United States Environmental Protection Agency Air and Energy Engineering Research Laboratory Research Triangle Park NC 27711 Research and Development EPA/600/S7-86/049 Mar. 1987 Project Summary Nonferrous Industry Particulate Emissions: Source Category Report Mark Burnett and Andrew Minden The objective of this study was to develop participate emission factors based on cutoff size for inhalable par- ticles for the nonferrous industry. After a review of available information char- acterizing participate emissions from nonferrous plants, the data were sum- marized and rated in terms of reliability. Size specific emission factors were developed from these data for the major processes used in the manufacture of nonferrous metals. A detailed process description was presented with em- phasis on factors affecting the genera- tion of emissions. A replacement fcr Sections 7.1 (Primary Aluminum Pro- duction), 7.3 (Primary Copper Smelt- ing), 7.6 (Primary Lead Smelting), 7.7 (Primary Zinc Smelting), and 7.11 (Secondary Lead Smelting) of EPA re- port AP-42, A Compilation of Air Pol- lutant Emissions Factors, was prepared, containing the size specific emission factors developed during this program. This Project Summary was developed by EPA's Air and Energy Engineering Re- search 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 In- formation at back). Introduction The purpose of this program was to summarize the best available information on emissions of inhalable particulate matter in the nonferrous industry. The main objective of the program was to develop reliable size-specific emission factors for the various processes used in the production of nonferrous metals. Both uncontrolled and controlled emission fac- tors are presented in the report. The uncontrolled factors represent emissions which would result if the particulate control device (e.g., baghouse, ESP) were bypassed, and the controlled factors represent emissions emanating from a particular type of control system. The size-specific emission factors are gen- erally based on the results of simul- taneous sampling at the inlet and outlet of the control device(s), utilizing a variety of particle sizing techniques. Other ob- jectives of this program were to present current information on the nonferrous industry as well as prepare a replacement for Sections 7.1,7.3,7.6,7.7, and 7.11 in EPA report AP-42, "A Compilation of Air Pollutant Emissions Factors." The above objectives were met by a thorough literature search which included: • Data from the inhalable particulate characterization program, • Fine Particle Emissions Inventory System (FPEIS), • AP-42 background file at EPA's Office of Air Quality Planning and Standards (OAQPS), • State and local air pollution control agencies, and • Various industry sources The emission data contained in the reference documents were reviewed, analyzed, summarized, and ranked ac- cording to the criteria established by OAQPS as published in the EPA report, "Technical Procedures for Developing AP-42 Emission Factors and Preparing AP-42 Sections," April 1980. After rank- ing the data, emission factors were cal- ------- Table 1. Uncontrolled Emission Factors and Particle Size Distribution For Roof Monitor Fugitive Emissions From Prebake Aluminum Cells EMISSION FACTOR RATING: C Particle size, nm IS 10 5 2.5 1.25 0.625 Cumulative mass% < stated size 65 58 43 28 18 13 Cumulative emission factors kg/MgAI 1.62 1.45 1.08 0.70 0.46 0.33 Ib/tonAI 3.23 2.90 2.15 1.40 0.92 0.67 Total 100 2.5 5.0 Table 2. Uncontrolled Emission Factors and Particle Size Distribution For Roof Monitor Fugitive Emissions From HSS Aluminum Cells EMISSION FACTOR RATING: D Particle size. nm 15 10 5 2.5 1.25 0.625 Cumulative mass% < stated size 39 31 23 17 13 8 Cumulative emission factors kg/MgAI 1.95 1.55 1.15 0.35 0.65 0.40 Ib/ton At 3.9 3.1 2.3 1.7 1.3 0.8 Total 100 5.0 10.0 Table 3. Uncontrolled Emission Factors and Particle Size Distribution For Primary Emissions From HSS Reduction Cells EMISSION FA C TOR RA TING: D Particle size, nm 15 10 5 2.5 1.25 0.625 Cumulative mass% < stated size 63 58 50 40 32 26 Cumulative emission factors kg/MgAI 30.9 28.4 24.5 19.6 15.7 12.7 Ib/ton Al 61.7 56.8 49.0 39.2 31.4 25.5 Total 100 49.0 98.0 culated using the highest quality data available. The quality of the data used to develop each emission factor is indicated by the emission factor rating. Process control system operating data as well as general industry information were also obtained and summarized as general background information. It was not part of this program to provide detailed engineering analyses, product specifica- tions, or detailed evaluation of trends in the industry. Summary of Results Primary Aluminum Aluminum metal is manufactured by the Hall-Heroult process, which involves the electrolytic reduction of alumina dis- solved in a molten salt bath of cryolite (Na3AIF6) and various salt additives. The electrolytic reduction occurs in shallow rectangular cells (pots), which are steel shells lined with carbon. Carbon elec- trodes extending into the pot serve as the anodes, and the carbon lining the steel shell is the cathode. Molten cryolite func- tions as both the electrolyte and the solvent for the alumina. Emissions from aluminum reduction processes consist primarily of gaseous hydrogen fluoride and particulate fluo- rides, alumina, carbon monoxide (CO), volatile organics, and sulfur dioxide (S02) from the reduction cells; and fluorides, vaporized organics, and SO2 from the anode baking furnaces. A variety of control devices have been used to abate emissions from reduction cells and anode baking furnaces. To control gaseous and particulate fluorides and particulate emissions, one or more types of wet scrubbers (spray tower and chambers, quench towers, floating beds, packed beds, Venturis, and self-induced sprays) have been applied to reduction cells and to anode backing furnaces. Also, particulate control methods — e.g., ESPs (wet and dry), multiple cyclones, and dry alumina scrubbers (fluid bed, injected, and coated filter types) — are used with baking furnaces and reduction cells. Also, the alumina adsorption systems are being used to control both gaseous and par- ticulate fluorides by passing the pot off- gases through the entering alumina feed, which adsorbs the fluorides. Baghouses are then used to collect residual fluorides entrained in the alumina and recycle them to the reduction cells. Uncontrolled emissions from aluminum reduction cells are given in Tables 1 to 3. Primary Copper In the U.S., copper is produced from sulfide ore concentrates principally by pyrometallurgical smelting. Because the ores usually contain less than 1 % copper, they must be concentrated before trans- port to smelters. Concentrations of 15- 35% copper are produced at the mine site by crushing, grinding, and flotation. The conventional pyrometallurgical copper smeiiing process includes roasting of ore concentrates to produce calcine, smelting of roasted (calcine feed) or unroasted (green feed) ore concentrates to produce matte, and converting of the matte to yield blister copper product (about 99% pure). Roasters, smelting furnaces, and con- verters are sources of both particulate matter and S02. Copper and iron oxides are the primary constituents of the par- ticulate matter, but other oxides (e.g., of arsenic, antimony, cadmium, lead, mer- cury, and zinc) may also be present, with metallic sulfates and sulfuric acid mist. ------- Single stage ESPs are widely used in the primary copper industry to control par- ticulate emissions from roasters, smelting furnaces, and converters. The process sources of particulate matter are also the potential fugitive sources of these emissions: roasting, smelting, converting, fire refining, and slag cleaning. The actual quantities of emissions from these sources depend on the type and condition of the equipment and on the smelter operating techniques. Although emissions from many of these sources are released inside a building, ultimately they are discharged to the atmosphere. Fugitive emissions from primary copper smelters are captured by applying either local or general ventilation. Once cap- tured, emissions may be vented directly to a collection device or be combined with process offgases before collection. Close fitting exhaust hood capture sys- tems are used for multiple hearth roasters and hood ventilation systems for smelt matte tapping and slag skimming. For converters, secondary hood systems or building evacuation systems are used. Size-specific process emission factors are given in Tables 4 and 5. Primary Lead Smelting Lead is usually found naturally as a sulfide ore containing small amounts of copper, iron, zinc, and other trace ele- ments. It is usually concentrated at the mine from an ore of 3-8% lead to a concentrate of 55-70% lead, containing 13-19 wt % free and uncombined sulfur. Processing involves three major steps: (1) sintering, in which the concentrated lead and sulfur are oxidized to produce lead oxide and S02, (2) reducing the lead oxide contained in the sinter to produce molten lead bullion, and (3) refining the lead bullion to eliminate impurities. Each of the three major lead smelting process steps generates substantial quantities of particulates. Particulate emissions from blast furnaces contain many different kinds of material, including a range of lead oxides, quartz, limestone, iron pyrites, iron-lime-silicate slag, arse- nic, and other metallic compounds as- sociated with lead ores. These particles readily agglomerate and are primarily submicron in size, difficult to wet, and cohesive. They will bridge and arch in hoppers. Minor quantities of particulates are generated by ore crushing and mate- rials handling. The most commonly used high effici- ency particulate control devices used in Table 4. Particle Size Distribution and Size Specific Emission Factors For Multiple Hearth Roaster and Reverberatory Smelter Operations" EMISSION FACTOR RATING: D Cumulative mass % < stated size Particle size, urn 15 10 5 2.5 1.25 0.625 Uncontrolled 100 100 100 97 66 25 ESP controlled 100 99 98 84 76 62 Cumulative emission factors Uncontrolled kg/Mg 47 47 47 46 31 12 Ib/ton 95 94 93 80 72 59 ESP controlled kg/Mg 0.47 0.47 0.46 0.40 0.36 0.29 Ib/ton 0.95 0.94 0.93 0.80 0.72 0.59 Total 100 100 47 95 0.47 0.95 * Expressed as units/unit weight of concentrated ore processed by the smelter. Table 5. Particle Size Distribution and Size Specific Emission Factors For Copper Converter Operations8 EMISSION FACTOR RATING: E Cumulative mass % < stated size Particle size, urn 15 10 5 2.5 1.25 0.625 Uncontrolled NR 59 32 12 3 1 ESP controlled 100 99 72 56 42 30 Cumulative emission factors Uncontrolled kg/Mg NR 10.6 5.8 2.2 0.5 0.2 Ib/ton NR 21.2 11.5 4.3 1.1 0.4 ESP controlled kg/Mg 0.18 0.17 0.13 0.10 0.08 0.05 Ib/ton 0.36 0.36 0.26 0.20 0.15 0.11 Total 100 too 18 36 0.18 0.36 " Expressed as units/unit weight of concentrated ore processed by the smelter. NR - not reported because of excessive extrapolation. lead smelter operations are fabric filters and ESPs, which often follow centrifugal collectors and tubular coolers (pseudo- gravity collectors). Size-specific emission factors for con- trolled emissions from a primary lead blast furnace are given in Tahie 6. Size- specific emission factors for fugitive emissions generated at a primary lead processing plant are given in Tables 7 through 9. Secondary Lead Processing The secondary lead industry processes a variety of lead-bearing scrap and residue to produce lead and lead alloy ingots, battery lead oxide, and lead pigments (Pb304 and PbO). Processing may involve scrap pretreatment, smelting, and refin- ing/casting. Scrap pretreatment is the partial removal of metal and nonmetal contaminants from lead-bearing scrap and residue. Processes used for scrap pretreatment include battery breaking, crushing, and sweating. Smelting is the production of purified lead by melting and separating lead from metal and nonmetallic contaminants and by reduc- ing oxides to elemental lead. Refining/ casting is the use of kettle type furnaces for remelting, alloying, refining, and oxidizing processes. Reverberatory smelting furnaces emit particulates consisting of oxides, sulfides, and sulfates of lead, antimony, arsenic, copper, and tin, as well as unagglomer- ated lead fume. Emissions are generally controlled with settling and cooling chambers followed by a baghouse. Wet scrubbers are sometimes used to reduce S02 emissions. However, because of the small particles emitted from reverberatory furnaces, baghouses are more often used than scrubbers for particulate control. Emissions from blast furnaces occur at charging doors, the slag tap, the lead well, and the furnace stack. Emissions from the charging doors and the slag tap are hooded and routed to the devices treating the furnace stack emissions. ------- Table 6. Lead Emission F Blast Furnace Fli Particle size, Co 15 10 6 2.5 1.25 1.00 0.625 Total Table 7. Uncontrolled Le Sinter Machine Particle size, Ct 15 10 6 2.5 1.25 1.00 0.625 Total :actors and Particle Size Distribution For Baghouse Controlled ue Gases EMISSION FACTOR RATING: C Cumulative emission factors imulative mass % < stated size 98 86.3 71.8 56.7 54.1 53.6 52.9 100.0 kg/Mg 1.17 1.03 0.86 0.68 0.65 0.64 0.63 1.20 Ib/ton 2.34 2.06 1.72 1.36 1.29 1.28 1.27 2.39 iad Fugitive Emission Factors and Particle Size Distribution For EMISSION FACTOR RATING: D Cumulative emission factors jmu/ative mass % < stated size 99 98 94.1 87.3 81.1 78.4 73.2 100.0 kg/Mg 0.10 O.JO 0.09 0.08 0.07 0.07 0.07 0.10 Ib/ton 0.19 0.19 0.17 0.16 0.15 0.15 0.14 0.19 Blast furnace particulates are smaller than those emitted from reverberatory furnaces and are suitable for control by scrubbers or fabric filters downstream of coolers. Emissions from oxidizing furnaces are economically recovered with baghouses. The particulates are mostly lead oxide, but they also contain lead and other metals. Size-specific emission factors for con- trolled blast furnace flue gases are given in Table 10. Primary Zinc Smelting Zinc is found primarily as the sulfide ore sphalerite (ZnS). Zinc ores typically contain 3-11% zinc. Zinc ores are pro- cessed into metallic slab zinc by the electrolyte process or the pyrometal- lurgical smelting process. Electrolytic processing involves four major steps: roasting, leaching, purifica- tion, and electrolysis. Pyrometallurgical processing involves three major steps: roasting, sintering, and retorting. Each of the two zinc smelting processes generates emissions along the various process steps. Most of the particulate emissions in the primary zinc smelting industry are generated in the ore con- centrate roasters. Particulate emission controls are generally required for the economical operation of a roaster: cy- clones and ESPs are the primary controls used Table 8. Uncontrolled Lead Fugitive Emission Factors and Particle Size Distribution For Blast Furnace Total mass emission factors for con- trolled and uncontrolled emission factors for point sources in a zinc smelting plant are given in Table 11. EMISSION FACTOR RATING: D Particle size. Cumulative emission factors Cumulative mass % < stated size kg/Mg Ib/ton 15 10 6 2.5 1.25 1.00 0.625 94 89 83.5 73.8 65.0 61.8 54.4 0.11 0.11 0.10 0.09 0.08 0.07 0.06 0.23 0.21 0.20 0.17 0.15 0.15 0.13 Total 100.0 0.12 0.24 ------- Table 9. Uncontrolled Lead Fugitive Emission Factors and Particle Size Distribution For Reverberating Furnace EMISSION FACTOR RATING: D Panicle Cumulative emission factors size. Cumulative mass % urn < stated size kg/Mg Ib/ton 15 99 0.24 0.49 10 98 0.24 0.48 6 92.3 0.22 0.45 2.5 80.8 0.20 0.39 1.25 67.5 0.16 0.33 1.00 61.8 0.15 0.30 0.625 49.3 0.12 0.24 Total 100.0 0.24 049 Table 10. Emission Factors and Particle Size Distribution For Baghouse Controlled Blast Furnace Flue Gases3 EMISSION FACTOR RATING: D Particle size, fim 15 10 6 25 1.25 1.00 0.625 < stated size 93.0 89.0 83.5 71.0 44.5 33.0 14.5 Cumulative emission factors kg/Mg 0.22 0.21 0.20 0.17 0.11 0.08 0.03 Ib/ton 0.45 0.43 0.40 0.34 0.21 0.16 0.07 Total 700.0 0.24 0.48 a Units are for lead, as produced. ------- Table 11. Paniculate Emission Factors For Primary Slab Zinc Processing3 Process Roasting Multiple hearthb Suspension0 F/uidized beer Sinter plant Uncontrolled With cyclone' With cyclone and ESP1 Vertical retort Electric retort Electrolytic process Emission Uncontrolled Factor Controlled kg/Mg 113 1000 1083 62.5 NA NA 7.15 100 3.3 nanny Ib/ton kg/Mg Ib/ton 227 E — — 2000 E 48 2167 E — — 125 E - - NA 24. 1 48.2 NA 8.25 16.5 14.3 D — — 200 E — — 6.6 E — — Emission Factor Rating E D D 3 Based on quantity of slab zinc produced. NA = not applicable Dash = no data. b Averaged from an estimated 10% offeed released as paniculate emissions, zinc production rate at 60% of roaster feed rate, and other estimates. c Based on an average 60% of feed released as paniculate emission and a zinc production rate of 60% of roaster feed rate Controlled emissions based on 20% dropout in waste heat boiler and 99 5% dropout in cyclone and ESP. "Based on an average 65% of feed re/eased as paniculate emissions and a zinc production rate of 60% of roaster feed rate e Based on unspecified industrial source data. 'Data not necessarily compatible with uncontrolled emissions. M. Burnett and A. Minden are with A cur ex Corporation, Mountain View, CA 94O39. Dale L. Harmon is the EPA Project Officer (see below). The complete report, entitled "Nonferrous Industry Paniculate Emissions: Source Category Report, "(Order No. PB 87-140 935/A S; Cost: $24.95, subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA Project Officer can be contacted at: Air and Energy Engineering Research Laboratory U.S. Environmental Protection Agency Research Triangle Park, NC 27711 ------- United States Center for Environmental Research Environmental Protection Information Agency Cincinnati OH 45268 Official Business Penalty for Private Use $300 EPA/600/S7-86/049 OC00329 PS U S ENVIR PROTECTION AGENCY REGION 5 LIBRARY 230 S DEARBORN STREET CHICAGO IL 60604 ------- |