October 1997 Ref : 02003Ren9771

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Continuous emission monitoring in power stations and combined heat and power plants
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Thermal Generation Study Committee

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The Union of the Electricity Industry - EURELECTRIC, formed as a result of a merger in 1 December 1999 of the twin Electricity Industry Associations, UNIPEDE and EURELECTRIC2, is the sole sector association representing the common interests of the European Electricity Industry and its worldwide affiliates and associates. Its mission is to contribute to the development and competitiveness of the Electricity Industry and to promote the role of electricity in the advancement of society. As a centre of strategic expertise, the Union of the Electricity Industry - EURELECTRIC will identify and represent the common interests of its members and assist them in formulating common solutions to be implemented and in coordinating and carrying out the necessary actions. To that end it will also act in liaison with other international associations and organisations, respecting the specific missions and responsibilities of these organisations. The Union of the Electricity Industry - EURELECTRIC is also the association of the Electricity Industry within the European Union representing it in public affairs, in particular in relation to the institutions of the EU and other international organisations, in order to promote the interests of its members at a political level and to create awareness of its policies. The reports published by EURELECTRIC are the result of the work of its structure of expertise: they represent one of the most direct methods of circulating knowledge and information throughout the sector, on subjects of common interest. They are intended for wide circulation both within the electricity supply industry and outside it. Please do not hesitate to ask for the latest available printed EURELECTRIC publications catalogue (with summaries of EURELECTRIC reports) from:

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1 2

International Union of Producers and Distributors of Electrical Energy European Grouping of Electricity Undertakings
The Union of the Electricity Industry EURELECTRIC has been formed through a merger of the two associations

and

TABLE OF CONTENTS EXECUTIVE SUMMARY .................................................................................................. 1 ACRONYMS........................................................................................................................4 ACKNOWLEDGEMENT ...................................................................................................4 1. INTRODUCTION ............................................................................................................5 1.1 BACKGROUND...................................................................................................................5 1.2 OBJECTIVES ......................................................................................................................5 1.3 IMPLEMENTATION .............................................................................................................5 2. REASONS FOR CONTINUOUS EMISSION MONITORING.....................................6 2.1 DEVELOPMENTS IN MONITORING WORK BY UTILITIES ........................................................7 3. TECHNICAL ASPECTS OF CONTINUOUS EMISSION MONITORING ................ 9 3.1 EXTRACTIVE CEM ............................................................................................................9 3.2 IN-SITU CEM .................................................................................................................. 10 3.3 PERFORMANCE CRITERIA ................................................................................................ 11 3.4 DETERMINATION OF MASS FLOW MEASUREMENT AND PEM............................................ 14 3.5 REPORTING ..................................................................................................................... 14 4. EXPERIENCE WITH CEM.......................................................................................... 17 4.1 EXTRACTIVE CEM .......................................................................................................... 17 4.2 IN-SITU CEM .................................................................................................................. 19 4.3 ACCURACY ..................................................................................................................... 21 4.3.1 Uncertainties of the Measurement Systems .................................................................. 21 4.3.2 Experience with accuracy reported in the different countries....................................... 22 4.4 REPORTED EXPERIENCE OF A GENERAL NATURE.............................................................. 25 4.5 INVESTMENT AND OPERATING COSTS .............................................................................. 26 5. GENERAL DISCUSSION ............................................................................................. 27

LIST OF TABLES pag e TABLE 1 National and regional criteria for CEM ............................................................ 4 TABLE 2 Extractive sampling principles reported for the different flue-gas components in each country.................................................................................................. 13 TABLE 3 In-situ principles reported for the different flue-gas components in each country14

EXECUTIVE SUMMARY The necessity for Continuous Emission Monitoring (CEM) for process and emission control of combustion plants is increasing in line with the increased automation of new plants and additional regulatory requirements. This report presents experience and trend information from utilities regarding continuous emission monitoring (CEM) at power and Combined Heat and Powr (CHP) production units in Europe. Topics covered include; reasons for installations, experience and future expectations of the quality, performance, long-term availability and costs of CEM installations. The following components are covered; NOx, SO2, CO, dust, "secondary" flue-gas components (mainly NH3) and the continuous monitoring of flue-gas velocity. Most of the experience comes from those utilities represented in the UNIPEDE-THERNOX group. Other utilities in these countries may therefore have differing experiences. It has also been difficult to collect all the relevant experience for some of the countries. The most important trend apparent is the increasing requirement for CEM measurements, driven particularly by new requirements of the regulatory authorities. The utilities have performed many investigations into CEM and its advantages. CEM is consequently used not only for control of the environmental performance of a plant but also (particularly in the case of NOx, CO and dust) for optimisation and control of the operation of the plant. Existing and new plants continue to be fitted with emission control measures such as low-NOx burners and deNOx. An increasing number of CEM installations are therefore required, not only for measurement of NOx for deNOx process control, but also for measurement of NH3 slip when using SNCR. CEM is also widely used in Sweden for the determination of fees and taxes for NOx and SO2 emissions respectively. Continuous emission monitoring can be done with either extractive or in-situ systems. The use of extractive CEM to date has greatly exceeded that of in-situ CEM. A trend towards greater use of in-situ systems is now becoming apparent on the market. The experience reviewed in this study shows no definite trends for choice of extractive or in-situ CEM, both have been applied successfully in many countries. The sampling principle of most of the extractive CEM systems is based on extraction of flue gas with condensation of water vapour - all countries in this study have reported experience of this sampling principle. There are, however, also some countries that have reported experience of extractive sampling systems with dilution and/or heated extractive systems. The reported experience with CEM based on extraction with condensation is better than that of CEM based on extraction with dilution or heated extractive CEM. The most common in-situ CEM method is single point measurement with a probe, but many in-situ CEM systems measure across the duct. Most countries in this study have experience with both types of in-situ CEM. The most common analytic principles for CEM are IR/UV-absorption. Extractive based CEM mostly uses NDIR or NDUV while the in-situ systems also use differential optical absorption spectroscopy (DOAS) or IR/UV-absorption. Electrochemical cell-based methods could be used for both extractive and in-situ systems. In-situ CEM systems for the measurement of dust are mostly based on opacity. A common practice in extractive CEM for

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NOx is the use of converters for the reduction of NO2 followed by analysis for NO to determine total (NO + NO2). Manufacturers of extractive CEM in Europe reported in this study include; Hartmann & Braun, ADC, Siemens, Rosemount, Bodenseewerk and Maihak. ADC produces CEM based on extraction with dilution while the remaining manufacturers mainly produce extractive CEM with condensation. Bodenseewerk also produce heated extractive CEM. Manufacturers of in-situ CEM in Europe reported in this study include; Lear Siegler, SICK, OPSIS, Codel, Land and Durag. SICK, Codel and OPSIS mostly measure across the duct while Lear Siegler and Land use in-situ probes. The reported experience (accuracy, performance, long term availability, operating costs etc.) with extractive and in-situ CEM systems show no major differences. The main advantages with in-situ CEM are the removal of the need for sample conditioning and the fact that it is possible to measure components, such as NH3 and NO2, that otherwise are partly or totally removed during sample conditioning. A number of plants are equipped with SNCR-systems and accurate measurement of the NH3 slip is therefore useful. Measurement of NH3 with insitu CEM can easily be combined with measurement of NOx and/or SO2. A disadvantage of most in-situ systems is the problem of calibration on a regular and routine basis. Extractive CEM, on the other hand, is very easy to calibrate. It takes time and due care to apply CEM in daily operation with adequate accuracy. In general there have been few problems with extractive CEM. Almost all difficulties reported relate to the sampling and calibration systems. Condensate management requires careful attention if problems are to be avoided. Maintenance requirements can be high unless the system is carefully designed with e.g. provision for back purging of probe filters. Although low levels of maintenance are reported concerning in-situ CEM it is clear that there is a need for a minimum level of essential maintenance e.g. cleaning of windows and checking of optical path alignment. It is not possible from the survey to recognise any clear trend regarding the performance and availability of CEM systems. It is clear from many responses that some calibration systems pose problems and require further attention. A common difficulty appears to be the quality and reliability of calibration gas standards. The accuracy of gaseous emission concentrations in flue gas is expected to be high if calibrations are performed carefully and with certified calibration gases or calibration cells. One reported experience from an accredited laboratory is that the deviation between a stationary CEM and a mobile extractive CEM in most cases is below 4% of the measured values. The accuracy of dust CEM, especially at low concentrations, is low though. The accuracy of yearly emission depends also on uncertainties in fuel flow and mass flow calculation. A study on three coal fired power plants reports +/- 5 to 11 % uncertainty for NOx-emission and +/- 25 to 30 % for SO2-emission at low concentrations after FGD (mainly due to concentration gradients in flue gas ducts and single point measurement). In most countries measurements are made at a single location (extractive CEM or single point in-situ probes) which is often determined by grid testing. Most analysers are provided with systems for automatic calibration. There are also purge air systems to clean the measurement windows (in-situ CEM). In most of the countries, performance criteria for CEM have been
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established. Only in Germany (and anticipated in Ireland) does a standard approval system for the CEM instruments exist. The mass flow are mostly calculated from the measured concentrations in conjunction with the fuel consumption, the excess air level and the fuel analysis and seldom from the measured concentrations and the measured flue gas velocity. In the future it is possible that other flue gas components will be measured more widely and other analytic technologies used. Typical examples of such components are NH3 and N2O for process optimisation. FTIR and diode laser are example of new measurement techniques coming into use. It is also very possible that existing analysers will be developed further and their availability and performance improved the electrochemical analysis principle is an example of such an technique. In some countries Predictive Emission Monitoring (PEM) has been tested for the determination of NOx emissions. A PEM system can be verified by multivariate data analysis or based on predictions by neural network. The plant must be fired with fuels of constant quality if a PEM system is to be used.

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ACRONYMS AFNOR - French Standards Organisation. BEES - Besluit Emissie Eisen Stookinstallaties: Ordinance on Emission Limit Values for Combustion Installations in the Netherlands. BS - British Standard CEM - Continuous Emission Monitoring. Chemiluminescense - detection based on the luminescense reaction of NO with O3. DOAS - Differential Optical Absorption Spectroscopy. EPA - Environmental Protection Agency. FGD - Flue-gas desulphurisation (deSOx). FTIR - Fourier Transformed Infra-Red. Extractive CEM - The analysis takes place outside the flue gas duct. HMIP - Pollution Inspectorate (United Kingdom)- now part of the UK Environment Agency. In-situ CEM - The analysis takes place inside the flue gas duct. IR-absorption - Infra-Red absorption. The analysis principle is based on the transmission of characteristic wavelengths in the infra-red spectrum. LCPD - Large Combustion Plant Directive of the EC (88/609/EEC). NDIR - Non Dispersive Infra-Red. NDUV - Non Dispersive Ultra-Violet. PDA - Photo Diode Array. PEM - Predictive Emission Monitoring or (Parameter Monitoring). PEN - National Energy Plan (Spain). SCR - Selective Catalytic Reduction (deNOx). SEPA - Swedish Environmental Protection Agency. SNCR - Selective Non-Catalytic Reduction (deNOx). TA-luft - Technical rules that prescribe the required conditions for CEM in Germany. TV - Technischer berwachungs-Verein, Organisation of Technical Inspection Agencies in Germany. The required conditions for CEM are defined by TA-luft and verified by (TV) test laboratories. USEPA - US Environmental Protection Agency. UV-absorption - Ultra-Violet absorption. The analysis principle is based on the transmission of characteristic wavelengths in the ultra-violet spectrum. ACKNOWLEDGEMENT In addition to the authors, the following persons have made major contribution to the report; Mr. Brendan BARRY - ESB (Electricity Supply Board) Mr. Roland CSADER - Badenwerk AG Mr. Mark ELSWORTH - National Power PLC Mr. Daniel MAILLIET - EDF (Electricite de France) Mr. Henk SPOELSTRA - KEMA

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1. 1.1

INTRODUCTION Background

In 1993 the UNIPEDE THERNOX report on NOx control Technologies was published. In this report a short statement was made about NOx measurement technologies. Widespread use of NOx reduction measures as well as a requirement to meet emission limit values means that NOx measurement is required under all operating conditions. Only robust measuring instruments are suitable for power plant operation conditions. Factors such as high mass flows, large flue gas channel cross sections, particulate containing flue gas and relatively low NOx and SOx concentrations which are all characteristic of power station emissions, pose difficulties for representative emission measurements. In recent times much work has been directed at improving measurement facilities. In 1994 the Thermal Generating Study Committee charged THERNOX to report in more detail on CEM in power stations and CHP plants. After that a working group was established to report on the European situation regarding CEM. Decision was made to collect the information by means of an inventory on experiences of CEM among the THERNOX members. 1.2 Objectives

The objectives of this study were; - To document the reasons for CEM installations in Europe; are they installed to meet the requirements of the regulatory authorities?, or for process monitoring and control?, or for both purposes? - To follow-up reported studies and to survey current CEM studies in Europe. - To follow-up experience and opinions about the quality, performance, long-term availability and costs of CEM installations. 1.3 Implementation

To collect (and document) the necessary information a questionnaire was sent to the THERNOX Group- members. The questionnaires were filled in by all members in the THERNOX group and were evaluated and processed by the working group. It should be noted that the results from this study are not fully comprehensive for all countries. Practice and experience is reported mainly from those utilities represented in the UNIPEDE-THERNOX group.

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2.

REASONS FOR CONTINUOUS EMISSION MONITORING

Continuous monitoring of emissions is required principally to meet the requirements of the regulatory authorities. In the EC the LCPD 88/609/EEC prescribes the minimum requirements; -continuous monitoring of NOx, SO2, O2 and dust in new plants > 300 MWth, (with a possibility to exclude SO2 and dust from the CEM demands of the authorities), determination of annual emissions for SO2 and NOx in new plants and -emission inventory of SO2 and NOx in existing plants. Appendix A contains the text of article 15 and annex 9 of the LCPD which describe CEM. Also, many countries have had CEM requirements before the adoption of the LCPD. Monitoring of other flue gas components is required in some countries. There can be variations at national and regional levels, mostly depending on the thermal rating of the plant. Typical requirements for continuous monitoring are listed in table 1. TABLE I Country Austria Belgium France National and regional criteria for CEM Component NOx, SO2 CO, dust NOx, SO2, dust NOx, SO2, CO dust HCl NOx, SO2, CO, dust NOx, SO2, dust NOx, SO2 CO dust NOx, SO2, dust NOx, SO2, dust CO NOx SO2 CO Dust NOx, SO2, dust NOx SO2 Criteria > 30 MWth > 10 MWth > 300 MWth > 150 kg/h > 5 kg/h > 20 kg/h yes there will be requirements within 2 years national law (>300 MWth), local authorities national and regional limits > 300 MWth, local authorities > 300 MWth emission limits authority requirements 30 kg/h 50 kg/h 100 kg/h large combustion plants all plants > 50 MW which produce more than 50 GWh/year, local authorities, fees all peat and coal fired plants > 50 MW which produce more than 50 GWh/year, taxes some local limits national and cantonal (regional) authorities

Germany Ireland Italy

Netherland s Poland Portugal

Spain Sweden

Switzerlan d
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Hg, NH3, N2O, dust NOx, SO2, CO, dust

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Country United Kingdom

Component NOx, SO2

CO Dust

Criteria new plants > 50 MWth, existing plants (>50 MWth) within 3 years , local limits also exists some new plant >50 MWth -

Secondary reasons for CEM include process monitoring and control - e.g. monitoring of NOx, CO and dust for combustion control, of SO2 for control of FGD and of NOx to control deNOx processes. NH3 may also be measured (as in Sweden and United Kingdom) to control NH3-emissions from deNOx processes and conditioning of dust control devices respectively. Measurement of SO2 to control deSOx processes is required in some countries - in the Netherlands the efficiency of an FGD must be better than 85 % and be controlled by CEM. Velocity may be measured for the calculation of mass flow, it is possible to direct measure the velocity but that is normally not preferred. CEM is also used for combustion modifications or other primary NOx control measures. In Sweden there is a fee-system for emissions of NOx. Plants with energy production greater than 25 GWh/year are included and must quantify their emissions of NOx either by CEM or by estimation using an officially-defined fixed high level. The principle of the fee-system is that plants which qualify must report their emissions of NOx (as NO2) and their energy production to SEPA (the Swedish Environmental Protection Agency) each year. For every kg of NOx emitted the plant must pay SEK 40 (about 4). The total payments made by all plants are refunded. The refund to each plant is based on the ratio of its total energy production to the total energy production of all the qualifying plants. Plants with low emissions and high efficiency therefore make money at the expense of plants with high emissions and low efficiency. In Sweden there are also taxes on sulphur (SEK 30/kg S). This tax is based on the sulphur content in the fuel. A plant emitting less sulphur than that contained in the fuel receives a refund. CEM must be used for the determination of this refund. 2.1 Developments in Monitoring Work by Utilities

the Netherlands; (NOx and SO2); Multi-component analysers such as FTIR (Fourier Transform Infra Red) and PDA (Photo Diode Array) are in use. There is a gradual improvement of emission monitoring through improvements in the quality of the system in all its aspects and through an increase in the number of CEM-systems. Studies are being made on the precision and accuracy of the reported data, both for each installation and for the aggregate emissions of all power stations. Poland; In Poland there is a need for a rapid reduction in emissions from utility boilers. An increasing number of CEMs are being installed for process control. Portugal; (NOx); Measures include research and development to assess the influence of typical measures for NOx abatement and to establish engineering relationships between operating variables influencing NOx emissions and global boiler performance in terms of energy
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efficiency, fouling, slagging, safety and reliability. Several engineering tools are under development for the prediction of NOx emissions and boiler performance (as a function of operating conditions and fuel type) and these are being assessed at present. Sweden; (SO2, CO, NOx, NH3); Gradual improvements are planned such as more cost-effective CEM, "stripped" versions of established techniques and CEM based on analysis by electrochemical cells. Predictive emission monitoring (determination of the NOx-emission from other process parameters; e.g. combustion temperature, oxygen concentration, fuel flow etc.) for oil and gas burners is being studied. Recently, diode lasers have been used for NH3 measurement. In the future; testing of continuous measurements by use of FTIR (hydrocarbons) will take place. Switzerland; (NOx); Installation of CEM to study all parameters of the NOx-emissions and to optimise the emissions through primary measures. (SO2); Oil with very low sulphur content will be used. CEM is not applied to oil fired boiler because the fuel analysis gives a better accuracy. United Kingdom; (SO2, NOx); Independent reviews by power producers are planned on the relative accuracy of predictive calculation methods versus direct measurement. Cost effective instrumentation is currently being reviewed. (NOx); A watching brief will be maintained on developments in predictive emission monitoring e.g. neural networks etc. (All components); More cost-effective CEM is being sought this will be done through reviews of new instruments as and when they appear on the market.

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3.

TECHNICAL ASPECTS OF CONTINUOUS EMISSION MONITORING

Continuous emission monitoring can be done with either extractive or in-situ systems. To date the use of extractive CEM for gaseous emissions has greatly exceeded that of in-situ CEM. A trend towards greater use of in-situ systems is now becoming apparent in the marketplace. To reduce uncertainties in the flue gas because of concentration profiles there are international standards for location of representative sampling point(s). Standard rules or guidelines for the location of sampling points for CEM have been reported from four countries (France, Poland, Sweden and United Kingdom). In most countries measurements are made at locations where the flue gas inhomogeneity is low at a single location (extractive CEM or single point in-situ probes) which is often determined by grid testing. In all countries the measurement point for emission control is located either at the stack or in the gas duct leading to it. For process control there can also be measurements before and after the deNOx/de-SOx process. A number of manufactures in Europe are listed in appeendix B. 3.1 Extractive CEM

The sampling principle of most of the extractive CEM systems is based on extraction of flue gas with condensation of water vapour all countries surveyed in this study have experience of this sampling principle. Experience of extractive sampling systems with dilution has also been reported by Austria, France, Poland, Spain, Sweden, Switzerland and the United Kingdom. Heated extractive systems are used for sampling condensable components such as NH3 and HCl. Experience of such systems has been reported by France, the Netherlands, Sweden and United Kingdom. Table II contains details of the flue gas constituents monitored and the sampling principles reported for each country. The most common analytic principles used are NDIR or NDUV-absorption. Chemiluminescence is also used for analysis of NOx. Use of converters for the reduction of NO2 followed by analysis for NO to determine (NO + NO2) is also a common principle. Analysis by electrochemical cells has been done in the United Kingdom and Sweden. Use of UV fluorescence for the determination of the SO2-concentration has been reported from Poland, Sweden and United Kingdom. Dust has been measured by absorption gauges in France and Sweden. Equipment manufacturers that were mentioned in the answers include Hartmann & Braun, ADC, Emission S.A., Siemens, Rosemount, Bodenseewerk and Maihak. The operating principle of most of those analysers is based on absorption in the IR or UV spectrum of samples extracted with condensation. ADC, however, operates by extraction with dilution and uses Chemiluminescence and UV fluorescence for analysis of NOx and SO2 respectively. Heated extractive analysers, based on 2nd derivative IR-spectroscopy combined with gas filter correlation, are produced by Bodenseewerk.

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TABLE II

Extractive sampling principles reported for the different flue-gas components in each country Sampling principles reported extractive with condensation heated extractive extractive with dilution extractive with condensation* extractive with condensation extractive with dilution heated extractive extractive with condensation extractive with condensation extractive with condensation extractive with condensation heated extractive extractive with condensation extractive with dilution extractive with condensation heated extractive extractive with condensation extractive with dilution extractive with condensation extractive with dilution heated extractive extractive with condensation extractive with dilution extractive with condensation, extractive with dilution heated extractive Components NOx, SO2, CO NH3 " NOx, SO2, CO NOx, SO2, N2O NOx, SO2 HCl, dust NOx, SO2, CO CO NOx, SO2, CO NOx SO2, NOx NOx, SO2, CO " NOx, CO SO2 NOx, SO2 " NOx, SO2, CO, N2O NOx, SO2, CO NH3, HCl, dust, N2O, NOx, CO NOx, CO NOx, SO2 NOx, SO2, CO NOx, SO2, CO NOx, SO2, CO

Country Austria

Belgium France

Germany Ireland Italy Netherlands Poland Portugal Spain Sweden

Switzerland United Kingdom

*Gas turbines only 3.2 In-situ CEM

The principle of most in-situ CEM systems is single point measurement with a probe. The most common example of an in-situ CEM, the ZrO2-cell which is used for the determination of Oxygen, is not discussed in this report. There are also in-situ CEM systems which measure across the duct and which are therefore less sensitive for siting. Most countries studied have experience with both types of in-situ CEM. All flue gas components discussed in this report except N2O have been measured by in-situ CEM techniques. The analytic principles for in-situ CEM are IR/UV-absorption or electrochemical cell-based methods. In-situ CEM systems based on opacity are used for the measurement of dust. There is also, normally, a purge air supply to clean the sample windows.

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TABLE III Country Austria Belgium

IN-SITU PRINCIPLES REPORTED FOR THE DIFFERENT FLUEComponents dust SO2, NOx, NH3, H2O NO, SO2 CO dust NOx, SO2 NOx CO dust NO, SO2 dust NOx, SO2 NO, SO2 NO, SO2 NO, SO2, NH3 NOx, SO2, NH3, Hg, H2O, HCl CO NO, SO2 dust NH3 CO NO, SO2 NO, CO NOx, SO2

GAS COMPONENTS IN EACH COUNTRY

France Germany Ireland Italy Netherlands Poland Portugal Spain Sweden

Monitoring principles reported opacity, light absorption DOAS (UV) 2nd derivative UV-spectroscopy IR opacity, light absorption DOAS (UV) electrochemical cells IR opacity, light absorption UV, 2nd derivative UV-spectroscopy opacity, light absorption DOAS, UV, 2nd derivative UVspectroscopy UV, electrochemical cells 2nd derivative spectroscopy (IR/UV) UV DOAS (UV) NDIR 2nd derivative UV-spectroscopy opacity, light absorption diode laser IR UV NDIR, IR electrochemical cells

Switzerland United Kingdom

The most commonly reported manufacturers of in-situ CEM are Lear Siegler, SICK, OPSIS, Codel, Land and Durag. SICK, Codel and OPSIS mostly measure across the duct while Lear Siegler and Land are based on measurement by in-situ probes. 3.3 Performance Criteria

Performance criteria or guidelines for CEM systems have been established in most countries reported in this survey. Only Germany (anticipated in Ireland) has official approval procedures for CEM instruments, only approved types of instruments can be used. Switzerland does not have an official approval procedure as such, but in some cantons (regions), the measurement instruments must be of a type that is officially approved by the German TV. In Poland the General Environmental Inspectorate have established guidelines for the design of CEM systems.

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Practice in the USA can be mentioned in this chapter. Germany only approves the specific components in the monitoring system. In contrast, the plant owner in the USA must implement a QC/QA-program for the entire measurement system. This approval includes very detailed tests. Although it may appear that the systems are very different, there are developments on EMAS and QA that tend to go in the same direction in Europe. Austria; NORM M9410, 9411. The extraction point is fixed by an authorised institute during commissioning ; The availability of data per month must be > 90 %; Zero point and span calibrations must be done at least once per week; A "technical service" is required every three months. The equipment and criteria are checked every year by the authorised institute; An independent system calibration is done by this institute every 3 years. France; (NOx and SO2); Measurements must be carried out according to AFNOR standards (French Standards organisation) which includes sampling and measurement methods. The license issued by the local authority contains general requirements on regular checking and requires an annual test to be carried out by an accredited independent test laboratory. (Dust); The French authorities require CEM for plant emitting more than 5 kg/h. If the emission exceed 50 kg/h periodic measurements by gravimetric techniques are required also. Germany; (SO2, NOx and dust); TA-luft prescribes the required conditions. TV inspection verifies this. Ireland; (NOx and SO2); The Irish EPA have expressed a preference for CEM which meets TA-luft or which complies with USEPA requirements. Italy; (All flue gas components); Precision, rise time, fall time, response time, detection limit, sensitivity, repeatability, linearity, zero drift, span drift, immunity to interference are some of the instrument characteristics influencing selection in the purchasing process. The Netherlands; (SO2, NOx and dust); Performance criteria are set according to the "Regulations of Measuring Methods of the BEES". CEM should be used in accordance with generally accepted measuring practice. Poland; In Poland there is an official issue of guidelines and technical requirements for CEM. If power plants install CEM according to these requirements, results of the monitoring are accepted by the Regional Environmental Inspectorate. At other plants the Regional Environmental Inspectorate can perform spot emission measurements. If emissions for certain components exceed upper allowable limits, the power plant must pay a penalty until measurements show that the emissions are below the legal limit. (NOx and SO2); Detection limit = 2 % of measurement range; Zero point drift (between two calibrations) = 2 % of measurement range; Effect of interferences = 4 % of measurement

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range or automatic compensation for interfering components; Response time = 240 seconds; The measurement range should be 150 % of average measured value. (NOx and SO2); Analysis should be possible with correction of results for the measured oxygen concentration and (sometimes) the content of water vapour in the flue gas - since oxygen and water vapour determine the dilution level in flue gas. (CO); Detection limit = 0,2 %; Effect of interferences = 0,5 %; Zero drift = 0,5 %; Temperature affect = 0,2 %/10 oC. (Gas velocity); Error +/- 2 % of range (Zero and test point drift within 2 % of limit). Portugal; (NOx, SO2 and CO); The measurement equipment must be submitted to periodic calibration according to the relevant legislation. The span and calibration gases should be certified and differ at most by 2 % from the stated value. Spain; (NOx, SO2); There are standard requirements for the installation of CEM equipment. All equipment is installed at the same location where the flow is homogeneous. Sweden; (NOx, SO2 and O2 /CO2 ); Criteria for CEM for the determination of NOx fees and sulphur taxes; Detection limit % of measurement range; Zero point drift (between two 2 calibrations) 2 % of measurement range; Span drift (between two calibrations) 4 % of measurement range; Effect of interferences 4 % of measurement range; Response time (the whole measurement system) 200 seconds. The measurement ranges should be about twice the highest expected concentrations in the flue gas. The span and calibration gases should be certified and differ by a maximum of 2% from the stated value. (Velocity); Criteria for CEM for measurement of velocity where this is used for the calculation of the mass emission of NOx and sulphur; Detection limit 10 % of measurement range; Zero point drift (between two calibrations) 2 % of measurement range; Span drift (between two calibrations) 4 % of measurement range; Response time (the whole measurement system) 30 seconds. (NOx, SO2 and CO2, O2 or velocity); The whole monitoring system shall be verified by an accredited laboratory once a year (by parallel measurement). There are then two other criteria; The standard deviation between the utilities CEM and the accredited laboratory s CEM result or measured velocity data must be 5 % of measurement range; Systematic error between the two systems must be 2 % of measurement range. Switzerland; (All components); Use of the best measurement technology is required; the Swiss authorities set the specification for official measurements; the performance of CEM systems must be accepted by the Cantonal authorities also; the instruments must generally be approved by the German TV. (NOx); Measurement according to VDI 2456; overall NOx uncertainty +/- 10 %. (SO2); Measurement according to VDI 2462. (CO); Measurement according to VDI 2459; overall CO uncertainty +/- 10 %.

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3.4

Determination of Mass Flow Measurement and PEM

The dominant method for determination of mass flow is stoichiometric calculation on the basis of fuel composition, flue gas O2 content and fuel consumption. This applies in most countries. Use of direct measurement of flue gas velocity is normally not used. Predictive emission monitoring (PEM) for the determination of NOx emissions has been tested in some countries. This has involved prediction by neural network or multivariate data analysis. Italy; (NOx and SO2); Periodic measurements have been made on thermal units < 300 MWth. Mass flow rate is calculated stoichiometrically on the basis of fuel consumption and O2 content in flue gas. Netherlands; It is permissible to determine NOx emissions by the continuous measurement of one or more characteristic parameters. A relationship is derived between these characteristic parameters and NOx emissions which is verified every 3 years. The statement is only true when a simple relationship exists between NOx-emissions and load e.g. in natural gas-fired power stations with constant gas quality but never in coal-fired power stations. Poland; In those cases where there is no direct measurement of the flue gas mass flow, the mass flow rate is calculated stoichiometrically on the basis of fuel consumption and the O2 content of the flue gas. Portugal; Assessment is being done on several engineering tools which are under development for the prediction of NOx emissions and boiler performance as a function of operating conditions and fuel type. Sweden; The principle of predictive emission monitoring (PEM) is accepted by SEPA for determination of NOx-emissions. The first applications have been for two biofuel-fired boilers in two separate saw-mills during 1996. The performance criteria for PEM must be similar to the performance criteria for a CEM (chapter 5.3). Mass flow rate is calculated stoichiometrically on the basis of fuel composition and flue gas O2 content. Switzerland; The principle of predictive emission monitoring (PEM) is generally accepted by the authorities (for gas and oil combustion). The NOx emissions can be determined by the continuous measurement of characteristic parameters. The accuracy must be similar to direct measurements. United Kingdom; A watching brief is being kept on developments in PEM e.g. neural networks. 3.5 Reporting

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The EC LCPD stipulate reporting of emission from new (large) plants. LCPD describes monitoring of concentrations of SO2, NOx and dust and the statistical procedures in order to assess compliance with ELV. In addition national or regional authorities may formulate obligations for existing plants, smaller plants and for other pollutants. Also, reports may be required for other purposes, such as emission fee-systems. The mass flow are mostly calculated from the measured concentrations in conjunction with fuel consumption, the excess air level and the fuel analysis and seldom from the measured concentrations and the measured flue gas velocity. Some of the additional national and regional limits can be simply concentration limits (ppm or mg/m3n) rather than mass emission limits. In such a case it is necessary to correct measurements to a fixed level of O2 or CO2 if emissions are to be made comparable. Otherwise it is not possible to take dilution by excess air or moisture into account. Some examples of reporting to the authorities are as follows; Austria; (NOx, SO2, dust and CO); At least one set of data are measured per minute, mean values are calculated for every half hour and daily mean values are also calculated. A yearly report is made to the regulatory authorities; part 1 covers emission mass flows/month and part 2 covers compliance with the legal limits: Legal requirements are met if no daily value > limit, if less than 3 % of half hour values > 120 % of the limit and if no half hour value > 200 % of limit. Belgium; (SO2, NOx and dust); Collection of measurement data is done every 15 seconds, the NOx concentrations are calculated, standardised (for O2) and stored every half-hour. Daily mean values are calculated from the half-hour mean values. Daily, monthly and annual reports are available. The mass flows and a classification of the half-hour mean values (frequencies > 1,2 and > 2 times the limit values) are detailed in these reports. An annual report is sent to the authorities. France; (NOx, SO2, dust and HCl); Collection of measurement data is done every 10 seconds and minute-average figures are calculated as basic data. An average concentration is calculated every hour from calculated mass flows. Daily and monthly mass flows, exceedances, average and maximum concentrations are reported monthly to the regional authority. An annual report is sent to the Environment Ministry. Germany; (NOx, SO2 and CO); An annual report is made. Italy; (NOx, SO2 and dust); The monthly arithmetic mean, summary statistics of the 48 hourly averaged values over the year and the total annual mass emission must be reported on a periodic report (usually yearly). The Netherlands;
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(NOx, SO2 and dust); Reporting is done for both existing and new installations, annually or more frequent, on an individual basis. Poland; (SO2, NOx and CO); Half hourly data must be available to the authorities. If limits are exceeded a report is made on a special form. Portugal; (NOx, SO2 and CO); The measurements of emissions are sent to the authorities every three months in the case of CEM, and within 30 days for any spot measurements. Regarding CEM, the statistical parameters are determined with a minimum of 75 % of possible values, measured in normal conditions during a reference year (1 April - 31 March). The same approach is applied to the calendar year i.e. the period between 1 January and 31 December. Spain; (NOx and SO2); Half-hourly data is reported to the national authorities in a standard format. Sweden; (NOx ); Reporting of NOx for determination of fees; Hourly mass flows are calculated. These mass flows are summated to produce daily mass flows and the daily masss flow are used to generate annual mass flows. The annual mass flows are reported to the Swedish EPA. (SO2); Reporting of SO2 for determination of taxes; Hourly mass flows are calculated. These mass flows (sulphur) are summated to produce daily mass flows and the daily mass flows are summated to produce annual mass flows. The annual mass flows are declared to the taxation authority. (All components); There are also requirements from the regional authorities, generally involving annual reporting. These requirements refer mostly to specific emission rates (mg/MJ) but in some cases reporting is required of emission concentrations normalised to a fixed concentration of O2 or CO2. Continuous monitoring of emissions is not necessary for these purposes. Switzerland; (NOx, SO2 and CO); The cantonal (regional) authorities assume that the emission limits are complied with. They verify the power plant emissions (by official measurements) every ~ 2 years. A detailed report, based on CEM or PEM of all power plant emissions (NOx, SO2, CO, dust, volatile organic compounds,..), must be given (~yearly) to the authorities: This covers the type of emission, the emission concentration and its mass flow as a function of time and further statistical information to fully describe the situation. The SO2 emissions can be calculated from the fuel analysis for oil fired boilers. United Kingdom; (SO2, NOx, and CO); Hourly averages are determined every 10 minutes. No averages must exceed 150 % of the set limit. 95 % of the hourly averages in a month must be below the limit. Annual mass emissions are reported.

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4.

EXPERIENCE WITH CEM

Experience in different countries of the two measurement systems (extractive and in-situ) is reviewed in this chapter. A common theme in many responses was difficulty in obtaining a consistent reliable supply of calibration gas. 4.1 Extractive CEM

There is variable experience with extractive CEM but most countries have had good experience while the availability in some countries has been poor. In general there have been few problems specifically with the analysers and almost all difficulties reported relate to the sampling and calibration systems. Condensate management requires careful attention if problems are to be avoided. Maintenance requirements can be high unless the system is carefully designed with e.g. provision for back purging of probe filters. Only a few reports about dilution systems was given and the experience was mixed. A major advantage of extractive systems is their ease of calibration. Experience in each country is as follows; Austria; (All components); Extractive with condensation - generally good experience for all components even at high dust concentrations, some problems with leakage (difficult to detect) and with interferences from moisture in the flue gas (NDUV/NDIR). (All components); Extractive with dilution - generally satisfactory for all components, can only be used in gases with a low dust content, problems with calibration exist (dilution can vary with temperature), difficulties exist for correction of measurements to standard dry conditions (NDUV/NDIR). Heated extractive CEM - is used in two cases for measurement of NH3. Experience is acceptable. Belgium; (SO2, NOx and CO); Use of NDIR for plant monitoring has been abandoned because of high maintenance costs. It is still used for comparative measurements but the sampling system adds many uncertainties. Extractive systems work satisfactorily on gas turbines where they are the only type suitable for gas monitoring at high temperature (550 C). (CO); Good with clean flue gases; for gas turbines (NDIR). France; (SO2 and NOx); No important problems with NDIR instruments which are fitted to most EDF power plants. (Dust); -absorption method is used. Maintenance is made difficult by the sampling location - generally in the upper portion of stack. Germany; (NOx, SO2 and CO); Good experience is reported for one utility (NDUV/NDIR). Ireland; (NOx); Highly labour intensive based on a single experience. (CO); Poor performance. Condensation causes blockage of gas flow, leakage problems at pumps and cooler, probe filter plugging (NDIR).

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Italy; (NOx, SO2 and CO); Installed in all ENEL power plants > 300 MWth. Principle is NDIR/NDUV. > 80 installations for NOx and SO2. Problems with automatic calibration procedures due to the quality of calibration gases. Problems also with the gas dehumidification system. Netherlands; (NOx); Attention must be paid to representative and proportional sampling. Good agreement with independent measurements. Novel techniques such as FTIR or PDA (photo diode array) are still not sufficiently developed to be used for CEM. (SO2); All parts must be heated to avoid loss of SO2 in condensate, attention must be paid to representative and proportional sampling (NDIR/NDUV). (NH3); All parts in the sampling system must be heated to avoid condensation of water vapour and ammonium salts (NDIR). (N2O); The interferences of CO, CO2 and NO must be checked regularly (NDIR). (Dust); Dust monitoring is installed after the FGD plant. Sampling systems may clog when the plant is restarted after a shutdown. Monitors are adjusted monthly (zeroed) and are maintained twice yearly. Poland; (All components); There are about 40 systems installed, but, within each power plant, the same CEM type is normally used for measurements on the different boilers. Generally there is good experience of extractive CEM with condensation, some problems arise relating to leakage (difficult to detect) and moisture. Maintenance problems occur with sample conditioning. It is of limited usefulness for on-line process control because of the long response time (NDIR/NDUV). Portugal; (NOx and SO2); Calibration problems are often encountered. Minor problems related to the condensate drain pump are sometimes reported (NDIR, NDUV). (SO2); Problems related to H2SO4 formation and associated corrosion (NDIR). (CO); Calibration problems (NDIR). Spain; (NOx, SO2); Generally good experience. Maintenance problems with sample conditioning equipment (NDUV/NDIR/Chemiluminescence). Sweden; (NOx, SO2, CO, N2O); Extractive with condensation - generally good experience (availability and performance), problems with leakage at connections, coolers or pumps, plugging of the probe filter or with drain pumps. CO could not be measured in series after the NOxconverter. The maintenance can be much reduced if systems for automatic calibration and back purging of the probe filter are installed (NDIR/NDUV). (N2O); Hydrocarbons can interfere (NDIR). (NH3, H2O, HCl); Heated extractive. Problems with condensation of moisture and ammonium salts (2nd derivative IR-spectroscopy combined with gas filter correlation). Switzerland;
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Extractive with condensation: (NOx, CO); Good experience with multi-point probe. Frequent calibration is important. To check for leakage, it is important to be able to inject the different calibration gases near the sample probe and also near the CEM instruments. The fast response time allows the detection of small combustion changes in optimisation (chemiluminescense/NDIR). United Kingdom; (NOx); Generally good availability, some problems with drain pumps (NDIR). (SO2); Problems with high moisture content flue gas analysis (NDIR) after FGD processes (limited experience). (CO); Problems with drain pump and condensation of sample in lines, trace heating recommended (NDIR). 4.2 In-situ CEM

There is generally good experience with in-situ CEM. A disadvantage of most in-situ systems is the problem of calibration on a regular and routine basis. The main advantage is the removal of any need for sample conditioning. Although low levels of maintenance are reported it is clear that there is need for a minimum level of essential maintenance e.g. cleaning of windows and checking of optical path alignment. All dust CEM which uses light absorption or opacity must be calibrated against a manual gravimetric dust measurement. The opacity and light scattering from particles from different fuels normally varies. Some experience in the different countries is as follows; Austria; (Dust); Problems with water droplets after FGD. (SO2, NOx, NH3, H2O and CO2); Generally good experience is reported with DOAS after a lengthy adjustment period in a waste incineration application. Belgium; (All components); No severe systematic defaults has been observed. Measurement of the emission parameters requires extremely reliable sensors which provide self calibration, including auto/zero correction, auto/span checks and correction. Highly encouraging results have been achieved. (SO2, NO); Thirty analysers of the 2nd derivative UV type have been in use since 1990. Accurate, free of interferences, calibration intervals are of the order of 6 months. Very low instrument drift, inaccuracy is frequently a result of bad calibration, air leakage is a possible source of inaccuracy. Equipment intervention has been limited almost completely to replacement of the UV-lamp. (Dust); ~ 60 dust density monitors in use since 1990. The calibration of optical density to mass concentration varies with type of coal. Although not easily quantifiable, the error amounts to at least 30 %. France; (NOx and SO2); A test of DOAS has been in progress for some months in an EDF power plant.

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Ireland; (NOx); Good experience with electrochemical cell, but problems have occurred with vibration and dampness. Cells have a very short life (4 to 6 months). Good auto calibration system. (CO); Good experience with IR cross duct systems, problems occur with cleanliness of windows, one type of system cannot be calibrated on load, the other is calibrated by filter only. Italy; (SO2 and Dust); Limited experience with in-situ CEM for SO2 monitoring. Extensive experience with dust monitoring by optical techniques (100 units). No specific problems reported. The Netherlands; (NOx and SO2); Good experience with (ND)UV, problems with contamination of mirrors and windows, disturbance in the alignment of the optical path due to vibration of the installation, calibration of cross-stack systems is difficult. (Dust); Dust monitors are installed after FGD plant. Generally there are few or no problems with fouling. Monitors are adjusted (zeroed) each month. Maintenance is done every 6 months. Poland; (NOx and SO2); About 60 installations. Better availability compared to extractive CEM. Portugal; (NOx and SO2); No major problems (UV). Spain; (NO and SO2); Very robust and reliable equipment. Low maintenance (2nd derivative IR/UV). Sweden; (NOx, SO2, NH3, H2O); Good experience (availability and performance), general problems are; soiling of windows, interferences and problems with calibration (DOAS). (CO); Good experience (IR). (NOx, SO2, NH3); Across the duct in-situ analyser (DOAS/UV) can handle a maximum level of (ppm * m) and it is also difficult to use them in medium to small gas ducts. An in-situ analyser needs a minimum measurement length and is difficult to install in the small plants (25 - 40 GWh/year) which will be included in the Swedish NOx-fee system from 1997. (Dust); Good experience with light scattering transmissometer. Switzerland; (CO); The accuracy is sufficient for the detection of increased CO due to a reduction in excess air levels. It thus enables optimum adjustment of combustion conditions to be made (IR).

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United Kingdom; (NOx, SO2); Mixed reports, some appear to perform well with long availability periods and few maintenance requirements. On a number of occasions the degree of confidence in system accuracy has been questionable. General problems are fouling of windows, misalignment of transmitter and receiver, mechanical problem with the chopper wheel and cross sensitivity with interfering species (UV). (CO); Low maintenance (IR). 4.3 Accuracy The general emission registration process can be split up into several parts. 4.3.1 Uncertainties of the Measurement Systems Sampling of flue gases Representativeness of sampling is one of the major sources of uncertainty. Sampling can be performed at one point in the flue gas duct (point sampling), at several points (grid sampling) or across the flue gas duct with optical system (line sampling). There is always a concentration profile in the flue gas duct. A theoretical statistical approach gives the following examples of uncertainties. When sampling at one (random) point in the flue gas duct the deviation of the measured concentration from the average concentration in the flue gas duct can be 8 % when the ratio between the lowest and highest concentrations in the flue gas duct is a factor of 1,2 and up to 34 % at a ratio of 2. Performing sampling with a 4 x 4 grid the uncertainty (which is 2 times the standard deviation) reduces to 3% at a ratio between the highest and lowest concentrations of 1,2 and to 10 % for a ratio of 2. Increasing the number of sampling points reduces the uncertainty. Deviations from the average concentration in the sampling plane with a single random sampling point and with grid sampling are shown in figure 1 and 2.

% deviation with respect to the average concentration in the sampling plane

50 40 30 20 10 0 1 2 3

Standard deviation (%)

10 8 6 4 2 0 0 10 20 30 40 50 60 70 80 Number of grid sampling points 1.5 1.3 1.1 2.5 2

Ratio between the highest and lowest concentration in the sampling plane

Figure 1. Uncertainty with a single random sampling point

Figure 2. Uncertainty with grid sampling for different ratios between the highest and lowest concentration in the sampling plane

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Besides concentration gradients velocity gradients can also be present. In principle the correct average concentration is determined when the concentrations are velocity weighted. This is however very impractical and costly for continuous emission monitoring systems. The systematic error when no velocity weighted sampling is performed is only about 4 % at a ratio of 2 between the highest and lowest concentration (and velocity). Transport and conditioning of the flue gas sample When using extractive sampling systems losses of SO2 up to 20 % can occur at levels below 50 ppm (about 140 mg/m3) when using flue gas coolers (for sampling). Analysis and calibration Other important systematic errors occur due to drift and incorrect calibration (adjusting or incorrect calibration gases) of the measuring equipment. These errors are however small when correct calibrations are carried out regularly. Determination of the volumetric flue gas flow The determination of the flue gas flow by means of direct measurements is in general less accurate than calculations based on the fuel input and the excess air ratio. Variation in the 24-hour average For the determination of the uncertainty in the annual emission the variation in the 24-hour average is also of importance. The smaller this variation is, the smaller will be the uncertainty in the annual emission.. 4.3.2 Experience with accuracy reported in the different countries

The accuracy of the different CEM types for gaseous compounds is generally considered to be good by users. However, it is important to note that in most cases emission concentrations are discussed and in the Netherlands and in Sweden also the question of total annual mass emissions are considered. This makes direct comparison of experience difficult. It is not possible to recognise any clear trend regarding the performance and the availability of CEM systems from the survey response. The accuracy of gaseous emission concentrations in flue gas is expected to be high if calibrations are performed carefully and with certified calibration gases or calibration cells. Experience reported from a Swedish accredited laboratory is that the deviation between a stationary CEM and a mobile extractive CEM (owned by the laboratory) is below 4 % of the measured values in most cases. The accuracy of dust CEMs are low, especially at low concentrations. The accuracy of calculations of yearly emissions depends also on uncertainties in fuel flow and volumetric flow calculation. A study of three coal fired power plants gives +/- 5 to 11 % uncertainty for NOx and +/- 25 30 % for SO2 in low concentrations after FGD, mainly due to concentration gradients in flue gas ducts. Belgium; In-situ: (SO2, NO); During 1988 seven different types of in-situ gas analysers from different manufacturers were tested on a power plant. The test extended over six months and an extractive CEM was used as reference. It was found that the mean relative error on NOxmeasurement is < 7 % when the calibration is done carefully.
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(CO); Low accuracy and sensitivity. (Dust); Accuracy is uncertain for dust contents below 100 mg/m3. Netherlands; A study has been performed for the estimation of the total uncertainty in the determination of SO2 and NOx emissions by means of continuous emission monitoring systems at three coalfired power plants in the Netherlands. The power plants were equipped with primary NOx control and with flue gas desulphurisation units (FGD). The NOx-concentrations were in the range between 250 and 500 mg/m3 and the SO2-concentrations in the range between 50 and 200 mg/m3 . Two plants were equipped with a (single point) in-situ SO2 and NOx monitoring system (UV absorption; Lear Siegler) and the third power plant was equipped with an extractive emission monitoring system (UV-PDA; Ametek) for SO2, NO and NO2. The sampling occurred at a single point in the flue gas duct. The following major types of uncertainties were determined and quantified: - systematic errors (such as representativeness of sampling, uncertainty in calibration gases, interferences) - random errors (such as variation in 24-hour average, calculation of the volumetric flue gas flow) In table IV the uncertainties (expressed as standard deviation) are quantified. Table IV. Uncertainties (expressed as standard deviations) in the emission registration process for three coal fired power plants (I, II and III) with FGD. I II III NO representativeness of 1,3 % 0,7 % 1,5 % samplingaverage 24-hour 5,2 % 10 % 18,9 % SO2 representativeness of 11,3 % 11,4 % 12 % samplingaverage 24-hour 27,2 % 24 % 28,1 % O2 representativeness of 0,8 % 2,2 % 2% samplingaverage 24-hour 0,62 % 0,52 % Calibration gases (NO, SO2 and O2) 1% 1% 1,5 % Interferences (NO, SO2 and O2) 0,5 % 0,5 % 0,5 % Water vapour content 2,6 % 3% Volumetric flow calculation stoichiometric flue gas volume 2,3 % 5,2 % 2,6 % Coal flow 0,5 % 0,62 % 2,5 %

For the three individual coal fired power plants the uncertainty in the total annual emission of NOx were around 5 % for two plants and 11 % for the other. This higher value is due to the fact that this power plant uses only one and the same stoichiometric flue gas volume for the calculation of the volumetric flue gas flow for all fired coal blends during the whole year. If the stoichiometric flue gas volume for each coal blend is used then an uncertainty of about +/5 % in the annual emission of NOx can also be reached. For SO2 the uncertainty in the annual emission was in the range between +/- 20 and 25 % for all three power plants. This uncertainty is mainly due to the single point measurements and the concentration gradients in the flue gas duct after the flue gas desulphurisation unit.
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If a sampling grid of about 16 sampling points (4 x 4 grid) is used then an uncertainty of about +/- 15 % can be achieved. A further reduction of the uncertainty to a level of +/- 5 % requires at least 100 sampling points. These uncertainties are solely based on the quantifiable errors in the total emission recording process. Any bias due to incorrect calibration, leakage, calculation errors (wrong conversion factors), the inclusion of faulty measuring values etc. are not included in these figures. (Dust); Comparison measurements against a manual method are made only at installation. Monitors are not calibrated against manual reference methods. Dust levels are very low, generally below 10 mg/m3 this is substantially below the legal limit value which is usually 20 or 50 mg/m3 depending on the date of the first license. Sweden; (NOx, SO2, CO); The relative error in CEM concentration measurements has been calculated to be about 4 % in some Vattenfall studies. These studies have been done for mobile extractive CEM but the value is also representative for stationary CEM. The following parameters have been included; uncertainty in the representativeness of the sampling point (extractive CEM), uncertainty in the calibration gases, uncertainty in the zero point, uncertainty in the linearity, uncertainty because of interferences and finally uncertainty because of accidental errors in the recording unit. The uncertainty in the determination of the mass emissions (kg/h) have been estimated to about +/- 12 % in another study. In this study the gas flow is calculated from the fuel analysis and continuous measurement of oxygen. The experience from the accredited laboratory owned by Vattenfall is that the deviation between a stationary CEM and a mobile extractive CEM (owned by the laboratory) is in most cases below 4 % of the measured values. Another experience of the same laboratory is that there are almost never concentration gradients in the flue gas duct or the stack. The laboratory have verified about 30 CEM installations in small to average plants (10 - 100 MW). During such a procedure two different CEMs with different probes are used, the first probe is moved across the duct while the other probe is fixed at one point. Concentration gradients have occurred in a few cases and if the concentrations from the two different CEM were standardised to the same level of O2, the concentrations corresponded in all cases except one. The value of possible differences was, with the exception of the one problematic case, always less than 10 % (without normalisation to the same O2concentration). In the problematic case the corresponding concentration levels were measured at 7 out of 10 measurement points, in the remaining 3 the difference was up to 30 %. The measurement points were, in all cases, located after the de-dusting and also after any deSOx-or deNOx-processing. In no cases were the measurement points located close to a flue-gas cleanup process, a rotating air preheater or a fan. Switzerland;
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Extractive with condensation: (SO2); Uncertainty +/- 15 % (multi-point grid measurement and NDIR). Extractive with dilution: (NOx, SO2); The accuracy is not sufficient for a heavy oil fired power plant applications (Chemiluminescence, fluorescence). In-situ: (CO); Uncertainty +/- 20 ppm, reproducibility +/- 10 ppm (IR). United Kingdom; (CO); Satisfactory accuracy and reliability (extractive with condensation and NDIR). 4.4 Reported Experience of a General Nature

Experience of CEM is good overall based on extensive experience in many countries reviewed here. Experience is better with CEM based on extraction with condensation compared to CEM based on extraction with dilution or heated extractive CEM. Based on limited data it appears that the experience (accuracy, performance, long term availability, operating costs etc.) of extractive (with condensation) and in-situ CEM are about the same. Belgium has reported better experience of in-situ CEM and Sweden has reported slightly better experience with extractive CEM. There have been no reports of any difficulties with data collection/processing systems for CEM although major problems with data systems have been widely reported in the US. Further information on data collection/processing, whether of a positive or negative nature, would be of value in completing this review of CEM experience. Italy; In Italy the trend is toward the application of extractive with condensation CEM for monitoring of SO2, NOx and CO and of in-situ CEM for monitoring of dust. A unified calibration and maintenance program has now been developed and is being applied for quality control and insurance. Some problems has been met in automatic calibration due to the difficulties in finding good calibration gases. Sweden; In Sweden there are two trends concerning extractive or in-situ CEM. The new small plants (25 - 40 GWh/year in produced energy) which now are included in the fee-system have chosen extractive CEM or in some cases PEM because it is difficult to measure with an insitu CEM in small diameter gas ducts. Also, the price of extractive CEM is lower in Sweden compared to in-situ CEM. The larger plants, however, have mostly chosen in-situ CEM. An increasing number of plants are gradually being equipped with deNOx and measurement of NH3 slip is therefore desirable. Measurement of NH3 with in-situ CEM is more accurate and is also easier. Regarding calibration, a recommendation which can be made is to calibrate the analyser weekly in the month following installation. If the accuracy is satisfactory then the analyser can subsequently be calibrated monthly. Most of the new plants that will be included in the NOx-fee system during 1997 are equipped with calibration cells. These CEM systems are

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therefore only checked with calibration gases 1 - 2 times/year. This strategy have been accepted by SEPA. Some CEM suppliers had problems with their data collecting systems when the NOx-fee system first started (1991). There have not been any important difficulties with the collection of data in recent years and most established CEM suppliers have developed suitable data collection programs. Switzerland; NOx measurement by Chemiluminescence can suffer drift through use of ambient air for the ozoniser this is due to a high sensitivity to the air moisture content. 4.5 Investment and Operating Costs

The costs of CEM-systems depends on several factors; number and types of components, number of sampling points, sampling system, analysis principle and so on. Direct comparison of reported CEM costs has not been possible. The reported investment span is considerable; from 20.000 - 200.000 and annual operating costs are reported from 3.000 to 9.000. The lower costs are reported for example from highly standardised CEM used in the Swedish NOx-fee system and only for monitoring of O2 and NO. The reported experience in this study indicate that costs are lower (both investment costs and maintenance costs) for in-situ CEM than for extractive CEM. In some countries additional cost arises each year for independent verification by an accredited laboratory this is currently a moderate cost.

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5.

GENERAL DISCUSSION

The most important trend in all the countries reporting is the increasing requirement for CEM measurements, driven particularly by new requirements by the regulatory authorities. The utilities have performed many investigations into CEM and its advantages. CEM is consequently used not only for control of the environmental performance of a plant but also (particularly in the case of CO and dust) for optimisation and control of the plant operation. Existing and new plants continue to be fitted with primary measures such as low-NOx burners or with secondary measures deNOx. An increasing number of CEM installations are therefore required, not only for measurement of NOx for deNOx process control but also, in some countries, for the measurement of NH3 slip when using SNCR techniques. The experience reviewed in this study shows no definite trends for choice of extractive or insitu CEM, both have been applied successfully in many countries. Use of CEM by the extractive condensation principle has, thus far, been more frequent than in-situ CEM. In most countries the experience (accuracy, performance, long term availability, operating costs etc.) of extractive and in-situ CEM has been similar. Some countries e.g. Belgium have reported better experiences of in-situ CEM while Sweden has reported better experiences of extractive CEM. The reported experience with CEM based on extraction with condensation is, however, better than that of CEM based on extraction with dilution or heated extractive CEM. In Sweden, despite the slightly better experiences from extractive CEM, there have been many new in-situ installations. This is because an increasing number of plants are being equipped with SNCR-systems and therefore often, mainly for process control, measure the NH3 slip. Measurement of NH3 is more accurate and easier with in-situ CEM which also can often combine the measurement of NOx and NH3. The trend in Sweden is therefore; plants with deNOx - in-situ CEM and other plants - extractive with condensation. In most of the countries, performance criteria for CEM have been established. Only Germany (anticipated in Ireland) has a standard approval system for the CEM instruments. Also some cantons (regions) in Switzerland require German TV approved CEM instruments. It is not possible to recognise any clear trend regarding the performance and the availability of CEM systems from the survey response. A high accuracy can be expected if the CEM is installed and managed correctly. A much poorer accuracy can be expected if the relevant flue gas concentrations are very low or with a considerable concentration profile e.g. measurement of SO2 after a deSOx unit. It is clear from many responses that calibration systems pose problems and require further attention. A common difficulty appears to be the quality and reliability of calibration gas standards. Trends which are apparent include the facts that the more conventional CEM methods are becoming more cost effective and that the simpler CEM methods are being improved. New measurement techniques such as FTIR and diode laser are also coming into use. The electrochemical analysis principle is one example of a technique which may be improved further.
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In some countries PEM for determination of NOx emissions has been tested (Portugal, Sweden, Switzerland, the Netherlands and United Kingdom). A PEM system can be verified by multivariate data analysis or based on predictions by neural network. If a PEM system is to be used the plant must be fired with fuel of constant quality.

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Appendix 1 page 29 of 3 Article 15 1. In the event of continous measurements, the emission limit values set out in Annexes III to VII1 shall be regarded as having been complied with if the evaluation of the results indicates, for operating hours within a calender year, that: a) none of the calendar monthly mean values exceeds the emission limit values; and b) in the case of: - sulphur dioxide and dust: 97% of all the 48 hourly mean values do not exceed 100% of the emission limit values, oxides of nitrogen: 95% of all the 48 hourly mean values do not exceed 110% of the emission limit values.

The periods referred to in Article 82 as well as start up and shut down periods shall be disregarded. 2. In cases where only discontinuous measurements or other appropriate procedures for determination are required, the emission limit values set out in Annexes III to VII3 shall be regarded as having been complied with if the results of each of the series of measurements or of the other procedures defined and determined according to the rules laid down by the competent authorities do not exceed the emission limit values. In the cases referred to in Article 5 (2) and (3)4, the rates of desulphurization shall be regarded as having been complied with if the evaluation of measurements carried out pursuant to Annex IX, point A.25, indicates that all of the calendar monthly mean values or all of the rolling monthly mean values achieve the required desulphurization rates. The periods referred to in Article 86 as well as start up and shut down periods shall be disregarded.

3.

1 2 3 4 5 6

Council Directive 88/609/EEC Council Directive 88/609/EEC Council Directive 88/609/EEC Council Directive 88/609/EEC Council Directive 88/609/EEC Council Directive 88/609/EEC

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Appendix 1 page 30 of 3 Annex IX METHODS OF MEASUREMENTS OF EMISSIONS A. Procedures for measuring and evaluating emissions from new plants 1. Concentrations of SO2, dust, NOx and oxygen shall be measured continously in the case of new plants with a rated thermal input of more than 300 MW. However, monitoring of SO2 and dust may be confined to discontinous measurements or other appropriate determination procedures in cases where such measurements or procedures, which must be verified and approved by the competent authorities, may be used to obtain concentration. In the case of plants which must comply with the desulphurization rates fixed by Article 5 (2) and (3)7, the requirements concerning SO2 emission measurements established under paragraph 1 shall apply. Moreover, the sulphur content of the fuel which is introduced in the combustion plant facilities must be regularly monitored. 3. The competent authorities shall be informed of substantial changes in the type of fuel used or in the mode of operation of the plant. They shall decide whether the monitoring requirements laid down in paragraph 1 are still adequate or require adaption. Continously-operating measuring systems shall be checked at regular intervals in consultation with the competent authorities. The instruments for the measurement of concentration of SO2, dust, NOx and oxygen shall undergo basic calibration and an examination of their operation at appropriate regular intervals. The continouslyoperating measuring equipment shall be calibrated in accordance with a reference measuring method approved by the competent authority.

4.

B. Determination of total annual emissions of new plants The competent authorities shall obtain determination of the total annual emissions of SO2 and NOx. When continous monitoring is used, the operator of the combustion plant shall add up separatelys for each pollutant the mass of pollutant emitted each day, on the basis of the volumetric flow rates of waste gases. Where continous monitoring is not in use, estimates of the total annual emissions shall be determined by the operator on the basis of paragraph A.1 to the satisfaction of the competent authorities. Member States shall communicate to the Commission the total annual SO2 and NOx emissions of new combustion plants at the same time as the communication required under paragraph C.3 concerning the total annual emissions of existing plants.

Council Directive 88/609/EEC

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Appendix 1 page 31 of 3 C. Determination of the total annual emissions of existing plants 1. Member States shall establish, starting in 1990 and for each subsequent year, a complete emission inventory for existing plants covering SO2 and NOx: - on a plant by plant basis for plants above 300 MWth and for refineries; - on an overall basis for other combustion plants to which this Directive applies. The methodology used for these inventories shall be consistent with that used to determine SO2 and NOx emissions from combustion plants in 1980. By 1990 Member States shall inform the Commission of full details of methods and base data used for establishing the emissions of SO2 and NOx from existing combustion plants, referred to respectively in Annexes I and II8, column 0. 3. The results of this inventory shall be communicated to the Commission in a conveniently aggregated form within nine months from the end of the year considered. The methodology used for establishing such emission inventories and the detailed base information shall be made available to the Commission at its request. 4. The Commission shall organize a systematic comparison of such national inventories and, if appropriate, shall present proposals to the Council aiming at harmonizing emission inventory methodologies, for the needs of an effective implementation of this Directive.

2.

Council Directive 88/609/EEC

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Appendix 2

Extractive CEM Manufacturer Hartmann & Braun * Bodenseewerk * ***

Siemens * Maihak * Rosemount * Servomex * Tecan* ADC (Monitor Labs) ** (NO + NO2) CO SO2 * Extractive with condensation ** Extractive with dilution (wet gas) *** Heated extractive (wet gas) In-situ CEM Manufacturer Lear Siegler * OPSIS */** Rosemount ** SICK */** Durag ** LAND * Codel Procal ** * In-situ probes ** Cross-duct measurement

Component NO (NO+NO2) CO, SO2, N2O NO, CO, N2O, NO2 CH4, C2H6 etc NO, CO, N2O, HCl, NH3, H2O, CH4, C2H6 etc NO, CO, SO2 (NO + NO2) NO, CO, SO2 (NO + NO2) NO, CO NO2, SO2 NO, NO2, SO2, CO NO, NO2, NOx NO

Monitoring principle NDUV or NDIR NDUV or NDIR + converter NDIR 2nd derivative spectroscopy + gas filter correlation (IR) NDIR NDIR + converter NDIR NDIR + converter NDIR NDUV NDIR Chemiluminescence + converter Chemiluminescence Chemiluminescence + converter IR Fluorescence

Component NO, SO2 CO NO, NO2, H2O, SO2, NH3 CO NO, SO2, NH3, dust CO dust NOx CO NO, CO, H2O NO, SO2

Monitoring principle 2nd derivative spectroscopy (IR/UV) 2nd derivative spectroscopy (IR) DOAS (UV) IR UV NDIR Opacity, light absorption Electrochemical cell IR IR IR

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Publications Order Form Name: ............................................................................................................................................... Position:............................................................................................................................................ Undertaking: ..................................................................................................................................... Address:............................................................................................................................................ Town: .......................................................Country:.......................................................................... (with postal code) Telephone: .......................................................Fax:.......................................................................... (with regional code) E-mail: EURELECTRIC member: Title1 p Yes p No (Tick the appropriate box)

Reference No.

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To be returned to: Concetta PALERMO Union of the Electricity Industry - EURELECTRIC Documentation 66, Boulevard de l Impratrice BE-1000 Brussels Tel.: Fax: + 32 2 515 10 00 + 32 2 515 10 10 E:mail: cpalermo@eurelectric.org Web: http://www.eurelectric.org

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