point] b.5 [6.5 Additional data outputs] b.6 [6.6 Display of operational status signals] b.7 [6.7 Prevention or compensation for optical contamination] b.8 [6.8 Degrees of protection provided by enclosures] b.9 [6.9 Response time in laboratory test] b.10 [6.10 Repeatability standard deviation at zero point] b.11 [6.11 Repeatability standard deviation at span point] b.12 [6.12 Lack of fit in laboratory test] b.13 [6.13 Zero and span drift] b.14 [6.14 Influence of ambient temperature] b.15 [6.15 Influence of sample gas pressure] b.16 [6.16 Influence of sample gas flow for extractive AMS] b.17 [6.17 Influence of voltage variations] b.18 [6.18 Influence of vibration] b.19 [6.19 Cross-sensitivity] b.20 [6.20 Excursion of measurement beam of cross-stack in-situ AMS] b.21 [6.21 Converter efficiency for NO X measuring AMS] b.22 [6.22 Response factors]... 70

8 Page 8 of 541 6c Performance criteria common to all AMS for field testing c.1 [7.1 Calibration function] c.2 [7.2 Response time during field test] c.3 [7.3 Lack of fit during the field test] c.4 [7.4 Maintenance interval] c.5 [7.5 Zero and span drift] c.6 [7.6 Availability] c.7 [7.7 Reproducibility] c.8 [7.8 Contamination check of in-situ systems] d Measurement uncertainty d.1 [14 Measurement uncertainty] Maintenance work, functional test (AST) and calibration (QAL2) Tasks to be performed during maintenance interval Functional check and calibration Literature Annex Manual

9 Page 9 of 541 List of Tables Table 1: Tested components and their certification ranges during laboratory test...25 Table 2: Supplementary measuring range to be tested with reduced program...25 Table 3: Set certification ranges during the field test...26 Table 4: Response times during laboratory test...48 Table 5: Response times during laboratory test (supplementary range)...48 Table 6: Repeatability standard deviation at zero point...50 Table 7: Repeatability standard deviation at span point...51 Table 8: Lack of fit test, certification range mg/m³...53 Table 9: Lack of fit test, supplementary range mg/m³...54 Table 10: Temperature test...58 Table 11: Influence of sample gas flow rate...61 Table 12: Influence of the voltage variations...63 Table 13: Concentrations of interference components...65 Table 14: Cross-sensitivities, system Table 15: Cross-sensitivities, system Table 16: Parameter of the 1 st calibration of system Table 17: Parameter of the 1 st calibration of system Table 18: Parameter of the 2 nd calibration of system Table 19: Parameter of the 2 nd calibration of system Table 20: Variability test of system Table 21: Variability test of system Table 22: Response times at the beginning of the field test (0 196 mg/m³)...81 Table 23: Response times at the beginning of the field test (0 588 mg/m³)...82 Table 24: Response times at the end of the field test (0 196 mg/m³)...82 Table 25: Response times at the end of the field test (0 588 mg/m³)...82 Table 26: Lack of fit test at the beginning of the field test (0 196 mg/m³)...84 Table 27: Lack of fit test at the beginning of the field test (0 588 mg/m³)...85 Table 28: Lack of fit test at the end of the field test (0 196 mg/m³)...87 Table 29: Lack of fit test at the end of the field test (0 588 mg/m³)...88 Table 30: Results of the drift check for the certification range (0 196 mg/m³)...92 Table 31: Results of the drift check for the measuring range (0 588 mg/m³)...93 Table 32: Presentation of the availability...95 Table 33: Reproducibility...97 Table 34: Relative total expanded measurement uncertainty for all components Table 35: Data of repeatability standard deviation at zero point Table 36: Data of repeatability standard deviation at span point Table 37: Data of linearity test for system Table 38: Data of linearity test for system Table 39: Data of linearity test for system 1 (supplementary range) Table 40: Data of linearity test for system 2 (supplementary range) Table 41: Data of temperature test Table 42: Data of test on influence of sample gas flow Table 43: Data of test on influence of voltage supply Table 44: Data of cross-sensitivity test for system Table 45: Data of cross-sensitivity test for system Table 46: Calibration data for N 2 O Table 47: Data of linearity test at the beginning of the field test (0-196 mg/m³) Table 48: Data of linearity test at the beginning of the field test (0-588 mg/m³) Table 49: Data of linearity test at the end of the field test (0-196 mg/m³) Table 50: Data of linearity test at the end of the field test (0-588 mg/m³) Table 51: Calculation of total uncertainty

10 Page 10 of 541 List of Figures Figure 1: Emerson NGA 2000 MLT Figure 2: Display of the MLT 2 measuring system showing its software version...22 Figure 3: Mounting plate set-up...23 Figure 4: Installation during laboratory test...24 Figure 5: View of the measurement site with heated pressure regulators...27 Figure 6: System 2 in measurement container...28 Figure 7: Inner view of the heated pressure regulator in the field...29 Figure 8: Diagram illustrating the response time...47 Figure 9: Linearity of system 1, mg/m³...53 Figure 10: Linearity of system 2, mg/m³...54 Figure 11: Linearity of system 1, mg/m³...55 Figure 12: Linearity of system 2, mg/m³...55 Figure 13: Presentation of the results of the 1 st parallel measurement, system Figure 14: Presentation of the results of the 1 st parallel measurement, system Figure 15: Presentation of the results of the 2 nd parallel measurement, system Figure 16: Presentation of the results of the 2 nd parallel measurement, system Figure 17: Presentation of the results of both parallel measurements, system Figure 18: Presentation of the results of both parallel measurements, system Figure 19: Linearity of system 1 at the beginning of the field test (0 196 mg/m³)...84 Figure 20: Linearity of system 2 at the beginning of the field test (0 196 mg/m³)...85 Figure 21: Linearity of system 1 at the beginning of the field test (0 588 mg/m³)...86 Figure 22: Linearity of system 2 at the beginning of the field test (0 588 mg/m³)...86 Figure 23: Linearity of system 1 at the end of the field test (0 196 mg/m³)...87 Figure 24: Linearity of system 2 at the end of the field test (0 196 mg/m³)...88 Figure 25: Linearity of system 1 at the end of the field test (0 588 mg/m³)...89 Figure 26: Linearity of system 2 at the end of the field test (0 588 mg/m³)...89 Figure 27: Graphic representation of the reproducibility...98 Figure 28: Certificate of accreditation according to EN ISO/IEC 17025: Figure 29: Test certificate on CE labelling

11 Page 11 of General 1.1 Certification proposal Due to the positive results achieved, the following recommendation is put forward for the notification of the AMS as a suitability-tested measuring system: AMS designation: Emerson NGA 2000 MLT 2 for N 2 O Manufacturer: Emerson Process Management GmbH & Co. OHG, Field of application: Measurement at plants requiring official approval Measuring ranges during performance testing: Component Certification range Supplementary range Unit N 2 O mg/m 3 Software version: Restrictions: 1. The measuring system shall only be employed at plants in which waste gas humidity does not exceed 3 Vol.-%. 2. The measuring system shall only be employed at plants in which the CO 2 concentration does not exceed 10 Vol.-%. Notes: 1. The maintenance interval is four weeks. Test report: TÜV Rheinland Energie und Umwelt GmbH, Cologne Report no.: 936/ /A of 11 October 2012

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13 Page 13 of Summary of test results Performance criterion Result Status Page Legend: Minimum requirement fulfilled Minimum requirement not fulfilled Minimum requirement not applicable + x General requirements: 5.1 Application of performance criteria The test laboratory shall test at least two identical automated measuring systems (AMS). All AMS tested shall meet the performance criteria specified in this document as well as the uncertainty requirements specified in the applicable regulations. 5.2 Ranges to be tested The certification range over which the AMS is to be tested shall comprise minimum and maximum values. The coverage shall be fit for the intended application of the AMS. The certification range(s) and the performance criteria tested for each range shall be stated on the certificate. The certification range for optical in-situ AMS with variable optical length shall be defined in units of the measured component concentration multiplied by the length of the optical path. 5.3 Manufacturing consistency and changes to AMS design Certification is specific to the AMS version that has undergone suitability testing. Subsequent design modifications that might affect the performance of the AMS can invalidate the certification. 5.4 Qualifications of test laboratories Test laboratories shall be accredited to EN ISO/IEC and the appropriate test standards for carrying out the tests defined in this European Standard. Test laboratories shall have knowledge on the uncertainties attributed to the individual test procedures applied during performance testing. Two measuring systems of identical design were tested for suitability. The measuring systems fulfil the minimum requirements for monitoring emissions from stationary sources and the requested uncertainty. The certification range is mg/m3. There are no specified emission limit values for N2O. One supplementary measuring range was defined for N2O and some additional tests were carried out to validate that range. A list of additionally admitted cross-sensitivity components and the results of the additional tests can be found in the respective sub-items of sections 6b and 6c. The lower limit of the certification range is zero for all tested components. The measuring system tested is not an in-situ AMS with variable optical path length. All tests were performed with the measuring systems described in section 3. The test results in this report and on the associated certificate refer to measuring systems that comply with the tested versions only. The manufacturer has been informed that any modification to the certified system has to be agreed upon with the test institute and that this may lead to additional or new tests of the measuring system. TÜV Rheinland Energie und Umwelt GmbH is accredited for performance testing (QAL1), functional tests (AST), calibrations (QAL2), and emission measurements according to EN ISO/IEC until Laboratory test: 6.1 AMS for testing The test shall be carried out with two complete measuring systems of identical design. The suitability-tested version comprises the entire measuring system including sampling system, analysers, data output, and manual. + 38

14 Page 14 of 541 Performance criterion Result Status Page 6.2 CE labelling AMS manufacturers shall supply verifiable and traceable evidence of compliance with the requirements applicable to the equipment. 6.3 Security The AMS shall have a means of protection against unauthorised access to control functions. 6.4 Output ranges and zero point The AMS shall have a data output with a living zero point so that both negative and positive readings can be displayed. The AMS shall have a display that shows the measurement response. 6.5 Additional data outputs The AMS shall have a data output allowing an additional data display and recording device to be fitted to the AMS. 6.6 Display of operational status signals The AMS shall have a means of displaying its operational status. The AMS shall also have a means of communicating the operational status to a data handling and acquisition system. 6.7 Prevention or compensation for optical contamination An AMS that uses an optical method as the measuring principle shall have provisions for either prevention of contamination of the optical system and/or compensation for its effects. 6.8 Degrees of protection provided by enclosures Instruments limited to be mounted in ventilated rooms or cabinets, where any kind of precipitation cannot reach the instrument, shall meet at least IP40 as specified in EN Instruments limited to being mounted in areas where some kind of shelter against precipitation is in place, but where precipitation can reach the instrument due to wind, shall meet at least IP54 as specified in EN Instruments that are designed to be used in the open air and without any weather protection shall at least meet the requirements of IP65 as specified in EN Response time in laboratory test The AMS shall meet the performance criteria for response time: Gases 200 s, O s, NH3, HCl and HF 400 s. The certificate of CE labelling was presented to the test institute. The AMS is protected by password against unauthorised access to control functions. The output range can be set on the measuring system. At 4 ma, zero point amounts to 20% of the analogue system output. The AMS can also display negative values. All relevant limit values can be monitored. The additional check of higher measuring ranges for component N2O also ensures monitoring at higher emission concentrations. An additional signal output is available. The different signal outputs of the AMS display identical values The status messages were output correctly In-built filter elements prevent contamination of the optical surfaces. The system is in compliance with degree of protection IP65. Response times of 40 s were obtained from the test with dry test gas

15 Page 15 of 541 Performance criterion Result Status Page 6.10 Repeatability standard deviation at zero point The AMS shall meet the performance criteria for repeatability standard deviation at the zero point: Gases 2.0 %, O Vol.-% Repeatability standard deviation at span point The AMS shall meet the performance criteria for repeatability standard deviation at the span point: Gases 2.0 %, O Vol.-% Lack of fit in laboratory test The AMS shall have a linear output and shall meet the performance criteria for lack of fit: Gases 2.0 %, O Vol.-% Zero and span drift The manufacturer shall provide a description of the technique used by the AMS to determine and compensate the zero and span drift. The test laboratory shall assess that the chosen reference material is capable of monitoring any relevant change in instrument response not caused by changes in the measured component or stack gas condition. The AMS shall allow recording the zero and span drift. If the AMS has a means of automatic compensation for contamination and calibration and re-adjustment for zero and span drift, and such adjustments are not capable of bringing the AMS within normal operational conditions, then the AMS shall set a status signal Influence of ambient temperature The deviations of the AMS readings at the zero and span points shall not exceed the performance criteria for influence of ambient temperature: Gases 5.0 %, O Vol.-%. This is applicable for the following test ranges of the ambient temperature: from -20 C to +50 C for assemblies installed outdoors; from +5 C to +40 C for assemblies installed indoors. The manufacturer submitting an AMS for testing may specify wider ambient temperature ranges to those above. The maximum repeatability standard deviation at zero point was 0.1 % of the certification range for component N2O. The maximum repeatability standard deviation at span point was 0.1 % of the certification range for component N2O. The relative residuals do not exceed 0.26 % of the certification range. The AMS allows for recording zero and span drifting and thus fulfils the requirements of QAL3 according to EN The maximum deviation for the temperature range C amounts to -2.2 % of the upper limit of the certification range. The maximum sensitivity coefficient is

16 Page 16 of 541 Performance criterion Result Status Page 6.15 Influence of sample gas pressure The deviations of the AMS reading at the span point shall not exceed the following performance criterion when the sample gas pressure changes by 3kPa above and below atmospheric pressure: Gases 2.0 %, O Vol.-% Influence of sample gas flow for extractive AMS The deviations of the AMS reading at the zero point and span point shall not exceed the following performance criterion, when the sample gas flow is changed in accordance with the manufacturer s specification: Gases 2.0 %, O Vol.-%. A status signal for the lower limit of the sample gas flow shall be provided Influence of voltage variations The deviations of the AMS reading at the zero and span points shall not exceed the following performance criterion when the voltage supply to the AMS varies from -15 % from the nominal value below to +10 % from the nominal value above the nominal value of the supply voltage: Gases 2.0 %, O Vol.-%. The AMS shall be capable of operating at a voltage that meets the requirements of EN Influence of vibration The deviations of the AMS readings at the zero and span points caused by vibrations typically expected at an industrial plant shall not exceed the following performance criteria: Gases 2.0 %, O Vol.-% Cross-sensitivity The manufacturer shall describe any known sources of interference. Tests for non-gaseous interference sources, or gases other than those listed in Annex B, shall be agreed with the test laboratory. The AMS shall meet the performance criteria at the zero and span point for cross-sensitivity: Gases 4.0 %, O Vol.-% Excursion of measurement beam of cross-stack in-situ AMS In the event of an excursion of the measurement beam within an AMS, the deviation of the AMS reading shall not exceed the performance criterion for the maximum allowable deviation angle specified by the manufacturer: Gases 2.0 %. This angle shall not be smaller than 0.3. Since the Emerson NGA 2000 MLT 2 measuring system is an extractive AMS, this performance criterion is not relevant. The maximum deviation of the measured signals amounts to 0.3 %. The AMS produces a status signal when the flow rate drops below the specified lowest flow rate. The maximum deviation is 0.4 % at zero and 0.2 % at the span point. The maximum sensitivity coefficient is at zero and at the span point. The Emerson NGA 2000 MLT 2 measuring system is an extractive AMS. Testing the influence of vibration is not required for this type of instruments. The highest deviation is 3.41 % at zero and 2.85 % at the span point. With interferents H2O and CO2, a concentration of 3 Vol.-% and 10 Vol.-% was used respectively. The Emerson NGA 2000 MLT 2 measuring system is an extractive AMS

17 Page 17 of 541 Performance criterion Result Status Page 6.21 Converter efficiency for NOX measuring AMS Manufacturers shall specify, when seeking certification for AMS for measuring NO X, whether certification is required for the measurement of nitrogen monoxide (NO) and/or nitrogen dioxide (NO 2). If a converter is used, the converter shall meet the performance criteria for the converter efficiency: 95.0 % 6.22 Response factors The response factors for TOC measuring AMS shall lie within the permissible ranges (see test item). The Emerson NGA 2000 MLT 2 measuring system does not measure NOX. The Emerson NGA 2000 MLT 2 measuring system does not measure total carbon Field test: 7.1 Calibration function The calibration function shall be determined by parallel measurements carried out using a SRM. The calibration function shall have a determination coefficient R² of the regression of at least The variability attached to the calibration function and determined in accordance with EN shall meet the maximum permissible uncertainty specified by the applicable regulations. 7.2 Response time during field test The AMS shall meet the performance criterion for the response time evaluated during the laboratory tests. 7.3 Lack of fit during the field test The AMS shall meet the performance criterion for lack of fit evaluated during the laboratory tests. 7.4 Maintenance interval The minimum maintenance interval of the AMS shall meet the following performance criterion: min. 8 days. 7.5 Zero and span drift The zero and span drift within the maintenance interval shall not exceed the specified performance criteria: Gases 3.0 %, O Vol.-%. The span materials applied during testing shall produce an AMS response between 70 % and 90 % of the upper limit of the certification range. The determination coefficient R² of the calibration function lies between and The AMS passed the variability test. A response time of maximum 25 s was determined for the measuring system during the field test. The relative residuals do not exceed 0.66 % of the certification range (0 196 mg/m³). For the supplementary range mg/m³, they have a maximum value of 1.31 %. A four-week period was specified as maintenance interval. The zero drift lay below 0.4 % of the certification range over the entire period. The span point drift was below 1.9 % of the certification range

18 Page 18 of 541 Performance criterion Result Status Page 7.6 Availability The AMS shall have an availability which meets the requirements of applicable regulations and in any case, the following performance criterion during the field test Gases 95 %, O 2 98 %. 7.7 Reproducibility AMS shall meet the performance criterion for reproducibility under field conditions: Gases 3.3 %, O Vol.-%. 7.8 Contamination check of in-situ systems The response of the AMS to soiling shall be determined in the field test by means of visual checks and, for example, by determining the deviations from the nominal values of the AMS output signal. If required, the AMS shall be provided with recommended air purging systems for three months as part of the field test. At the end of the test, the effect of the contamination shall be evaluated. The results with clean and soiled optical surfaces shall differ by no more than 2% of the upper limit of the certification range. The availability is 99.5 % The determined reproducibility is 0.7 %. This is equivalent to a RD-value of 139 (according to VDI 4203). Since the Emerson NGA 2000 MLT 2 measuring system is an extractive AMS, this performance criterion is not relevant Measurement uncertainty: 14 Measurement uncertainty The values of the uncertainties determined during the field and laboratory test shall be used to determine the combined standard uncertainty of the AMS measured values according to EN ISO The determined total expanded uncertainty of all components lies below the maximum permissible values, and therefore fulfils the requirements

19 Page 19 of Task Definition 2.1 Nature of Test Emerson Process Management GmbH & Co. OHG has commissioned TÜV Rheinland Energie und Umwelt GmbH to carry out performance testing of the Emerson NGA 2000 MLT 2 measuring system in accordance with the guidelines for continuous emission measurement. 2.2 Objective The application for the requested certification corresponds to measurements at plants requiring official approval. Performance testing of the measuring system was carried out applying the German and European directives regarding minimum requirements for testing and approving emission measurement systems. These include in particular: [1] Uniform Practice in monitoring emissions of the Federal Republic of Germany, provisions on: - Suitability testing of measuring and evaluation systems for continuous emission measurements, and the continuous acquisition of reference or operational values and for the continuous monitoring of emissions of special substances. Circular from the Federal Environment Ministry (BMU) of June 13, 2005 IG I /5, last amended by BMU circular of August 4, IG I /0. [2] Standard EN :2009 Air quality Certification of automated measuring systems Part 1: General principles [3] Standard EN :2009 Air quality Certification of automated measuring systems Part 2: Initial assessment of the AMS manufacturer s quality management system and post certification surveillance for the manufacturing process [4] Standard EN : 2007 Air quality Certification of automated measuring systems Part 3: Performance criteria and test procedures for automated measuring systems for monitoring emissions from stationary sources. [5] Guideline VDI 4203 Part 1, October 2001 Testing of automated measuring systems General concepts [6] Standard EN 14181, July 2004 Stationary source emissions Quality assurance of automated measuring systems 2.3 Determination of the total uncertainty The total expanded uncertainty was determined by means of the data obtained during the laboratory and field tests. See test item 6d Measurement uncertainty.

20 Page 20 of Description of the AMS tested 3.1 Measuring principle The AMS tested is an IR spectrometer designed for the determination of N 2 O. It measures the absorption of infrared radiation by the sample gas. The radiation intensities coming from the measuring and reference side of the analysis cell produce periodically changing signals within the detector. The detector signal amplitude thus alternates between concentrationdependent and concentration-independent values. The various signals are produced within a filter cell with dividing wall. A chopper wheel conducts the IR radiation generated by a heating coil alternately to the measurement side and to the reference side of the analysis cell. The difference between the two signals is a reliable measure of the concentration of the component. Behind the analysis cell, the radiation passes a second filter cell and arrives at a pneumatic detector, which captures de IR radiation intensities from the measurement and reference sides and converts them with help of a pre-amplifier into an AC voltage signal proportional to the intensity. The detector consists of a gas-filled absorption chamber and a compensation chamber, both of which are connected by a flow channel. The detector is filled with N 2 O. For this reason it is only sensitive to this particular component. When the IR radiation passes through the measurement side of the analysis cell into the detector, a part of it is absorbed. The gas in the detector cools down, it becomes constricted and part of it passes through the flow channel into the absorption chamber. When the IR radiation passes through the reference side of the analysis cell into the detector, no pre-absorption occurs. The gas in the detector heats up, expands and part of it passes through the flow channel into the compensation chamber. The flow channel geometry is designed in such a way that it hardly impedes the gas flow by restriction. The different radiation intensities lead to a periodical repetition of flow pulses within the detector. The microflow sensor measures this flow and converts it into electrical voltages. Downstream electronics evaluate the signals and convert them into the corresponding display format. 3.2 AMS scope and set-up The waste gas is sampled through a stainless steel probe and carried through a heated waste gas line to a heated pressure regulator (overpressure operation). A second heated stainless steel gas line leads the gas to a mounting plate, from which it is led by means of a pump (no-pressure operation) and a vortex cooler into the analyser. The process by which the AMS is operated can either use overpressure or no pressure at all. If the overpressure process is used, the upstream pressure is adjusted on the pressure regulator and the gas is carried through a pump bypass. If no pressure is used, the pressure in the heated pressure regulator is relieved and the gas is drawn by the pump. In addition, the mounting plate has connections for feeding zero and span gas. It is possible to carry out automatic zero and span point calibrations. The gas lines, pumps and valves on the mounting plate are not heated.

21 Page 21 of 541 Figure 1: Emerson NGA 2000 MLT 2

22 Page 22 of 541 Figure 2: Display of the MLT 2 measuring system showing its software version

23 TÜV Rheinland Energie und Umwelt GmbH Figure 3: Page 23 of 541 Mounting plate set-up

24 Page 24 of 541 Figure 4: Installation during laboratory test

25 Page 25 of Test program 4.1 Laboratory test The laboratory test was carried out with two complete and identical devices of the type Emerson NGA 2000 MLT 2 with the serial numbers: S/N 1: and S/N 2: In conformity with the applicable standards, the following performance criteria were tested in the laboratory: AMS for testing CE labelling Security Output ranges and zero point Additional data outputs Display of operational status signals Prevention or compensation for optical contamination Degrees of protection provided by enclosures Response time Repeatability standard deviation at zero point Repeatability standard deviation at the span point Lack of fit Zero and span drift Influence of ambient temperature Influence of sample gas flow for extractive AMS Influence of voltage variations Cross-sensitivity The following tables show the measured components and their certification ranges, for which this or a reduced test program was carried out. Table 1: Tested components and their certification ranges during laboratory test Component Certification range Unit N 2 O mg/m 3 Table 2: Supplementary measuring range to be tested with reduced program Component Measuring range Unit N 2 O mg/m 3

26 Page 26 of Field test The field test was carried out in the exhaust gas of a nitric acid plant, with two complete and identical measuring systems of the type Emerson NGA 2000 MLT 2 with serial numbers S/N1: and S/N2: (same instruments as in the laboratory). Type of plant: Exhaust gas cleaning system (before the measuring point): Measuring devices installed in the following positions: Exhaust gas boundary conditions: Moisture: Temperature: Dust concentration: CO 2 : Nitric acid plant Catalytic converter The measuring systems were installed in a horizontal exhaust duct. Inflow section is > 3 d, outflow section is 1.5 d. The duct has a round cross-section with a diameter of approx. 1 m. The measurement sections are lined up at a distance of approx. 1 m from each other in the exhaust duct Vol.-% approx. 100 C < 20 mg/m³ 0.05 Vol.-% The plant was selected because it conforms to a typical nitric acid plant. The field test started on 6 June 2012 and ended on 26 September The following performance criteria were tested in the field: Functional test Calibration function Response time Lack of fit Maintenance interval Zero and span drift Availability Reproducibility During the test, the instruments were set to the following specifications: Table 3: Set certification ranges during the field test Component Certification range Unit N 2 O mg/m 3 Since the values recorded at the field test site lay permanently in a range >200 mg/m 3, a measuring range of mg/m 3 was set for the field test. For this reason, the tests of response time and linearity were carried out both for the ranges mg/m 3 and mg/m 3.

27 Page 27 of 541 Figure 5: View of the measurement site with heated pressure regulators

28 Page 28 of 541 Figure 6: System 2 in measurement container

29 Page 29 of 541 Figure 7: Inner view of the heated pressure regulator in the field

30 Page 30 of Standard reference measuring methods 5.1 Method of measurement (discontinuous measurement) N 2 O Measurement method: VDI 2469 Part 1 Analysis: C-determination with ECD / VDI 2469 Part 1 Sampling equipment Sampling probe: Particle filter: Titanium N/A Gas volume measuring instrument: DESAGA GS 312 Gas collection container: Sample line before gas treatment: Distance between sampling probe and collection element: Sample gas treatment: Time between analysis and sample: Transport and storage: Analytical determination Analytical instruments: Sample bags, 22l 30 m, PTFE 1 m + sample gas line Drying with MgCl 2 in absorption bottles < 7 days Tightly sealed and protected from light SRI 8610C gas chromatograph with electron capture detector Columns: Packed column, Hayesep D, 15 cm, Ø 0.32 mm Carrier gas / Feeding: Temperature of detector 380 C Nitrogen / Sample loop, 1 ml Temperature-time program: Isothermal 50 C Evaluation: Standard: Performance characteristics Influence of accompanying substances: Detection limit: Measures for quality assurance: Area analysis with external standard N 2 O test gas 66.9 mg/m³, 6 concentrations diluted with nitrogen by a Horiba sample divider (5 fixed steps) with accuracy class 0.5 None, when separating SO 2 and moisture completely 0.5 mg/m³ Leak check, determination of overall blank sample, blank values

31 Page 31 of Determination of waste gas boundary conditions Dynamic pressure in the waste gas duct: SIKA GMH Static pressure in the waste gas duct: SIKA GMH Air pressure at the sampling point: LUFFT portable measuring instrument Last check / calibration: July 2012 Waste gas temperature: Temperature measuring device Model / type: Proportion of water vapour in the waste gas (waste gas moisture): Waste gas density: Ni-Cr-Ni thermocouple Voltkraft K101 The evaluation of present waste gas boundary conditions was necessary to determine a representative measuring point for comparison measurements in accordance with Standard EN Test gases and test standards Test gases used to adjust the analyser during the test (tested systems and TÜV-measuring systems): (The test gases mentioned below were used during the entire test and, if necessary, diluted with the help of a sample divider or a mass flow control station.) Zero gas: Test gas N 2 O in N 2 : Compressed air 498 mg/m³ Number of test gas cylinder: Manufacturer / date of manufacture: Praxair, 9 May 2012 Stability guarantee / certified: 5 years Certificate checked by [name] / on [date]: TÜV Rheinland, 5 June 2012 Rel. uncertainty according to certificate: 2 % Test gas N 2 O in N 2 : mg/m³ Number of test gas cylinder: Manufacturer / date of manufacture: Air Liquide, 10 December 2010 Stability guarantee / certified: 1 year Certificate checked by [name] / on [date]: TÜV Rheinland, 3 February 2012 Rel. uncertainty according to certificate: 2 % All materials and measuring systems used for the tests complied with the TEU quality management according to EN at the time of testing.

32 Page 32 of Test results 6a General Requirements 6a.1 [5.1 Application of performance criteria] Evaluation The test laboratory shall test at least two identical automated measuring systems (AMS). All AMS tested shall meet the performance criteria specified in this document as well as the uncertainty requirements specified in the applicable regulations. Two measuring systems of identical design were tested for suitability. The measuring systems fulfil the minimum requirements for monitoring emissions from stationary sources and the requested uncertainty. Sections 6a, 6b and 6c describe the tests and the results. Section 6d describes the results regarding the required measurement uncertainty.

33 Page 33 of 541 6a.2 [5.2 Ranges to be tested] Evaluation Certification range The certification range over which the AMS is to be tested shall comprise minimum and maximum values. The coverage shall be fit for the intended application of the AMS. The certification range shall be specified as follows: a) for waste incinerators as the range usually begins from zero, if the AMS is able to measure zero, and a value no greater than 1,5 times the daily average emissions limit value (ELV); b) for large combustion plants as the range usually begins from zero, if the AMS is able to measure zero, and a value no greater than 2,5 times the daily average emissions limit value (ELV). c) for other plants in relation to the corresponding emission limit value or any other requirement related to the intended application. The AMS shall be able to measure instantaneous values in a range that is at least 2 times the upper limit of the certification range in order to measure the half-hour values. If it is necessary to use more than one range setting of the AMS to achieve this requirement, these supplementary ranges will require additional testing (see 5.2.2). The certification range(s) and the performance criteria tested for each range shall be stated on the certificate. The test laboratory should choose for the field test an industrial plant with challenging measuring conditions. This means that the AMS can also be used under less demanding measuring conditions. The certification range is mg/m 3. There are no specified emission limit values for N 2 O. The certification ranges and minimum requirements tested for each range are stated on the certificate. Section 4.2 contains a detailed description of the field test site.

34 Page 34 of 541 Evaluation Supplementary ranges If a manufacturer wishes to demonstrate performance over one or more supplementary ranges larger than the certification range, some limited additional testing is required over all the supplementary ranges. This additional testing shall at least include evaluations of the response time and lack of fit. Cross-sensitivity has to be tested for interferents that have shown relevance during testing in the certification range. The concentration of the relevant interferents shall be proportionally higher than the values specified in Table 13, where the proportionality factor is given by the ratio of the considered supplementary range to the certification range. Supplementary ranges and the performance criteria tested for these ranges shall be stated on the certificate. One supplementary measuring range was defined for N 2 O and some additional tests were carried out to validate that range. A list of additionally admitted cross-sensitivity components and the results of the additional tests can be found in the respective sub-items of sections 6b and 6c. All additionally tested ranges are included in the certificate. Evaluation Lower limit of ranges The lower limit of the certification range is usually zero. The lower limit of the certification range is zero for all tested components.

35 Page 35 of 541 Evaluation Expression of performance criteria with respect to ranges The performance criteria are expressed in terms of a percentage of the upper limit of the certification range for each measured component except for oxygen where the performance criteria are expressed as volume concentrations. A performance criterion with respect to ranges is a value that corresponds to the largest deviation allowed for each test, regardless of the sign of the deviation determined in the test. The deviations are expressed in terms of percentage of the upper limit of the certification range for all tests. The deviations for oxygen are expressed in terms of volume concentration. Evaluation Ranges of optical in-situ AMS with variable optical length The certification range for optical in-situ AMS with variable optical length shall be defined in units of the measured component concentration multiplied by the length of the optical path. The path length used for testing shall be stated on the certificate. The measuring system tested is not an in-situ AMS with variable optical path length.

36 Page 36 of 541 6a.3 [5.3 Manufacturing consistency and changes to AMS design] Evaluation Certification is specific to the AMS version that has undergone performance testing. Subsequent design modifications that might affect the performance of the AMS can invalidate the certification. Manufacturing consistency and changes to AMS design are described in EN All tests were performed with the measuring systems described in section 3. The test results in this report and on the associated certificate refer to measuring systems that comply with the tested versions only. The manufacturer has been informed that any modification to the certified system has to be agreed upon with the test institute and that this may lead to additional or new tests of the measuring system. No guarantee shall be provided for the continued validity of the certification if the equipment configuration for hardware and/or software is modified.

37 Page 37 of 541 6a.4 [5.4 Qualifications of test laboratories] Evaluation Test laboratories shall be accredited to EN ISO/IEC and the appropriate test standards for carrying out the tests defined in this European Standard. Test laboratories shall have knowledge on the uncertainties attributed to the individual test procedures applied during performance testing. CEN/TS provides an elaboration of EN ISO/IEC for application to emission measurements which should be followed when using specified standard reference methods in Annex A of Standard EN TÜV Rheinland Energie und Umwelt GmbH is accredited for performance testing (QAL1), functional tests (AST), calibrations (QAL2), and emission measurements according to EN ISO/IEC until Figure 28 in the annex shows the Certificate of Accreditation.

38 Page 38 of 541 6b Performance criteria common to all AMS for laboratory testing 6b.1 [6.1 AMS for testing] Equipment All AMS submitted for testing shall be complete. These specifications do not apply to the individual parts of an AMS. The test report shall be issued for a specified AMS with all its parts listed. An AMS that uses extractive sampling systems shall have appropriate provisions for filtering solids, avoiding chemical reactions within the sampling system, entrainment effects and effective control of water condensate. Measuring systems with different options for the sampling line length shall be tested with an appropriate sampling line length agreed between the test laboratory and the manufacturer. The length shall be quoted in the test report. The test laboratory shall describe in the test report the type of sampling system. The test was performed with two complete and identical measuring systems of the Emerson NGA 2000 MLT 2 type. The length of the sampling lines was 29 m. Section 3.2 describes the sampling system in detail. Software version is implemented in the measuring device. Method It was checked whether the two AMS and the manual were complete. Pictures of both systems were taken before and during the test. Evaluation Both systems were identical and comprised the extractive sampling system and analyser module, including data output. An instruction manual is available. Assessment The suitability-tested version comprises the entire measuring system including sampling system, analysers, data output, and manual. This complies with the minimum requirements.

39 Page 39 of 541 Detailed presentation of test results The AMS tested comprises the following parts: - Sampling probe (stainless steel), lockable - Pressure regulator in heated enclosure, including 1 m long heated hose to the sampling probe - 29 m long heated hose to the analyser - Mounting plate (unheated), assembled on top are: - NGA 2000 MLT 2 analyser - Pump - Cooler - Complete pipework (including magnetic valves) for connection of zero and calibration gas lines, etc. Images of the system are presented in section 3.2. A copy of the manual is available in the annex (page 121 ff.).

40 Page 40 of 541 6b.2 [6.2 CE labelling] Equipment The AMS shall comply with the requirements for CE labelling specified in applicable EU Directives. These include, for example: Electro-Magnetic Compatibility Directive 89/336/EEC and its amendments 92/31/EEC and 93/68/EEC, and Low-Voltage Directive 72/23/EEC and its amendment 93/68/EEC covering electrical equipment designed for use within certain voltage limits. AMS manufacturers or suppliers shall supply verifiable and traceable evidence of compliance with the requirements of the relevant EU Directives applicable to the equipment. No equipment is necessary to test this performance criterion. Method The manufacturer presented the certificates and the supporting test documentation. Evaluation The following documents were presented to the test institute: CE certificate Certificate of electromagnetic compatibility Certificate according to Directive 72/23/EEC Assessment The certificate of CE labelling was presented to the test institute. This complies with the minimum requirements. Detailed presentation of test results Figure 29 in the annex shows a copy of the certificate (p. 106).

41 Page 41 of 541 6b.3 [6.3 Security] Equipment The AMS shall have a means of protection against unauthorised access to control functions. No equipment is necessary to test this performance criterion. Method The AMS was started by following the instructions of the manual. Then, the safety provision for protection against unauthorised access to control functions of the AMS (password protection) was activated. The reliability of the safety device was then tested. Evaluation Not necessary in this case. Assessment The AMS is protected by password against unauthorised access to control functions. This complies with the minimum requirements. Detailed presentation of test results Not required for this performance criterion.

42 Page 42 of 541 6b.4 [6.4 Output ranges and zero point] Equipment The AMS shall have a data output with a living zero point (e.g. 4 ma) so that both negative and positive readings can be displayed. The AMS shall have a display that shows the measurement response. The display may be external to the AMS. The test laboratory shall check whether the output ranges on the AMS can be adjusted and whether such ranges are appropriate for the intended applications. The emission limit values to be monitored with the AMS should be documented, together with an indication of the suitability of the AMS ranges for applicable EU Directives and other intended applications. The test laboratory shall use reference materials to verify that the output range is at least twice as great as the certification range. The test was carried out with zero and test gas. A multi-meter was used for collecting analogue signals Method It was checked whether the desired measuring ranges could be adjusted under consideration of the measurement task. Using zero and test gas, the signal output was checked for compliance with the requirements such as living zero and measuring range. Evaluation The position of zero point can be adjusted to 4 ma. The output range of the AMS can be adjusted to the requirements of the relevant directives. Assessment The output range can be set on the measuring system. At 4 ma, zero point amounts to 20% of the analogue system output. The AMS can also display negative values. All relevant limit values can be monitored. The additional check of higher measuring ranges for component N 2 O also ensures monitoring at higher emission concentrations. This complies with the minimum requirements. Detailed presentation of test results Not required for this performance criterion.