Emission Monitoring and Reporting (EMR) Manual for European Countries

Transcription

1 Emission Monitoring and Reporting (EMR) Manual for European Countries HGRS-CTS/MT J. Waltisberg HGRS-CIE/ETPS Th. Lang Version: /E ( ) 1/51

2 TABLES OF CONTENTS 1. INTRODUCTION / GENERAL General Situation with regard to EMR EMR implementation deadlines are Supporting Documents EMISSION MEASUREMENTS: GENERAL General Design of Air Emission Regulations in Europe Air Emissions Protection against Air Emissions Control Measurement Procedures and Reporting Assessment of Emission Emission Measurements in Cement Plants Dust Inorganic Substances Mainly in Dust Particles ( Heavy Metals ) Gaseous or Vaporous Inorganic Substances Organic Substances in the Form of Gases, Vapors or Particles Carcinogens Emission Measurements in Cement Plants Main Stack Cooler Stack Bypass Stack Coal Mill Stack Cement Mill Stack Separate Raw Mill Stack / Separate Raw Material Dryer SAMPLING PORTS AND MEASURING STATION Measuring Location for Discontinuous Measurements and Extraction Point for Continuous Extractive Measurements Additional Requirements for Discontinuous Measurements STANDARDIZIDED EMR MEASUREMENTS Continuous Emission Measuring Devices Recommended Dust Measuring Devices /51

3 4.1.2 Recommended Continuous Emission Measuring Devices (CEM) for Inorganic Gases FTIR-Analyzers (Fourier Transformed Infrared Spectroscopy) Differential Optical Absorption Spectrometroscopy Extractive Hot with IR-Technology Recommended Flame Ionization Detector (FID) Discontinuous Emission Measurements Calibration Measurement Discontinuous Emissions Measurement Number of Measurements Calibration Measurement with Continuous Operating Analyzers Calibration and Discontinuous Measurement with Reference Methods STANDARDIZED REPORTING Continuous Emission Measurement: Standardized Reporting on Basis of TIS The TIS Module EMR Annual Air Emission Report HTC - The Naming Convention for Environmental Data HTC Location HTC Identifier HTC Material Examples Discontinuous Emission Measurement Report Part 1: The Report about the Emission Measurements at the Stack Part 2: The Report about the Operating Conditions of the Measured Kiln GUIDE TO A FIRST PLAUSIBILITY CHECK OF RESULT OBTAINED Check of the Emission Ranges Volume Stream Carbon Dioxide Nitrogen Monoxide NO x Sulfur Dioxide SO Carbon Monoxide CO Volatile Organic Compounds VOC Further Plausibility Check Possibilities Emissions from Cement Kiln Stacks according to VDZ Measurements of German Cement Kilns in QUALITY ASSURANCE OF TEST HOUSES AND ANALYTICAL LABORATORIES Basic Principles /51

4 7.1.1 EuroNorm EN 45001, ISO (Dec. 1999) Neutrality, Independence and Integrity Legal Aspects Legal Recognition Collaboration with the Client Subcontractors Management and Organization Technical Competence Employee Qualification Physical Facilities and Equipment Operation of Measuring Instruments Checking the Measuring Instruments and Methods Working with Calibration Gases Checking the Standards (Calibration Gases) Working Instructions Organizing Workflows, Standard Working Instructions Instrument Logs Work Log Verifying Plausibility of Raw Data Accreditation References OTHER ITEMS OF INTEREST / ANNEXES The European Union Directive on the Incineration of Waste (CO-incineration in Cement Plants) Backgrounds: European Directive on Incineration of Waste Reporting Requirements according to EPER Emission Benchmark Values /51

5 1. INTRODUCTION / GENERAL 1.1 General Situation with regard to EMR: With the adherence to the WBCSD Holcim has accepted to publish a corporate SD report (Including a chapter on environment) within three years from the date of adherence. In discussions around AFR implementation the lack of a systematic record of emission data always again is a matter of concern. Authorities more and more proceed to the issuing or revision of emission limit values for industries and thus also need reliable back-up data. Holcim's engagement for continuous (environmental) improvement, too, needs reliable emission data for adequate preparation of decisions and monitoring of success. To this ends, the Holcim ExCo has adopted the EMR scheme which requires the Group plants: A) To install and operate continuous emission monitoring (CEM) equipment for Dust, NOx, SO 2, VOC (and O 2 ). B) To measure HCl, NH 3, C 6 H 6 (benzene), D/F and HM emissions (at least) once per year. C) To calibrate CEM equipment (at least) once per year. D) To report in a standardized form once per year (01.03.xy) to HGRS-CIE. E) To see for it that organizations entrusted with work according to points B) and C) above are capable of delivering quality work. Note: Points C) and E) are not directly subjects of the above cited Exco decision, but mandatory to assure a high quality level of information according to points A) and B). 1.2 EMR implementation deadlines are: For European Group plants: For Extra-European Group plants: Implementation in 2001/2002 Implementation in 2002/2003 First EMR reporting as per First EMR reporting as per /51

6 1.3 Supporting Documents: In order to standardize and streamline emission measuring and reporting in the Group, to facilitate EMR implementation and generally to assure a high EMR quality level, three documents were prepared by HGRS CIE and CTS, namely: Emission Monitoring and Reporting Manual for European Countries (Document on hand) Guidelines for Continuous Emissions Measurements in Holcim Cement Plants Guidelines for Annual Discontinuous Emissions Measurements in Holcim Cement Plants All three documents can be found in ENVIROnet on HolSpace. The EMR Manual and Guidelines are intended to be living documents thus subject to continuous improvement. Any comments are therefore welcome and will be int e- grated in new versions of the manual. 6/51

7 2. EMISSION MEASUREMENTS: GENERAL 2.1 General Design of Air Emission Regulations in Europe Air Emissions An air emission is an air pollution with potentially harmful or nuisance effect relative to human beings, animals, plants, their biological communities and habitats and the soil Protection against Air Emissions Regarding protection against air pollution, authorities can take the following measures: Maximum permitted air pollution (ambient air quality standards) Preventive measures to limit emissions from installations (emission limits) Requirements with regard to fuels Control Anyone who operates an installation, which causes air pollution, shall provide the authorities with an emission declaration including type and level of emissions as well as time period of discharge. The authorities supervise the compliance of the emissions with the limits. Measures: - Control measurements 1 Measurements or control of the emissions repeated in regular intervals (e.g. every one to three years) 1) - Continuous measurements Continuous measurements for installations, with high levels of emissions 2) Measurement Procedures and Reporting Emission measurements must be carried out according to the rules of the art and with standardized measuring techniques. 3) The measurements must be related to the operating modes which are important for the assessment of the emissions 4) The measured and calculated values, the measuring methods used and the operating conditions of the installation during the measuring period must be recorded. 5) 1 Control measurements check the compliance of an installation with the applicable prescriptions and produce activities as follows: a) None in case of compliance b) An authoritarian request to rectify the situation within given deadlines, etc. 7/51

8 Emissions are expressed as: - Concentrations: Mass of emitted polluting substance per volume unit of the flue gas e.g. [mg/m 3 ] Values indicated as concentrations and the oxygen content refer to the volume of the flue gas under standard conditions (0 [ C], 1013 [mbar]) after subtraction of the moisture content (dry). The values refer to the volume of the flue gas, which is diluted no more than technology and operating conditions require or to a reference value (e.g.: 10 [%] O 2 ) 6) - Mass flows: Masses of emitted substances per unit of time e.g. [g/h], [t/a] - Emission factors: Ratios of the masses of emitted substances to the masses of the product generated by the process in the same time period, e.g. [g/t clinker] Assessment of Emission For the assessment, the measured values of all emissions shall be converted to averages over a defined time period. 7) The authorities can define suitable time periods for averages of specific emission compounds. 8) In the case of control measurements, the emissions are in accordance with the emission limits if none of the average values exceeds the limits. For continuous measurements statistical criteria for the assessment of the emission are formulated. Example Switzerland: The emissions are in accordance with the emission limit values, if in the time period of one calendar year - none of the daily average values (calculated from the hourly average values) exceeds the emission limits - 97 percent of all hourly average values are no more than 1.2 times the limit - none of the hourly average values are more than twice the limit. Example Emission Benchmark Values: The emissions are in accordance with the emission benchmark values, if in the time period of one calendar year - 97 % of the daily averages do not exceed the s Remarks: 1) Measurement: Measuring campaign during a sufficiently long time interval; e.g. 1 day, 1 shift, 1 week Control: Control of parameters, which influence the emission; e.g. control of the mercury concentration in the fuel and the raw material. 2) In Practice: If the emission level exceeds a certain mass flow (expressed in e.g. in [kg/h], [t/year]) or exceeds a certain percentage (e.g. 20 [%]) of the limit. 8/51

9 3) Rules of the art: Approved measuring devices (e.g. TÜV approval according to 17. BimSchV in Germany) Standardized measuring techniques (e.g. VDI-Guidelines) 4) Operating modes: In a control measurement some emission compounds (e.g. SO 2 ) of a cement kiln should be measured in direct and in compound operation. In compound operation a part of this emission is adsorbed on the raw meal. 5) Operating conditions: A measurement report contains not only the emission values but also the operating condition of the installation. For a cement kiln parameters like clinker production, fuel and raw meal feed, etc. must be recorded. 6) Dilution/reference value: A reference value is the better solution than the definition of the dilution. According to EMR all emission values (concentrations) have to be given mandatory at an oxygen reference value of 10 [%]. 7) Average of defined time period: The bases for the assessments are the averages of the defined time interval (e.g. half-hourly- or hourly averages) Germany: ½ [h], Switzerland: 1 [h]) Example: A dust emission is in average 25 [mg/m 3 ] (hourly average) but during 3 minutes the emission reached a value of 150 [mg/m3]. In this case the emission value for the assessment is 25 [mg/m 3 ]. 8) Other time periods: The measurement of some emissions (e.g. heavy metals, dioxins) is not possible in the defined time intervals of ½ or 1 [h]. In this case other time periods are required. 2.2 Emission Measurements in Cement Plants Emission limits are usually implemented for Dust Inorganic substances mainly in dust particles ( heavy metals ) Gaseous or vaporous inorganic substances Organic substances in the form of gases, vapors or particles Carcinogens Dust In the catchword dust the emissions of coarse dust; fine dust, soot, particles and aerosols are summarized. Additionally, dust can contain a number of inorganic (e.g. heavy metals ) and organic compounds (e.g. polycyclic aromatic hydrocarbons, dioxins and furans). 1) 9/51

10 In cements plants three different types of dust emissions exist: Point emissions with important dust mass flows: - Main stack, grate clinker cooler stack, bypass stack (in special cases only) - Continuous measurements Emission points with small dust mass flows: - Bypass stack, coal mill stack, cement mill stacks - Control measurements or surveillance equipment 2) Fugitive dust emissions - Roads, quarries, open stockpiles - Material transfer points - Estimation of emissions required Inorganic Substances Mainly in Dust Particles ( Heavy Metals ) 3) Classification according to toxicity 4) The limits apply to the total mass of emitted substance, including gaseous and vaporous components If the flue gas contains several substances belonging to the same class, the limit applies to the sum of these substances A continuous measurement of these substances is not possible. Therefore this type of emission is measured by control measurements 5) List of inorganic substances mainly in form of dust particles (Substances important to cement factories in italic bold) Element Toxicity class Remarks Switzerland *) Germany **) Antimony Sb 3 3 ***) Arsenic As 2 Carcinogen ***) Cadmium Cd Carcinogen Carcinogen Chromium Cr 3 3 ***) Cobalt Co 2 2 ***) Copper Cu 3 3 Lead Pb 3 2 Manganese Mn 3 3 Mercury Hg 1 1 Nickel Ni 2 2 ***) Palladium Pd 3 Platinium Pt 3 Rhodium Rh 3 Selenium Se 2 2 Tellurium Te 2 2 Thallium Tl 1 1 Tin Sn 3 3 Vanadium V 3 3 Zinc Zn ****) 10/51

11 *) Switzerland; Ordinance on Air Pollution Control ( ) **) Germany, TA Luft ( )***) CH and or D: except specific compounds listed as carcinogen substances ****) The emission of the "heavy metal" zinc (Zn) is not limited, but often measured because some alternative fuels have a rather high concentrations of this element Gaseous or Vaporous Inorganic Substances Classification according to toxicity The limit applies to each substance and not to the sum of the substances in the same class. Gaseous or Vaporous Inorganic Substances (Germany, Switzerland) Substance Ammonia and ammonia compounds Measurement Control (Continuous) Expressed as Ammonia (NH 3 ) Remark 6) Chlorine compounds Control (Continuous) Hydrogen chloride (HCl) Fluorine (Control) Hydrogen fluoride (HF) Nitrogen oxides (nitrogen monoxide + nitrogen dioxide) Sulfur oxides (Sulfur dioxide + sulfur trioxide) Continuous Continuous (Control) Nitrogen dioxide (NO 2 ) Sulfur dioxide (SO 2 ) Vaporous or gaseous inorganic compounds, except cyanogen chloride and phosgene And its vaporous or gaseous compounds In cement kilns only measur e- ment of nitrogen monoxide (NO) 7) 8) 9) 10) Carbon monoxide (CO) is mostly not limited in cement plants. But it is recommended to measure this compound continuously for process control reasons. 11/51

12 2.2.4 Organic Substances in the Form of Gases, Vapors or Particles Two types of limits exist: Classification according to toxicity (e.g. Germany, Switzerland) Volatile Organic Compounds (Sum of emitted organic carbon) Due to a large number of organic compounds defined in the regulations there are problems with the class limits. Solution applied in practice: Measurement of Volatile Organic Compounds (VOC; other names: TOC --> Total organic carbon, THC --> Total hydrocarbons) and some further specific compounds Carcinogens Classification according to toxicity If the flue gas contains several substances belonging to the same class, the limit applies to the sum of these substances Important substances for cement plants are: Substance Formula Measurement Benzo(a)pyrene C 20 H 12 Control, but only in specific cases 11) Benzene C 6 H 6 Control measurement 12) Beryllium Be Control, but only in specific cases 13) Chromium (VI) compounds Cadmium Nickel in specific compounds Cr If total chromium below limit value of chromium (VI) then no chromium (VI) analysis is required. 14) Cd Ni Analogue chromium (VI) 15) Remarks: 1) PM10: In past years, medical studies have proven the importance of fine dust fractions as a risk factor to human health. Especially a correlation between the PM10 concentration (particulate matter < 10 [µm]) in the ambient air and diseases of the respiratory tract was found. Therefore PM10 emission limits could be established in the years to come. 12/51

13 2) Surveillance: For dust measurements cheap measuring devices do exist. They cannot be used for an accurate measurement but are good enough for a continuous surveillance. For instance: If a bag in a bag filter is damaged, the instrument indicate increased emission values. 3) Heavy metals: The list contains also some non-metals (e.g. cyanides, quartz dust, etc) 4) Toxicity classification: Mainly in three classes (e.g. Germany, Switzerland) 5) Continuous measurements: Continuous measuring devices for mercury are on the market. First tests in German cement plants have shown contradictory results. 6) Ammonia: If a non-catalytic (SNCR) or catalytic reduction (SCR) of nitrogen oxides is used, a continuous measurement may be required. 7) Hydrogen chloride: Of importance only in cases where materials with high chlorine content are added to the kiln (e.g. introduction of chlorinated materials for low alkali production). 8) Hydrogen fluoride: Of importance only in cases where fluorinated materials are added. 9) Nitrogen dioxide: The share of nitrogen dioxide (NO 2 ) in nitrogen oxides (NO x ) from a cement kiln is below 5 [%]. Therefore only nitrogen monoxide (NO) is measured in cement plants (but indicated as equivalent NO 2 emission). 10) Sulfur trioxide: The share of sulfur trioxide (SO 3 ) in sulfur oxides (SO x ) is below 5 [%]. Therefore only sulfur dioxide (SO 2 ) is measured in cement plants. 11) Benzo(a)pyrene: Possibility of relevant emission only if alternative raw material with high C 20 H 12 concentration is used. 12) Benzene: Emission mainly from raw material components 13) Beryllium: Possibility of relevant emission only if alternative raw material with high concentration is used. 14) Chromium(VI)compounds: In general the emission level of the sum of the measured heavy metals of class 3 (Sb, Cr, Pb) is below 200 [µg/m 3 ]. The limit of the carcinogen Cr(VI) is 1 [mg/m 3 ]. Therefore the emission of Cr(VI) is usually not measured separately. 13/51

14 15) Nickel: In general the emission level of the sum of the measured heavy metals of class 2 (As, Ni) is below 100 [µg/m 3 ]. The limit of the carcinogenic nickel compounds is 1 [mg/m 3 ]. Therefore the emission of specific nickel compounds is not measured. 2.3 Emission Measurements in Cement Plants The authorities (official measurements) require continuous and control measurements at different emission points. The requirements differ in each country. The following tables give an overview of the present requirements. EMR only requires emission measurements at the main stack Main Stack Official Measurements EMR Requirements Dust Dust Continuous Continuous Measurement 1) Inorganic Substances "Heavy Metals" Control First priority: Hg Second priority: Cd, Tl Third priority: As, Co, Ni, Sb, Cr, Cu, Pb, Mn, V Gaseous or vaporous inorganic substances NO x Mostly continuous SO 2 Continuous or control CO No measurement or control O 2 No measurement or control NH 3 No measurement or control HCl No measurement or control Control Hg, Cd, Tl, As, Co, Ni, Sb, Cr, Cu, Pb, Mn, V Continuous, only NO Continuous No measurement Continuous Control Control Organic substances VOC No measurement or control Continuous 9) Carcinogens Benzene C 6 H 6 No measurement or control Control Dioxins/Furans PCDD/PCDF No measurement or control Control 10) Remarks: 1) The dust emission at the main stack is in any case a high level emission and should be controlled by continuous measurements 2) The emission of inorganic substances from the main stack of a cement kiln is not a high level emission. 2) 3) 4) 5) 6) 7) 8) 14/51

15 The measurement of inorganic substances (heavy metals) is only possible by control measurements and not continuously. Continuous measuring devices for mercury are on the market. First tests in German cement plants have shown contradictory results. 3) The share of nitrogen dioxide (NO 2 ) in nitrogen oxides (NO x ) is below 5 [%]. Therefore only nitrogen monoxide (NO) is measured in cement plants (but indicated as equivalent NO 2 emission). 4) Depending on the raw material, it is possible that the SO 2 emission from a main stack of a cement plant is low. In this case authorities often allow measuring this compound by a control measurement. Holcim EMR, however, requires continuous measurement also in these cases. 5) For cement plants usually the CO emission is not limited. Modern CEM equipment allows measuring CO anyhow. Therefore it is recommended to make use of this built-in facility. Furthermore in some cases of AFR application authorities tend to require also CO emission data. 6) Official measurements of O 2 are only required if the concentration of the pollutants must be converted to a reference oxygen level (mandatory within EMR). 7) If a reduction measure using ammonia as reduction agent (e.g. selective noncatalytic reduction) is installed a continuous measurement of the ammonia slip may be required. 8) If chlorinated substances are introduced into the kiln system (e.g. production of low alkali clinker) 9) If an alternative fuel is used, very often the authorities require a continuous VOC measurement. 10) If alternatives fuels are used, very often the authorities require a control measurement Cooler Stack Dust Official Measurements Control or Surveillance Continuous, if emission level is high Remark At a clinker cooler stack air with clinker dust is emitted. Therefore only a dust measurement is convenient. Surveillance with a cheap instrument, if mass flow is small. 15/51

16 2.3.3 Bypass Stack Dust Inorganic substances Gaseous or vaporous inorganic substances Official Measurements Control or surveillance Continuous, if emission level is high Control First priority: Hg Second priority: Cd, Tl Third priority: As, Co, Sb, Cr, Pb Control Continuous, if emission level is high Remarks Usually the emission at the bypass stack is not a high level emission and only control measurements should be made. Some metals can be enriched in the kiln gas atmosphere; therefore a control measurement should be made. HCl, SO Coal Mill Stack Dust Gaseous or vaporous inorganic substances Organic substances Official Measurements Control or surveillance Control (CO, SO 2 ) Control Remarks CO: Emission of CO from the coal milling plant should be checked (Indicates potential expulsion of volatiles in cases of excessive grinding temperature). SO 2 : Only in cases where high emission levels are measured at the main stack. VOC: Emission of VOC from the coal milling plant should be checked. 16/51

17 2.3.5 Cement Mill Stack Dust Inorganic Substances Official Measurements Control or surveillance (Control) Remarks If (enriched?) dust from the kiln filter system is fed to the cement mill a measurement of mercury was ordered in some cases, but no relevant mercury concentrations were found in the mill stack Separate Raw Mill Stack / Separate Raw Material Dryer Dust Inorganic Substances Organic Substances Official Measurements Control or surveillance Control (NO x, SO 2, CO, O 2 ) Control Remarks Measurements only if an auxiliary furnace is installed Measurements only if an auxiliary furnace is installed 17/51

18 3. SAMPLING PORTS AND MEASURING STATION The configuration of the measuring station and choice of measuring location can significantly effect the representativeness of measurements. This should be considered in the planning phase of projects for new plants or expansions. Compromises may have to be accepted at some older plants. 3.1 Measuring Location for Discontinuous Measurements and Extraction Point for Continuous Extractive Measurements The measuring location and the extraction point of the gases for the continuous extractive emission measuring devices should be chosen to meet the following criteria: The exhaust-gas composition must be representative for the emissions. The pollutant distribution should be as homogeneous as possible across the cross-sectional measuring area. Gas flow should be straight and not disturbed. Bends, branches, dampers, fans, and equipment mounted in the exhaust channel create undesired flow patterns. Straight channel sections with continuous form and cross-section are suitable. Vertical channels are better than horizontal ones for dust measurements. The lengths of straight channel sections should meet these minimum requirements: Upstream of the measuring location (approach length): 5 hydraulic diameters Downstream of the measuring location (exit length): 3 hydraulic diameters Hydraulic diameter is calculated as follows: A D h = 4 U where: A = cross-sectional area of the exhaust-gas channel U = circumference of the exhaust-gas channel Examples: Circular: Dh = d (= diameter of circle) Square: Dh = a (= length of side) If this requirement cannot be met, the upstream channel length (approach length) should at least be chosen to be longer than the downstream length (exit length). 3.2 Additional Requirements for Discontinuous Measurements The size and number of sampling ports depends on the measuring equipment being used and the required measurement task. For isokinetic sampling (dust, heavy metals, dioxins) an appropriate number of measuring flanges is required. DIN 2573 recommends flanges with a nominal size of 125 [mm]. Normally 2 openings for the network measurement of dust (2 axes arranged at an angle of 90 ), in case of larger diameters 4 openings (2 axes under 90 ) are required. 18/51

19 FIGURE 1: Number of openings Minimum 2 Openings For measuring other issues (gaseous substances, temperature, pressure, etc.) at least four additional flanges are necessary (2-inch gas pipes with male threads). The measuring station should meet the following requirements: - Unobstructed and safe access, accessible with pallets if possible (elevator, crane). - Stable work area suitable to the measurement task (see example Figure 2): Width: At least 3 [m] Depth: At least one channel diameter [m], minimum 2 [m] Load-bearing capacity: At least 250 [kg/m 2 ] Weather protection (against rain, wind, extreme temperatures) - Safety: Railing, curb around platform base Connection to the plant alarm system - Communication: Link to cebtral control room (telephone or radio) - Utilities: Electrical power supply (e.g. 400 [V], 15 [A]) with ground fault circuit interruption. (location of the plant circuit panel to be verified) Water (supply and waste lines) if necessary. Compressed air if necessary. 19/51

20 FIGURE 2: Example of a measuring station Plan Stack diameter + 1 [m] First sampling port At least 3 [m] Second sampling port [m] Elevation References VDI/VDE Guideline 2448 page 1; Planning of spot sampling measurements of stationary source emissions; VDI Guideline 2066 page 1; Staubmessungen in strömenden Gasen Gravimetrische Bestimmung der Staubbeladung, Übersicht; (No English translation available) 20/51

21 4. STANDARDIZIDED EMR MEASUREMENTS The Holcim Exco has adopted the EMR scheme, which requires the Group plants to install and operate continuous emission monitoring equipments and to measure some pollutants (at least) once per year (discontinuous measurement). In the following the recommended continuous measuring devices and discontinuous measurement proceedings are defined. Technical details of both types of measur e- ments are documented in Guidelines for Continuous Emissions Measurements at Holcim Cement Plants Guidelines for Annual Discontinuous Emissions Measurements at Holcim Cement Plants 4.1 Continuous Emission Measuring Devices Complete emission measuring equipment covering the EMR requirements (dust, NO, SO 2, VOC and O 2 ) consists of three different analyzer types: Dust monitor (in-situ) Continuous emission measuring device for inorganic gases (CEM) Flame ionization detector for the measurement of volatile organic compounds (The FID can be integrated in the CEM but is in any case a special device) Recommended Dust Measuring Devices Suitable dust measuring devices are In-Situ monitors. The supplier of an emission measuring system buys usually one of the well-known and suitable dust analyzers and integrates the signal into the electronic part of the system Recommended Continuous Emission Measuring Devices (CEM) for Inorganic Gases The CEM must be able to measure the compounds NO, SO 2, CO and O 2 and can be easily extended to NO 2, HCl, NH 3 and other gases. The FID can be integrated in the system FTIR-Analyzers (Fourier Transformed Infrared Spectroscopy) Extractive hot with FTIR analyzer E.g. ABB, Advanced Cemas-FTIR Compounds: CO, NO, SO 2, HCl, NH 3, H 2 O, O 2 Integration of flame ionization detector possible Differential Optical Absorption Spectrometroscopy In-Situ E.g. Opsis, AR600/AR650/O2000 Compounds: CO, NO, SO 2, HCl, NH 3, H 2 O, O 2 VOC can only be measured by a separate FID line 21/51

22 Extractive Hot with IR-Technology Extractive hot with IR analyzer E.g. SICK, MCS100 HW Compounds: CO, NO, SO 2, H 2 O, CO 2, HCl, O 2 Integration of flame ionization detector possible Recommended Flame Ionization Detector (FID) The sum of the emitted organic carbon (volatile organic compounds) cannot be measured with any principle of light absorption (FTIR, DOAS, IR). Therefore a complete other measuring principle, a flame ionization detector, must be used and this means that the CEM set must be coupled with such a different analyzing system. 4.2 Discontinuous Emission Measurements The annual measurement of emission components to be measured at least once per year in the framework of Holcim s EMR scheme for cement kilns includes two parts. Standard Situation Plant has CEM equipment according to EMR Part 1: Calibration of the installed continuous emission measuring (CEM) devices. The goal of this calibration is the correct adjustment of all continuously measuring devices to guarantee correct measurements for the determination of the daily averages of the compounds specified by the EMR scheme. - Dust - NO (for NOx calculation) - SO 2 - VOC - O 2 (for the 10 [%] O 2 reference calculation) - CO (if desired) Part 2: Measurement of emission compounds which cannot be measured continuously or for which the EMR scheme does not require CEM devices. - Heavy metals - Dioxins/furans (PCCDD/PCDF) - Ammonia (NH 3 ) - Hydrogen chloride (HCl) - Benzene (C 6 H 6 ) The measurements shall be taken according to the recognized rules of metrology (e.g. VDI guidelines, EN norms, etc.). Local institutes (test houses), with an admission from the local authorities, should carry out the measurements. 22/51

23 Non-Standard Situation EMR CEMs are not yet installed. Use same procedure as in standard situation (parts 1 and 2) just without CEMs calibration evaluation. Reference (or Convention) Methods Based on physical effects for each pollutant, reference methods are defined. Other measuring procedures must be evaluated with these reference methods (validation). Pollutant VDI Guideline DIN or EN standard Dust 2066 p.1, 2, Heavy metals 3868 p p.1, 2, 3, 4 Mercury Sulfur dioxide 2462 p.8 Nitrogen monoxide/dioxide 2456 p.8 Basic nitrogen compounds 3496 p.1 Carbon monoxide 2459 p.1, 7 Hydrogen chloride /2/3 Organic compounds (VOC) 3481 p.1, 3, Dioxin / Furans /2/ Calibration Measurement During calibration the analysis function of the plant s continuously operating measuring equipment is set or checked. For this purpose comparative measurements are carried out using a convention procedure (on-line or off-line procedure). To meet the criterion of representativeness, chronological and spatial distribution of the emissions across the measuring cross-sectional area must be established. If the spatial variation of specific emissions is small (e.g. gaseous components, low dust stacks), it will suffice to make comparative measurements near the point of sample extraction by the measuring equipment to be calibrated (point-related analysis function). Otherwise, comparative measurements are to be carried out as matrix measur e- ments (network-related analysis function). Evaluation The analysis function is calculated using linear regression analysis of the value pairs. The distribution of y-values about this function is also calculated (see example). The sampling period is generally 60 minutes, unless longer periods are necessary due to technical reasons, or deviation from this requirement is justified. The number of measurements is laid down in /51

24 Linear Regression Regression analysis is used to study the correlation between the value pairs x i, y i being compared. It is generally assumed that a linear relationship adequately describes the analysis function: ŷ = B x + C Slope of the lines: Ordinate interval: s xy B = s C = y b x xx Variance of y-values about the regression line (analysis function) 2 s yy s 2 xy s = 1 n 2 s xx s yy Arithmetic mean of x i : Arithmetic mean of y i : n n 1 1 x = x i y = y i n n i= 1 n 2 2 s xx = ( x i x) s yy = ( y i y) s xy = ( x i x) ( y i y) i= 1 Example Dust measurement after electrostatic separation configuration: 0 to 20 [ma] <--> 0 to 100 [mg / m 3 n,tr] Measurement No. Instrument Response [ma] n i= 1 i= 1 n i= 1 Mass Concentration (Comparative Method) [mg / m 3 n,tr] Compound operation Direct operation Arithmetic mean of x i : x = 7.58 [ ma ] 3 Arithmetic mean of y i : y = [ mg / m ] Regression line: ŷ = x Variance s 2 of y-values: s 2 = /51

25 Figure 3: Regression analysis of measurements Concentration [mg/m3] Measurements Regression line 98.9 [mg/m3] [mg/m3] Instrument Response (x) [ma] Discontinuous Emissions Measurement Certain pollutants are not monitored by the plant s continuously operating measuring equipment because no appropriate device is installed (e.g. HCl, NH 3 ) or because the pollutant cannot be continuously monitored (e.g. dioxins). These pollutants are determined using special methods. The measurements must relate to the operating stages, which are important for assessment (e.g. direct and compound operation). The measured and calculated values, the measuring methods used and the operating conditions of the kiln shall be recorded in a measuring report. The sampling period is generally 60 minutes, unless longer periods are necessary due to technical reasons (e.g. dioxins), or deviation from this requirement is justified. The number of measurements is laid down in /51

26 4.2.3 Number of Measurements Calibration Measurement with Continuous Operating Analyzers If continuous operating analyzers are being used for the calibration of the CEMs, then the signals over at least 24 hours should be compared with each other. During this 24-hour period at least 16 pairs of one-hour mean values must be determined Preheater kilns must be switched from compound to direct operation (or vice versa) at least once. At least 4 one-hour mean values must be obtained for each of the two operating modes Calibration and Discontinuous Measurement with Reference Methods Calibration Measurement Component Dust from kilns with electrostatic precipitator Dust from kilns with bag filters Gaseous compounds NO x, SO 2, O 2 HCl, NH 3 Volatile organic compounds (VOC) Number of Measurements Preheater kilns: 3 each in direct and compound operation Lepol or wet kilns: 6 measurements 6 measurements in compound or direct operation 1) Preheater kilns: 3 each in direct and compound operation Lepol or wet kilns: 6 measurements 2) To be checked/calibrated by means of another (certified) FID operating in parallel. If no (certified) analyzer available, assume readings from the stationary FID to be correct 1) The dust emission behind a bag filter is in both operation modes approximately the same (quantitatively and qualitatively). Therefore it is recommended to measure only during one operation mode. 2) If CEM measures HCl and/or NH 3 26/51

27 Discontinuous Measurement Component Gaseous compounds HCl, NH 3 Benzene (C 6 H 6 ) Mercury Other heavy metals Dioxins / furans (PCDD/PCDF) Number of Measurements Preheater kilns: 3 each in direct and compound operation Lepol or wet kilns: 3 measurements Preheater kilns: 3 in direct operation Lepol or wet kilns: 3 measurements Preheater kilns: 3 each in direct and compound operation Lepol or wet kilns: 3 measurements Preheater kilns: 3 in direct operation Lepol or wet kilns: 3 measurements Preheater kilns: 1 measurement during direct operation Lepol or wet kilns: 1 measurement 3) 4) 3) Generally the emission of these substances is higher in direct operation. 4) The PCDD/PCDF emission of SP/PC kiln is very low. In tendency PCDD/PCDF can be absorbed on dust particles and retained in the kiln system. Therefore only a measurement during direct operation should be made. Used Fuels: The kiln should be operated with the normal fuel mixture, that means with the average fuel mixture used during the year. Alternative fuels, usually used, should not be stopped or reduced! 27/51

28 5. STANDARDIZED REPORTING 5.1 Continuous Emission Measurement: Standardized Reporting on Basis of TIS For standardized worldwide Holcim emission reporting a standard tool enabling fast and accurate acquisition and reporting of environmental information is to be used. The reporting comprises: Dust, SO 2, NO x, VOC resulting from continuous measurements on basis of daily, monthly and yearly averages. All emissions referred to 10 % O 2 /dry gas. Other also continuously measured compounds (e.g HCl, NH 3, benzene, etc) Calculation of the Emission Benchmark Values and indication of exceedances. Reporting is extendable/adjustable according to local requirements (e.g. CO, Hg, ) Standardized worldwide Holcim emission reporting is accomplished on basis of a respective TIS module. Important advantages are: Fast Accurate No manual work necessary Data storage over years Automatic calculation of the and indication of exceeding of limit It also facilitates surveying of tests (e.g. after introduction of new AFR materials of installation of new environmentally relevant process equipment) or tracking of problems The TIS Module Every minute TIS acquires the momentary emission concentration value of the respective emission component (also O 2 ) All concentration values acquired from wet exhaust gas have to be converted to dry gas condition (TIS feature) All concentration values have to be converted to the 10 [%] O 2 reference value (upwards and downwards, TIS feature) Exhaust gas mass/volume flow at 10 [%] O 2 content is not measured but calculated by TIS on basis of the specific heat consumption Hourly Averages The minute values are then aggregated to hourly averages For plant internal purposes a daily emission report on basis of hourly (½ hourly) averages can be produced An hourly average is generated if: - Kiln feed is above 70 [%] of nominal capacity during at least 40 minutes within that respective hour - Emission measurement device is operational during at least the same 40 minutes within that hour 28/51

29 Daily Averages The hourly (or ½ hourly) averages are aggregated to daily averages A daily average is generated if at least 16 hourly averages are available For plant internal purposes a daily emission report on basis of hourly (½ hourly) averages can be produced Monthly report The daily averages are then aggregated to a monthly report containing: - General: Date (days of the month) Daily kiln operating hours (i.e. with feed > 70 % nominal feed) - Per emission component: Daily average emission concentration [mg/m 3 ] (void if no daily average available) Daily mass flow [t] Daily kiln operating hours without emission monitoring - Summary (final) line: Monthly kiln operating hours Monthly average emission concentration [mg/m 3 ] Monthly mass flow [t] Monthly operating hours without emission monitoring Number of daily averages available Number of non-compliance days (daily average emission >) of the month The monthly report can be used for plant and company internal reporting Yearly report The monthly reports are then aggregated to a yearly report containing: - General: Months Monthly kiln operating hours (kiln feed > 70 [%] nominal) - Per emission component: Monthly average emission concentration [mg/m 3 ] Monthly mass flows [t] Monthly kiln operating hours without emission monitoring Monthly number of daily averages available Monthly number of non-compliance days - Summary (final) line: Yearly kiln operating hours Yearly average emission concentration [mg/m 3 ] Yearly mass flow [t] Yearly kiln operating hours without emission monitoring and respective percentage of kiln operating hours Yearly number of daily averages available Yearly number of non-compliance days and respective percentage of sum of number of daily averages available The yearly report is to be used for EMR reporting at Holcim Group level Pro rata yearly reports can be produced anytime and may be used to complete the above mentioned monthly reports 29/51

30 5.1.2 EMR Annual Air Emission Report EMR Annual Emission Report Continuous Measurements: Dust Benchmark value: 50 mg/nm3 Month Hours of kiln operation in mode 1 and 2 Operating hours w/o EMR Number of daily averages available Company: Plant: Kiln No.: Oper. Year: Average emission concentration Number of daily averages exceeding the benchmark value Unit [h] [h] [-] [mg/nm3] [-] [t] January February March April May June July August September October November December Mass flow Total year Average calculated *) 0 Average (input) *) Weighted average calculated from number of daily averages available and average emission concentration Mode 1 = Compound operation (with running raw mill) Mode 2 = Direct operation (with stopped raw mill) Same page for the compounds NO, SO 2, VOC and other mandatory compounds (CO, HCl, NH 3, etc) HTC - The Naming Convention for Environmental Data The raw data (and if necessary some important intermediate calculated values) are named by the Holcim Technical Code, the HTC. Basically there is a Location, Material and an Identifier as follows: HTC Location HTC Identifier Location HTC (HAC) Kiln Kiln Identifier Tons emitted Concentration [mg/m 3 ] HTC (unit) TEMI MGNM3 30/51

31 HTC Material Item Name Environment, dust Environment, sulfur dioxide Environment, nitrogen dioxide Environment, volatile organic components Environment, carbon monoxide Environment, oxygen Environment, hydrogen chloride Environment, ammonia Environment, heavy metals Environment, dioxin / furans Environment, benzene HTC (Material) DUST SO2 NOX VOC CO O2 HCL NH3 HM DF C6H Examples Example: Kiln 3 NOX emission in tons 403-TEMI-NOX The above show report will be shown in HTC as follows: Month Monthly kiln operating hours HTC 401- HOUR- Average [mg/m 3 ] Mass flow [t] 401- MGNM3- DUST 401- TEMI- DUST Dust ( = 50) Hours without EMR 401- HOUR-EI No. of DA available 401- DAY-EMI No. of NC days 401- DAYNC- EMI CLILNKE Jan Feb Discontinuous Emission Measurement Report Usually, external specialists are entrusted with measuring the emissions at the stack of a cement plant and with writing an emission measuring report. Generally, these specialists only have moderate knowledge of the cement production process and therefore they are often not able to exactly define the operating conditions of the cement kiln they are working upon. 31/51

32 As a consequence, the measuring reports of such institutes should be amended by an additional report of a cement process specialist. An emission measuring report thus has to include two essential parts: Part 1: The report about the emission measurements at the stack Part 2: The report about the operating conditions of the measured kiln Part 1: The Report about the Emission Measurements at the Stack The report about the measurements at the stack should contain at least the following information: List of Instruments used and Procedures applied Emission measurements must be carried out according to the rules of the art of measuring technique. In the report, the methods used must exactly be described. If standard methods (e.g. guidelines) are used, deviations from the described procedures must be stated. The Results It is important not only to clearly record the measured concentrations but also important other values (e.g. temperatures, pressures, volume streams, etc.). The following information is requested: - Dust - Number of measuring points per cross section measured - Number of cross sections measured - Result of each measurement and average of all measurements. If one of the measurement is not taken into consideration (e.g. outlayer) the reasons thereof have to be stated - Mean velocity or volume stream at the measuring section - Temperature, static pressure at the measuring section - Gas composition (CO 2, O 2, CO) and moisture content at the measuring section. - Heavy Metals - Number of measurements respectively number of expositions - Results of all measurements and average. If one of the measurement is not taken into consideration (e.g. outlayer) the reasons thereof have to be stated - Extraction volumes through the wash bottle respectively through the exposed filter. - Dioxines / Furanes - Number of measurements - Extraction volume and extraction time 32/51

33 - Other discontinuous measurements (e.g. NH 3, HCl, etc.) - Number of measurements - Results of all measurements and average. If one of the measurements is not taken into consideration (e.g. outlayer) the reasons thereof have to be stated - Extraction volume and extraction time - Continuous measurements - The signals of the instruments should be compressed to hourly or halfhourly averages. - Number, global average, standard deviation, maximum and minimum of hourly or half-hourly averages. - Concentration of used zero and calibration gas. Standardized Reporting on Basis of TIS EMR Annual Emission Report Control Measurements Company: Plant: Kiln No.: Oper. Year: Emission component Date of measurement Kiln operation mode Analytical method used Value measured Unit Remarks HCl *) [mg/nm3] NH3 *) [mg/nm3] C6H6 [mg/nm3] PCDD/DF [ng/nm3] Hg [µg/nm3] Tl [µm/nm3] Cd [µm/nm3] As [µm/nm3] Co [µm/nm3] Ni [µm/nm3] Sb [µm/nm3] Pb [µm/nm3] Cr [µm/nm3] Cu [µm/nm3] Mn [µm/nm3] V [µm/nm3] *) Benchmark value: 30 mg/nm3 Mode 1 = Compound operation (with running raw mill) Mode 2 = Direct operation (with stopped raw mill) 33/51

34 5.2.2 Part 2: The Report about the Operating Conditions of the Measured Kiln The report about the operating conditions of the kiln under consideration should contain at least the following information: Mass flow of raw meal fed to the kiln Mass flows of all fuels used The exact time periods of compound- or direct operation mode The exact time periods of gas extractions from the kiln systems (e.g. gas extraction for coal mill) The concentrations indicated by all plant measuring devices at kiln inlet, in the kiln system and at the stack. The signals of the instruments should be compressed to hourly or half-hourly averages. It is recommended to adjust these measuring devices prior to any emission measuring campaign by means of calibration gases. Additionally it is recommended to take representative samples of the raw meal, the clinker and all fuels during the measuring campaign. In the case of PCDD/PCDF measurements carried out, it is recommended that during the respective sampling campaign at the stack also a dust sample from the system dedusting device (bag filter/house or last chamber of the electrostatic precipitator) is taken. The samples should be stored in the plant and in cases of unexpected results be analyzed (e.g. by the expulsion test). 34/51

35 6. GUIDE TO A FIRST PLAUSIBILITY CHECK OF RESULT OBTAINED Emission measurements should be controlled by plausibility checks. Equations or emission ranges are indicated in the following. The given concentration ranges refer to standard conditions (1013 [mbar], 0 [ C]) and dry gas conditions. 6.1 Check of the Emission Ranges Volume Stream The volume stream must be measured to determine: The mass of the emitted substance per unit of time (concentration times volume stream) The dust concentration (on basis of the gas velocity profile) Heavy metals (on basis of the gas velocity profile) The measurement of the volume stream should be checked by the following approximation: v tot = ( 0.25 O2 q ) 1 + Ł ( 21- O 2 ) ł v tot : Specific exhaust gas volume at standard conditions (0 [ C], 1013 [mbar]) in dry gas state; unit: [m 3 /kg clinker] q: Heat consumption of the kiln; unit: [MJ/kg clinker] O 2 : Oxygen content at measuring point; unit: [vol%] (dry) A deviation between the measured and the calculated volume stream of more than ±15 [%] should not be accepted Carbon Dioxide The measurement of carbon dioxide concentration should be checked by the following approximation: 0.05 q e CO CO 2 = v tot CO 2 : Carbon dioxide content [%] (dry) ε CO2 : Emission factor [kg/gj] Fuel e CO2 Fuel e CO2 Coal 94 Rubber Products 80 Coke 104 Plastics 84 Wood 100 Oil (incl. waste oil) 75 Tires 80 Solvents 70 A deviation between the measured and the calculated CO 2 content of the exhaust gases of more than 2 [%] should not be accepted. 35/51