United States Environmental Protection Agency Atmospheric Sciences ~, Research Laboratory * Research Triangle Park NC 27711 ' i' Research and Development EPA/600/S3-86/055 Feb. 1987 &EPA Project Summary Characterization of Stack Emissions from Municipal Refuse-to-Energy Systems J. E. Howes, Jr., D. F. Kohler, F. L. DeRoos, R. M. Riggin, R. L. Barbour, and R. L. Bennett Stack emissions from three munici- pal refuse-to-energy systems were characterized: refuse-derived fuel (RDF), mass burning (MASS) and mod- ular (MOD). A comprehensive set of measurements was performed at each site to determine the physical and chemical properties of the particulate and gaseous stack emissions. The physical characterization in- cluded measurement of the mass con- centration, and size distribution of the stack particulate matter. Inorganic chemical characterization of the stack emissions included determination of gaseous HCI and HF emissions, and de- termination of volatile trace element levels. The characterization of organic materials in the stack emissions in- cluded specific measurements for polynuclear aromatic hydrocarbons (PAH), tetrachlorinated benzo-p- dioxins (TCDD) and dibenzofurans (TCDF), and aldehydes. Screening analyses were performed to provide tentative identification of organic com- pounds in the stack emissions. This Project Summary was devel- oped by EPA's Atmospheric Sciences Research Laboratory, Research Triangle Park, NC, to announce key findings of the research project that is fully docu- mented in a separate report of the same title. (See Project Report ordering infor- mation at back). Introduction Vast quantities of municipal refuse are generated daily throughout the United States. Although incineration has been used for reduction of refuse volume in the past, the most common and economical method of disposal has been the use of landfills or open dumps. However, the availability and cost of convenient landfill sites and public ac- ceptance makes this option less eco- nomically attractive as a future disposal method. A second important factor which will impact on future waste dis- posal practice is the increased empha- sis on energy conservation. Municipal refuse represents an energy source which when burned can supply steam for heat and electricity production. Be- cause of these land and energy conser- vation considerations, it is anticipated that there may be a significant increase in refuse-to-energy incineration of mu- nicipal refuse in the future. An important issue which must be ad- dressed in view of the expected prolifer- ation of energy-to-refuse incineration systems is the potential release of haz- ardous pollutants into the environment from these facilities. The information base is limited and additional work is needed to develop emission data to an- swer the environmental questions, par- ticularly in the case of newer refuse-to- energy incinerator systems. The purpose of the research program described in this report was to charac- terize the physical and chemical compo- sition of airborne emissions from mu- nicipal refuse-to-energy units. The study included a comprehensive set of physical and chemical measurements which identify and quantify the emis- sions of three refuse-to-energy units; a refuse-derived fuel, mass burning, and modular design. Thus, the emission data provides an important contribution ------- to the data base available to assess the environmental impact of refuse-to- energy systems, to identify specific pol- lutants which may have adverse health and/or environmental effects, and to de- termine the need for process and/or control technology modifications to re- duce pollutant emissions. Procedures The study involved a comprehensive set of measurements to characterize the physical and chemical composition of stack emissions from three refuse-to- energy units. A summary of the meas- urements that were performed and the sampling and analytical methods that were employed in the study is given in Table 1. Stack emission measurements were performed on three refuse-to-energy in- cineration units. A summary of the char- acteristics of the units is provided in Table 2. The sites included recently con- structed units of three different designs; refuse-derived fuel (RDF), mass burning (MASS) and modular (MOD). All three units were fueled with solid municipal refuse, however, approximately 30 per- cent of the modular unit feed came from industrial sources. Refuse feed for the RDF unit was shredded and pneumati- cally and magnetically classified while the MASS and MOD units burned un- classified bulk refuse. The feed rate data given in the table are estimates for the period during which tests were con- ducted and do not necessarily represent the design capacity of the units. At all sites, the emission measure- ments were performed by sampling from a duct or stack downstream of the control devices, if present. Operating conditions considered "normal" for each unit prevailed during the respec- tive test periods. Results and Discussion Particulate Mass and Size Distribution The particulate mass concentrations were measured in the emissions from the RDF, MASS, and MOD units with EPA Method 5. Additional mass concen- tration data were obtained from the SASS tests. Based on the Method 5 data, the mass concentration of particu- late material in the RDF emissions ranged from 272 to 441 mg/dscm and the emission rate ranged from 22.4 to 36.1 kg/hr. For the MASS unit, the ex- tremes in particulate mass concentra- tion were approximately 261 and 599 Table 1. Measurement Sampling and Analytical Methods Used for Characterization of Refuse-to-EnergyA System Stack Emissions ™ Sampling Method Analytical Method Particulate Mass Particle Size Distribution Elemental Composition of Flyash Volatile Trace Elements HCI/HF Anions in flyash Polyaromatic hydrocarbons (PAH) Tetrachlorodibenzo-p- dioxins/tetrachlorodibenzo furans (TCDD/TCDF) Aldehydes Organic compound screening Volatile organic compounds EPA Method 5 Gravimetric Andersen In-Stack Impactor Gravimetric Source Assessment Sampling System (SASS) (Cyclones/filter catch) SASS (impingers loaded with ammonium persulfate/silver nitrate solution Impinger train with IN NaOH solution SASS (Cyclones/filter catch) SASS (Cyclones/filter/XAD-2 catch) SASS (Cyclones/filter/XAD-2 catch) Impinger train with dinitrophenyl hydrazine solution SASS (Cyclones/filter/ XAD-2) Stainless steel cannister grab samples (1) Spark-source mass spectrometry (2) X-ray fluorescence (3) Combustion Atomic absorption Ion chromatography Ion chromatography Combined high resolution gas chromatography/ mass spectrometry (HRGC/MS) Combined high resolution gas chromatography/high resolution mass spectrometry (HRGC/HRMS) High performance liquid chromatography (HPLC/ fluorescence HRGC/MS—computer search/spectra matching Capillary column gas chromatography with FID and EC detection mg/dscm and the particulate emissions of the MOD unit based on two valid tests ranged from approximately 153 to 261 mg/dscm in mass concentration and from 2 to 3.6 k/g in mass emission rate. Particulate size distribution data were obtained for the three incinerator units. From the curves obtained, it is evident that the emissions from none of the units follow a log-normal distribution. The approximate mass median diame- ter of particulate emissions determined by measurements made with an An- dersen impactor were: 6 (im for the RDF unit, 12 fim for the MASS unit, and 0.8 H,m or less for MOD unit. The RDF and MASS units were equipped with elec- trostatic precipitators. Inorganic Emissions Elements detected in the particulate emissions of the three units at levels of 10 percent by weight or higher were C and Cf. Those generally present at or above 1 percent by weight were Ca, Zn, Fe, S, Si, KyAI; Madrid Pr>. The prmcipal anions common to samples from all three units were sulfate, chloride, and bromide. The soluble fraction of the fly ash from the three units varied from ap- proximately 13 to 77 percent by weight with the MOD sample exhibiting the least solubility. Of the volatile elements measured in the stack emissions of the three inciner- ator units, the most abundant element was Hg, which was found at widely varying levels; 16 to 6250 jixj/dscm. Concentrations of As, Se, Sb, and Pb were generally less than 10 n-g/dscm, although Sb was detected at a concen- tration of 42 fig/dscm in one of the MASS samples. Levels of HCI ranging from 352 to 516 mg/dscm (263 to 340 ------- Table 2. Summary of Study Site Characteristics Refuse-Derived Fuel Unit Mass Burning Unit Modular Unit Site Code Process characteristics Feed Estimated feed rate during study Emission control Stack gas temperature RDF • shredding • air classification • magnetic separation • semi-suspension stoker-grate boiler Municipal refuse 600 TPD Electrostatic precipitator 230°C MASS * mass burning • bulk refuse Municipal refuse 125 TPD Electrostatic precipitator 270°C MOD • Consumatunit • bulk refuse Municipal and commercial refuse SO TPD None 255°C ppm) were measured in the RDF and MASS units. Lower levels of HCI, 53 to 231 mg/dscm (35 to 153 ppm), were de- tected in the MOD emissions. The con- centration of HF in the emissions of the three units was fairly uniform, ranging from 0.3 to 1.4 mg/dscm (0.4 to 1.7 ppm). The results of the infrared analysis of emission samples from the refuse-to- energy units are summarized and the infrared spectra of the various samples are presented in the report. Identifica- tion of compounds in the paniculate emission samples from the three units are given as positive, probable or possi- ble. In all cases, those identifications which are only tentative (marked possi- ble) are of minor or trace components; because the component is present in such low concentration, a positive iden- tification is not possible. The three samples are similar in com- position in that they are mixtures of sul- fatesr, silicates and quartz. Perhaps more striking is the number of possible compound types not present, in particu- lar, metal oxides. Most fly ashes from combustion sources contain significant quantities of metal oxides. These sam- ples contain neither these nor any other oxide with the possible exception of the oxides which adsorb only in the far in- frared region. In addition, though less surprising, these samples show no indi- cation of nitrates, phosphates or ammo- nium compounds which are also fre- quently found in fly ash. Organic Emissions Concentrations of polynuclear aro- matic hydrocarbons (PAH) compounds found in the stack emissions of the refuse-to-energy systems varied widely for the same unit as well as among the three units. The lowest values were ob- served in the MOD emissions and the highest in the MASS emissions. Com- pounds present in emissions of all three units included: naphthalene, phenan- threne/anthracene, pyrene, ace- napthylene. The higher molecular weight PAH compounds, e.g., benzopy- renes were detected only in the MASS emissions. Data for the RDF and MASS units shows that the PAH distribution in the emissions heavily favors the gas phase at the temperature maintained during sample collection (205°C). Sepa- rate analysis of the paniculate and gas phase samples was not performed on the MOD samples. The TCDD and TCDF data show con- siderable variation in levels among tests on the same unit and between units, however, the variations are not as great as observed for the PAH com- pounds. The average total TCDD con- centrations measured in the RDF, MASS, and MOD stack emissions were 174, 245, and 11 ng/dscm, respectively. The 2,3,7,8-TCDD isomer constituted a significantly larger fraction of the total TCDD emission from MASS unit than from the other two incinerators. The av- erage total TCDF emissions from the RDF, MASS, and MOD units were 458, 385, and 73 ng/dscm, respectively. The distribution of TCDD generally appears to favor the paniculate phase although RDF Test No. 2 shows the major fraction in the gas phase. The TCDF data does not show a clear trend in distribution between the paniculate and gaseous phases of the emissions. The concentrations of aldehydes found in the incinerator emissions show large variations in aldehyde levels both within and between sites. Generally higher concentrations were observed in the MASS emissions. The Mass Test No. 2 data show that the aldehydes were efficiently collected by the im- pinger train. Conclusions and Recommendations This study provides physical and chemical characterization data to sup- port assessment of the impact of munic- ipal refuse-to-energy system emissions on public health and the environment and to guide future similar studies. The data show wide variations in the com- position and levels of various species in the stack emissions both among the various units studied and among repeti- tive measurements at the same unit. These variations may be due to influ- ences from one or a combination of the following factors: unit type, unit design, refuse composition, or operating condi- tions. The scope of this study did not encompass the collection of data and measurement of the parameters re- quired to evaluate the factors that influ- ence refuse-to-energy system emis- sions. It is assumed that "normal" operating conditions prevailed during the emission measurements, however, the possibility that abnormal operating events occurred during test period and that these events influenced the emis- sion characteristics, cannot be dis- counted. This possibility should be kept in mind in considering the following conclusions. The high concentration and the rela- tively large size paniculate emissions indicate either inefficient operation of the electrostatic precipitators (ESP) ------- on the RDF and MASS units or com- bustion conditions for which the ESP's were not designed. The paniculate emissions from the three types of refuse-to-energy units are similar in inorganic chemical composition. Inorganic compounds in the emissions are present primarily as chlorides and sulfates. The emissions from the municipal refuse-to-energy units varied greatly in organic chemical composition. This result is presumably due to design differences and variations in refuse feed composition and operating parameters of the units. The study has yielded a comprehen- sive data base to support environmen- tal assessment of municipal refuse-to- energy systems and to identify areas that may require additional research. The most urgent need of future studies is to acquire the supporting data re- quired to establish the incinerator oper- ating conditions during emission meas- urement periods. This information would identify abnormal conditions and, in general, would permit the eluci- dation of the relationship between de- sign and operating parameters and emission characteristics. Based on data obtained in this study, it appears that improvements in design or operation of municipal refuse-to- energy systems could be made to re- duce stack emissions. In general, modi- fications e.g., in refuse preparation, combustion air feed, etc., that increase combustion efficiency should signifi- cantly reduce emission levels. Control devices should also be selected and op- erated to provide more efficient capture of particles from the emission stream. Future studies should adopt a paramet- ric experimental design to clearly iden- tify the design and operational variables that influence emission levels and to op- timize conditions for emission reduc- tion. J. E. Howes. Jr., D. F. Kohler. F. L DeRoos, R. M. Riggin, and R. L. Barbour are with Battelle Columbus Laboratories, Columbus. OH 43201; the EPA author Roy L. Bennett (also the EPA Project Officer, see below) is with the Atmospheric Sciences Research Laboratory, Research Triangle Park, NC 27711. The complete report, entitled "Characterization of Stack Emissions from Municipal Refuse-to-Energy Systems." 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