United States Environmental Protection Agency Air and Energy Engineering Research Laboratory Research Triangle Park, NC 27711 Research and Development EPA/600/SR-93/181 January 1994 &EPA Project Summary Emission Test Report, Field Test of Carbon Injection for Mercury Control, Camden County Municipal Waste Combustor D. M. White, W. E. Kelly, M. J. Stucky, J. L. Swift, and M. A Palazzolo In 1992, the U.S. Environmental Pro- tection Agency (EPA) conducted a para- metric testing to evaluate the injection of powdered activated carbon to con- trol volatile pollutants in municipal waste combustor (MWC) flue gas. This testing was conducted at a spray dryer absorber/electrostatic preciprtator (SD/ ESP)-equipped MWC in Camden County, New Jersey. The primary test objectives were to evaluate the effect of carbon type, feed rate, feed method, and ESP operating temperature on emissions of mercury (Hg) and chlori- nated dioxins and furans (CDD/CDF), and to assess the impact of carbon injection on the particulate matter con- trol performance of the ESP. Second- ary objectives were to examine the impact of carbon injection on emissions of other metals and volatile organic com- pounds (VOCs). This testing included operation of three different carbon in- jection systems and examined 16 dif- ferent SD/ESP and carbon injection system operating conditions. This test was conducted as a follow-on to an EPA- funded test program at a SD/fabric filter- equipped MWC that focused on the performance of carbon injection for con- trolling Hg emissions. The test results indicate that carbon in- jection upstream of a SD/ESP can achieve high levels (greater than 90%) of Hg and CDD/CDF reduction. Key system operat- ing parameters are carbon feed rate, carbon feed method, and ESP tempera- ture. No detrimental impacts on ESP performance were identified. The study also found that carbon injection does not have a significant impact on emis- sions of the other metals sought or of VOCs. This Project Summary was developed by EPA's Air and Energy Engineering Research Laboratory, Research Tri- angle Park, NC, to announce key find- ings of the research project that is fully documented in a separate report of the same title (see Project Report ordering information at back), Introduction In June 1987, the U.S. EPA's Office of Air Quality Planning and Standards (OAQPS) announced its intention to de- velop new air pollution rules for MWC facilities. The following fall, EPA's Air and Energy Engineering Research Laboratory (AEERL) and OAQPS began a compre- hensive field test and engineering assess- ment program to evaluate technologies for controlling MWC emissions. The field test program focused on the use of a lime spray dryer absorber and fabric filter baghouse (SD/FF) or a lime SD/ESP sys- tem for controlling MWC emissions. Regu- lations for large MWCs were proposed in late 1989 and finalized in 1991. In November 1990, the Clean Air Act Amendment (CAAA) required EPA to add Hg emission limits to the MWC standards. Under the direction of EPA, Radian Cor- poration prepared a technical memoran- dum summarizing the effectiveness of various technologies in controlling Hg emissions. Based on U.S. field tests and research in Europe and Canada, it was concluded that the control of Hg emis- sions in MWC SD/particulate matter (PM) Printed on Recycled Paper ------- control systems depends on the amount of carbon in the fly ash. Modern mass burn combustors, which typically contain relatively low amounts of carbon in their fly ash, exhibited Hg control efficiencies with acid gas scrubbers ranging from 0 to 40%. Refuse-derived fuel combustors, which contain substantially more carbon in their fly ash, had Hg control efficiencies exceeding 95%. In these applications Hg vapor does not condense but is adsorbed on carbonaceous particles that can be subsequently collected in PM control de- vices. Research and field tests in Europe indi- cated that powdered activated carbon can be used to enhance control of Hg emis- sions in SD/PM control systems. EPA- sponsored tests in 1991 at the Ogden Martin Systems of Stanislaus, Inc. (OMSS) MWC indicated that powdered activated carbon was effective in controlling Hg emissions in mass burn MWCs with SD/ FF systems. It was found that carbon feed rate is the primary factor affecting Hg con- trol. The OMSS testing also indicated that there are no significant differences in Hg control performance as a function of the physical characteristics of the carbon (origi- nal material, particle size, pore size, and density), the method of injection (as a dry powder or mixed with the SD's lime slurry), or the location of injection (economizer exit, SD inlet, and into the SD). However, it was not possible to determine how much of the Hg is removed by adsorption onto carbon particulate in the free stream with subsequent PM collection and how much Hg is removed by adsorption as the flue gas flows through the FF cake containing captured carbon. Because of uncertainties regarding the mechanisms of Hg capture by carbon in SD/FF systems, it is not possible to di- rectly translate the data collected at SD/ FF-equipped MWCs to units equipped with SD/ESP systems. Available U.S. data on SD/ESP-equipped MWCs indicated incon- sistent and often poor Hg control. Data on the collection of Hg by SD/ESPs is of interest because of the number of such systems already operating commercially, as well as the potential for retrofitting ex- isting ESP-only systems with SDs as needed for control of acid gas and or- ganic emissions. In addition, very little data are avail- able from either SD/FF- or SD/ESP- equipped MWCs on the effectiveness of carbon injection for reducing emissions of CDD/CDF and various VOCs. In 1992 EPA sponsored tests at the Camden County, New Jersey, MWC facil- ity to evaluate the use of activated carbon for controlling emissions in SD/ESP sys- tems. The Camden County and the OMSS tests were directed by AEERL. The report summarizes the objectives and results of the Camden County tests. Purpose of Tests The purpose of the Camden County tests was to evaluate the effectiveness of powdered activated carbon for reducing emissions of Hg, "other" metals, and trace organic emissions from mass burn MWCs equipped with SD/ESP systems. Specific objectives of the tests were to evaluate: The relationship of carbon feed rate, the inherent carbon in fly ash, and Hg capture; The effects of carbon injection on the control of "other" metals, CDD/ CDF, and VOCs; The effect of carbon injection rate and method (dry powder or slurried with lime) on Hg and CDD/CDF control; The effect of ESP operating tem- perature on Hg collection, and Whether there are long-term im- pacts of carbon injection on ESP performance in collecting PM and "other" metals. Test Design Description of Facility The Camden County MWC is owned and operated by Camden County Energy Recovery Associates, a subsidiary of Fos- ter Wheeler Power Systems, Inc. Located in Camden, New Jersey, it began operat- ing in 1991. The facility contains three identical mass-burn waterwall combustion units, designated as Units A, B, and C. Each unit is capable of burning 317 tonnes (350 tons) per day of municipal solid waste (MSW), and collectively they provide steam for two 17-MW turbine generators. A gen- eral schematic of a test unit showing car- bon injection and sampling locations is given in Figure 1. The air pollution control system on each combustor consists of a Deutsche Babcock SD and a Belco five-field ESP. The flue gas leaves the economizer, passes down through a vertical circular duct, through a 90-degree elbow, and through a horizon- tal circular duct before entering a cyclone. The cyclone separates coarse PM from the flue gas and distributes flue gas to six vertical flow tubes that connect to the base of the SD vessel. A two-fluid nozzle lo- cated in the top of each flow tube injects lime slurry up into concurrently flowing flue gas. The lime slurry flow can be con- trolled by stack sulfur dioxide (SO2) con- centration or it can be set to provide a fixed lime flow rate. Dilution water flow is controlled by the SD's exit gas tempera- ture. After leaving the SD, flue gas passes through an inverted U-shaped circular duct before entering a five-field ESP. During normal operation, only four of the ESP fields are in operation. Flue gas from each ESP is ducted into a separate flue in the stack. The stack contains four circular flues, one per operating unit, and one for a future unit. The process control systems include a Bailey Net 90 for the boiler, a separate control and data display system for the SD/ESP, and two separate continuous emission monitoring (CEM) data acquisi- tion systems. The CEM systems include extractive monitors for SO2 and oxygen (O2) at the economizer exit and monitors for O2, carbon dioxide (CO2), water (H2O), carbon monoxide (CO), total hydrocarbons (THCs), methane (CH4), SO2, hydrogen chloride (HCI), nitrogen oxides (NOX), and opacity in the stack. Test Matrix The Camden County MWC test project encompassed three distinct testing efforts and was conducted in two phases (see Table 1). Phase I concerned only Unit B. These tests, defined as Phase I-B tests, were used to select the carbon type and carbon feed rates to be used for the Phase II performance tests. The Phase II tests included two distinct efforts. The primary effort, conducted on Unit B (II-B tests), investigated the effects of key carbon in- jection system operating variables on Hg control efficiency. The other Phase II tests, conducted on Unit A (II-A tests), investi- gated the potential long-term impacts of extended carbon injection on ESP perfor- mance. Triplicate sampling runs were conducted for each test condition and one test condi- tion was completed during each test day Plant process instruments and CEM equip- ment were used to monitor combustor and SD/ESP operating conditions during each run. Phase I-B Tests. During Phase I-B tests, carbon was injected as a dry pow der into the flue gas duct just upstream or the SD (see Figure 1). The tests evalu ated Hg control levels for two carbon types and two carbon feed rates. Both of the tested carbons, Darco PC-100 and Darco FGD from the American Norit Company, were used during the OMSS tests. The first carbon (PC-100) was a thermally ac tivated, bituminous-coal-based carbon with medium surface area and high tamped density. The second carbon (FGD) was thermally activated from lignite and had a lower surface area, smaller average par tide size, and lower tamped density than ------- Legend A : Inlet Sampling Location B: Dry Carbon Injection Location C : Slurry Carbon Injection Location D : Outlet Sampling Location Stack I.D. Fan Electrostatic Spray Ash Conveyors Predpitator Dryer Absorber Figure 1. Schematic of the Camden County Municipal Waste Combustor. Table 1. Test Matrix-Camden County MWC, Spring 1992 Phase- Condition I-B1 I-B2 I-B3 I-B4 I-B5 II-B6 II-B7 II-B8 II-B9 II-B10 II-B11 II-B12 II-B13 II-A1 II-A2 II-A3 II-A4 II-A5 ESP Inlet Temperature °C(°F) 132(270) 132(270) 132 (270) 132 (270) 132(270) 177(350) 177(350) 132 (270) 132(270) 132 (270) 132 (270) 132 (270) 132 (270) 132(270) 132 (270) 132(270) 132 (270) 132 (270) Number of Operating ESP Fields 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 4 3 Carbon Type None FGD PC-100 PC-100 FGD None FGD FGD FGD None FGD FGD FGD None FGD FGD FGD FGD Carbon Feed Method None Dry Dry Dry Dry None Dry Dry Dry None Dry Slurry Slurry None Slurry Slurry Slurry Slurry Nominal Carbon Feed Rate kg/hr (Ib/hr) None 4.5(10) 4.5(10) 27(60) 27(60) None 23 (50) 11(25) 2.3(5) None 23 (50) 23 (50) 11 (25) None 23 (50) 23 (50) 23 (50) 23 (50) Sample Analytes' Hg, PM, %C Metals, PM, %C Hg, PM, %C Hg, PM, %C Hg, PM, %C Hg, PM, %C Metals, PM, %C Hg, PM, %C Hg, PM, %C Metals, PM, %C, CDD/CDF, VOC Metals, PM, %C, CDD/CDF, VOC Metals, PM, %C, CDD/CDF Metals, PM, %C Hg, Cd, Pb, PM, %C, PSD" Hg, Cd, Pb, PM, %C, PSD Hg, Cd, Pb, PM, %C, PSD Hg, Cd, Pb, PM, %C, PSD Hg, Cd, Pb, PM, %C, PSD • Metals: Ag, As, Ba, Be, Cd, Co, Cr, Cu, Hg, Mn, Mo, Ni, Pb, Sb, Se, 77, V " PSD: Particle size distribution ------- the coal-based carbon. The lower target carbon feed rate was 4.5 kg/hr (10 Ib/hr), which equates to a flue gas concentration of approximately 60 mg of carbon per dscm of flue gas1 and is approximately equal to the high carbon feed rate for tests conducted at OMSS. The higher tar- get carbon feed rate of 27 kg/hr (60 Ib/hr) is about 360 mg/dscm and was expected to achieve Hg removals in excess of 90%. During each run, simultaneous sampling was conducted at the economizer exit and in the stack for total PM and Hg using the multiple metals sampling train. The ports at the economizer outlet are located ap- proximately 2 equivalent duct diameters from the nearest upstream flow disturbance and 1.6 diameters from the nearest down- stream disturbance. The stack ports are located near the 62-m (205-ft) elevation in the 112-m (366-ft) stack. Each sampling run was 1 hour long.2 In addition, an EPA Method 5 type sampling train was oper- ated at the economizer exit to collect a daily composite sample of PM. The com- posite sample was then used to deter- mine the percent carbon in the fly ash caused by incomplete combustion. Both carbon types indicated similar lev- els of Hg control during the I-B tests. Thus, the cheaper Darco FGD was se- lected as the carbon for use in the Phase II tests. Phase II-B Tests. The Phase I I-B para- metric tests included eight test conditions for evaluating the impact of carbon feed rate, carbon feed method, and flue gas temperature on Hg control (see Table 1). During each run, simultaneous sampling was conducted at the economizer exit and in the stack for total PM and Hg using the multiple metals sampling train. During six of the test conditions (five from II-B and one from I-B), the sampling fractions col- lected by the multiple metals train were analyzed for 16 other metals. These met- als were antimony (Sb), arsenic (As), barium (Ba), beryllium (Be), cadmium (Cd), chro- mium (Cr), cobalt (Co), copper (Cu), lead (Pb), manganese (Mn), molybdenum (Mo), nickel (Ni), selenium (Se), silver (Ag), thal- lium (Tl), and vanadium (V). In addition, a Method 5 type sampling train was oper- ated at the economizer exit to collect a daily composite sample of PM for deter- mination of percent carbon in the fly ash. 1 Based onafluegas flow rate of75,000 dscm/hr. Unless otherwise noted, all flue gas flow rates used in this paper are corrected to standard conditions [20°C (68°F), 101.3 kPa (14.7 psia)] and all concentrations to 7% O2 in dry gas. 2 All run durations in this paper are actual sampling times and exclude times for port changes and resolving equipment problems. Except for the three test conditions dis- cussed below, each sampling run was 1 hour long. The testing also included sampling for CDD/CDF emissions during Conditions B10, B11, and B12, and for VOCs during Conditions B10 and B11. Each sampling run during these three test conditions was 2 hours in duration. Phase II-A Tests. Phase II-A tests were conducted to evaluate potential detrimental impacts on ESP performance due to carbon injection over an extended time period, and to assess the relation- ship between PM collection efficiency and Hg control. To satisfy these objec- tives, 5 days of sampling were conducted over a 12-day period on Unit A. Follow- ing an initial day of testing without car- bon injection to establish baseline performance, Darco FGD carbon was added to the lime slurry feed tank and continuously pumped into the SD. As shown in Table 1, the first 4 days of sampling were conducted with four ESP fields in service. These tests were run on the day prior to the start of carbon injec- tion and on the first, third, and eighth days after the start of carbon injection. After completion of testing on the eighth day, the fourth ESP field was turned off (the fifth field was off for all tests), thus result- ing in operation with only three fields. The fifth day of sampling was conducted after the unit had been operating with three fields for 4 days. This sampling schedule was designed to allow the ESP to reach equilibrium operation with three fields. These tests were conducted to evaluate the effects of carbon injection on smaller three-field ESPs. During each run, simultaneous sampling was conducted at the economizer exit and in the stack for total PM, Hg, Cd, and Pb using the multiple metals sampling train. Also, during each run, two eight-stage Andersen impactors were used to mea- sure the particle size distribution (PSD) of PM in the stack gas. The two PSD trains were run throughout each test day to col- lect sufficient PM for quantitative mea- surement of the weight gain by each impactor stage. In addition, a Method 5 type sampling train was operated at the economizer exit to collect a daily com- posite sample of PM for determination of percent carbon in the fly ash. The PM and PSD data provided a direct method of evaluating degradations in ESP perfor- mance that might be associated with car- bon injection. Carbon Feed Systems Carbon was fed to Units A and B by two different methods using three differ- ent injection systems. The testing on Unit B included injection of dry carbon and addition of carbon into a slurry mix tank installed just prior to the SD. Carbon was injected into Unit A by addition of carbon to lime slurry in the feed tank. The dry injection system consisted of a screw feeder and a pneumatic transport system. The carbon injection probe con- sisted of a 0.025-m (1-in.) pipe inserted in. the flue gas duct upstream of the SD (see Figure 1). The end of the probe was cut at a 45° angle, which faced downstream. Experiments conducted prior to the Phase I tests suggested that the cyclone removed little, if any, of the dry injected powdered carbon. Prior to the start of the test project, the carbon feed system was calibrated. The carbon feed rate was confirmed for each test by recording the amount of each car- bon addition and the time between each pair of refillings. At the end of each testing day, the carbon feed rate was adjusted to the tar- get level for the next day of testing. The feeder was then operated overnight at this feed rate to condition the SD/ESP prior to the start of the next day of testing. The second carbon feed system for Unit B involved addition of carbon to the lime slurry in a feed tank installed near the SD inlet. Estimated carbon retention time in the slurry with this system was about 10 minutes. Lime slurry was supplied to this small feed tank from the plant's existing slurry system. Carbon feed rates were determined in the same manner as the dry injection system, and the carbon was carried in the lime slurry to the SD. During the Phase II-A tests, carbon was added to the plant's lime feed tank during each slaking cycle. The average carbon injection rates were calculated from the amount of carbon added during each timed slaking cycle. The lime/carbon slurry mix- ture was injected into the reactor with the existing slurry feed through the atomiza- tion system. The carbon retention time in the slurry during these tests is estimated at 3 to 8 hours, with an average of ap- proximately 5 hours. Interpretation of Results Mercury A summary of key operating data and Hg test results is presented in Table 2 ------- Table 2. Summary of Test Conditions and Mercury Test Results Phase- Condition I-B1 I-B2 I-B3 I-B4 I-B5 II-B6 II-B7 II-B8 II-B9 II-B10 I-B11 II-B12 II-B13 H-A1 Run 1 2 3 AVG 4 5 6 AVG 7 8 9 AVG 10 11 12 AVG 13 14 15 AVG 10 11 12 AVG 13 14 15R AVG 16 17 18 AVG 19 20 21 AVG 25 26 27 AVG 28 29 30 AVG 34 35 36 AVG 37 38 39 AVG 1 2 3 AVG Carbon Type None FGD PC-100 PC-100 FGD None FGD FGD FGD None FGD FGD FGD None Injection Method None Dry Dry Dry Dry None Dry Dry Dry None Dry Slurry Slurry None ESP Inlet Temperature °C(°F) 132 (269) 131 (267) 128 (262) 130 (266) 134 (274) 130 (266) 135 (275) 133 (272) 129 (264) 133 (272) 134 (273) 132 (270) 129 (265) 143 (290) 144 (291) 139 (282) 135 (275) 136 (277) 128 (262) 133 (271) 176(348) 177(350) 176(349) 176(349) 178(352) 178(352) 173(344) 176(349) 131 (267) 128 (263) 128 (262) 129 (264) 130 (266) 130 (266) 129 (265) 130 (266) 132 (269) 130 (266) 126 (258) 129 (264) 133 (271) 134 (273) 132 (269) 133 (271) 132 (269) 132 (269) 135 (275) 133 (271) 130 (266) ' 128 (263) 129 (264) 129 (264) 136 (277) 132 (270) 134 (273) 134 (273) Carbon Injection Concentration mg/dscm 0 0 0 0 73 79 78 77 89 73 88 83 477 456 418 450 430 444 450 441 0 0 0 0 313 329 324 322 173 149 190 171 30 46 43 40 0 0 0 0 357 342 387 362 324 325 336 328 183 194 200 192 0 0 0 0 Total Carbon at Cyclone Inlet mg/dscm 79 79 79 79 154 160 159 158 154 138 153 148 579 558 520 552 534 548 554 546 74 101 55 77 387 429 418 411 305 276 306 295 111 141 129 127 83 98 91 91 506 504 505 505 385 368 403 385 233 265 248 249 100 86 198 128 Mercury Concentration at Inlet u.g/dscm 356 1363 711 810 972 593 835 800 593 639 586 606 491 440 512 481 680 820 644 715 365 249 349 321 964 506 778 749 545 455 525 508 485 957 463 635 663 433 384 493 626 635 664 642 299 521 300 373 382 377 974 578 268 430 610 436 Mercury Concentration at Outlet ng/dscm 175 210 54 146 296 63 149 169 134 29 102 88 21 14 17 17 9 13 12 12 301 177 261 246 107 22 59 63 40 23 24 29 103 170 124 132 388 279 207 291 20 16 16 17 50 77 69 65 78 81 158 106 121 290 322 244 Mercury Removal Efficiency % 50.8 84.6 92.4 75.9 69.5 89.4 82.2 80.4 77.4 95.5 82.6 85.2 95.7 96.8 96.6 96.4 98.6 98.4 98.2 98.4 17.5 28.9 25.2 23.9 88.9 95.6 92.4 92.3 92.7 95.0 95.4 94.4 78.8 82.2 73.2 78.1 41.5 35.6 46.1 41.0 96.8 97.4 97.7 97.3 83.2 85.3 77.0 81.8 79.7 78.5 83.8 80.7 54.9 32.6 47.2 44.9 (continued) ------- Table 2. (Continued) Phase- Condition II-A2 II-A3 II-A4 H-A5 Run Carbon Type 4 FGD 5 6 AVG 7 FGD 8 9 AVG 22 FGD 23 AVG 31 FGD 32 33 AVG Injection Method Slurry Slurry Slurry Slurry ESP Inlet Temperature °C(°F) 129 (265) 129 (265) 130 (266) 129 (265) 137(278) 132 (269) 142 (288) 137(278) 141 (285) 139 (283) 140 (284) 139 (283) 139 (283) 140 (284) 139 (283) Carbon Injection Concentration mg/dscm 344 346 343 344 402 356 386 381 442 391 417 269 280 249 266 Total Carbon at Cyclone Inlet mg/dscm 427 468 450 448 579 412 629 540 640 567 604 381 404 356 380 Mercury Concentration at Inlet ug/dscm 302 403 1412 706 530 458 690 559 643 816 730 335 295 364 331 Mercury Concentration at Outlet ug/dscm 55 78 261 131 43 108 156 102 49 90 70 40 51 52 48 Mercury Removal Efficiency % 81.9 80.7 81.5 81.4 91.9 76.4 77.4 81.9 92.3 89.0 90.7 88.0 82.6 85.6 85.4 Note: Paniculate matter was not measured at the Inlet during Phase I; therefore, carbon concentrations were estimated using the average PM inlet concentration for all Phase II-B tests. All concentrations are referenced to 7% O2 in dry gas at 20°C (68°F) and 101.3 kPa (14.7 psia). Test II-B7-15R was conducted due to possible problems caused by interruption of carbon feed toward the end of Test 11-87-15. The table includes data on carbon type, injection rate and method, ESP inlet tem- perature, total carbon concentration at the cyclone inlet, inlet and stack Hg concen- trations, and Hg removal efficiency. Impact of Carbon Type. The influence of carbon type was examined during Phase I-B tests with dry injection of lignite-based carbon (Conditions B2 and B5) and coal- based carbon (Conditions B3 and B4). Conditions B2 and B3 were conducted at a low carbon feed rate corresponding to approximately 80 mg/dscm of flue gas. Conditions B4 and B5 were conducted at a high carbon feed concentration of ap- proximately 450 mg/dscm. At the low carbon feed rate, the calcu- lated removal efficiency was 70 to 89% with the lignite-based carbon and 78 to 96% with the coal-based carbon. At the high carbon feed rate, the removal effi- ciency was 98 to 99% with the lignite- based carbon and 95 to 97% with the coal-based carbon. While the coal-based carbon appeared to be marginally better at the low feed rate, both carbons re- sulted in similar performances at the high injection rate. Because there was no clear distinction in the removal efficiency of these two carbons, the remaining tests were conducted using the more eco- nomical lignite-based carbon. The simi- larity in performance of these two carbons when injected as a dry powder is consistent with the results of the OMSS testing. Impact of Carbon Injection Rate. Fig- ures 2 and 3, respectively, present Hg removal efficiency and stack gas Hg con- centration as a function of carbon injec- tion rate for all Unit B tests with lignrte- and coal-based carbons. These figures also include all tests for Unit A and Unit B without carbon injection. The rectangular data points show the removal efficiencies and stack gas concentrations measured during individual runs conducted at an ESP temperature of approximately 132°C (270°F) and while injecting either dry lig- nite-based carbon or no carbon. The spe- cific test conditions are A1, B1, B2, B5, B8, B9, B10, and B11. Carbon injection concentrations for these tests ranged from 40 to 450 mg/dscm. These figures show that increased car- bon injection concentrations increase Hg removal and decrease stack gas Hg con- centration. Increased injection concentra- tions also decrease the variability in Hg reduction and stack gas Hg concentration between individual runs of the same test condition. These tendencies were also observed during the OMSS test program. However, the carbon feed rates at Camden County were significantly higher than at OMSS, where the highest feed rate of dry carbon corresponded to an injection con- centration of about 70 mg/dscm.10'12 (Note that the pulse-jet-cleaned FF for the OMSS test unit had a cleaning cycle of about 12 minutes; thus the carbon in the filter cake had a much longer average contact time with "free stream" Hg than carbon col- lected in an ESP.) For a 132°C (270°F) ESP inlet tem- perature and dry carbon injection concen- trations above 150 mg/dscm, Hg removals were 93% or greater and stack gas Hg concentrations were less than 50 (ig/dscm At higher injection rates, there were rela- tively small incremental increases in Hg reduction and decreases in stack gas Hg concentration. At these feed rates, the variability in Hg reduction between runs of a given test condition was 3% or less. At carbon feed rates of less than 150 mg/ dscm, the Hg removal efficiencies were noticeably lower and the run-to-run vari- ability between individual runs was as much as 20% during a single test condi tion. The greatest variation in Hg reduction and stack gas Hg concentration was ob- served during tests without carbon injec- tion, Conditions A1, B1, and B10. In particular, during Runs 2 and 3 of Condi- tion B1, removal efficiencies were 85 and 93%, nearly 40% higher than other runs with no carbon injection. Stack gas Hg concentrations during Runs 2 and 3 were 210 and 54 u,g/dscm, respectively. It was initially believed that these high Hg re- moval efficiencies reflected poor combus- tion conditions caused by high waste moisture content (it rained heavily for sev era! days preceding the B1 tests) and in the case of Run 2, high inlet Hg concen- trations. However, similar "wet waste" con drtions during the B10 tests did not result ------- 700-r -^ 80 ^ 70 1 I- 30 10 0 50 100 150 200 250 300 350 400 450 500 Injected Carbon (mg/dscm) Dry Carbon @ 270F A Wet Carbon @ 270F * Dry Carbon @ 350F Figure 2. Dependence of mercury reduction on carbon injection rate and method at 132°C (270°F) and177°C(350°F). 400 I 200- 100 50 *.-.- 50 JOO 750 200 250 300 350 400 Injected Carbon (mg/dscm) 450 500 | • Dry Carbon @ 270F A Wet Carbon @ 270F * Dry Carbon @ 350F Figure 3. Dependence of mercury concentration on carbon injection rate and method at 132°C (270°F) and 177°C (350°F) in abnormally high Hg captures. Review of the three previous quarterly Hg emis sion tests from Unit B shows reductions during three-run tests of 41 to 43%, 41 to 55%, and 30 to 73% (all based on EPA Method 101 A). These data suggest that Hg removals without carbon injection at Camden are typically between 30 and 55%, but removals can be either higher or lower. Impact of Inherent Carbon. Hg cap- ture in SD/PM control systems is believed to depend on the amount of inherent car- bon contained in combustor fly ash. To quantify the amount of unburned carbon present in the flue gas, a composite PM sample was collected at the economizer exit during each test condition and ana- lyzed for carbon content. The carbon lev- els measured during each day were between 1.1 and 2.2% of the dried sample weight. The percent carbon found in each daily sample was then multiplied by the measured PM loading at the economizer exit for each run on that day. The result- ing estimate of inherent carbon was then added to the concentration at which acti- vated carbon was injected to estimate the total carbon level in the flue gas (see Figure 4). Note that this approach pro- vides only a rough estimate of the total entrained carbon. Specifically, this ap- proach provides a single estimate of the PM's carbon content for each day, and any run-to-run variations in combustion conditions that could result in increased carbon levels during an individual run are not measured. Also the amount of carbon available for Hg absorption at location; downstream of the SD's inlet cyclone is overestimated. Visual inspection of cyclone catches showed a substantial number of large inherent carbon particles in the col- lected fly ash. As shown in Figure 4, the 30-55% re- duction in emitted Hg at 132°C (270°F) in the absence of carbon injection could be explained by the presence of approxi- mately 100 mg/dscm of unburned carbon associated with the combustor fly ash. The high levels of Hg capture obtained during test conditions B11 and B5 can be partially explained by the high levels of inherent carbon during these two condi- tions (2.2% during B11 and 1.9% during B5). At OMSS, the carbon content of the fly ash from the combustor (0.5-1.0%) was approximately half the level at Camden County, and the Hg reduction without car- bon injection was also approximately half the average Camden level (25%). Impact of Carbon Injection Method. The relationship between the carbon in- jection method and Hg removal and stack ------- 700- 90 80 70 60 QC 50- | 40 I 30 20 10 —sir 200 300 400 Total Carbon (mg/dscm) 500 600 Dry Carbon @ 270F A Wet Carbon @ 270F * Dry Carbon @ 350F Figure 4. Mercury reduction as a function of total carbon concentration in flue gas and carbon injection method at 132°C (270°F) and 177°C (350°F). gas Hg concentrations is shown in Fig- ures 2 and 3, respectively. At the medium carbon injection concentration (149 to 200 mg/dscm), Hg removal efficiencies were 92 to 95% with dry carbon injection (Con- dition B8) and 79 to 84% when the carbon was injected with the lime slurry (Condi- tion B13). For medium carbon injection rates, dry injection resulted in stack gas Hg concentrations ranging from 23 to 40 (ig/dscm, while slurry injection resulted in stack Hg concentrations ranging from 78 to 158 u,g/dscm. At the carbon injection concentrations >324 mg/dscm, Hg removal efficiencies were 97 to 98% with dry injec- tion (Condition B11) and 77 to 85% with slurried carbon (Condition B12). For these tests, the dry carbon injection test stack gas Hg concentrations ranged from 16 to 20 u,g/dscm, while the slurry carbon injec- tion test stack gas Hg concentrations ranged from 50 to 77 u,g/dscm. This observation is in contrast to the OMSS results, which found that feed method did not have a significant impact on Hg emissions and Hg removal. The cause of this difference is uncertain, but may be due to the different carbon type used or the type of PM control device. The carbon used at OMSS during slurry testing was coal-based, rather than lig- nite-based as used during slurry testing at Camden County. Also, the carbon col- lected in the filter cake during the OMSS test was retained on the bags for about 12 minutes and thus was probably dry during most of its contact time with flue gas, thus effectively functioning like dry carbon relative to Hg capture. In contrast, a very short period (on the order of 10 seconds) was available for the carbon to dry out in the ESP. Carbon retention time in the slurry on Unit A was estimated to be 3 to 8 hours, but only 8 to 10 minutes for Unit B. The carbon feed concentration during each of these condi- tions was approximately 360 mg/dscm. The Hg removal efficiency for Units A and B was very similar, with both units aver- aging 82%. It can be concluded that the decreased Hg adsorbency of carbon when mixed with slurry occurred in less than 8 to 10 minutes. Impact of ESP Temperature. Figure 5 shows the effects of ESP inlet tempera- ture and total carbon concentration on Hg removal efficiency and stack gas Hg con- centration. When operating without car- bon injection and an ESP inlet temperature near 132°C (270°F) [Conditions B1 and B10], Hg removals ranged from 36 to 92% and stack gas Hg concentrations ranged from 54 to 388 (ig/dscm. At the higher ESP temperature of 177°C (350°F) [Con- dition B6], the Hg removals were 18 to 29% and the stack gas concentrations were 180 to 300 |ig/dscm. At high total carbon concentrations (360 mg/dscm) and 132°C (270°F) ESP temperature (Condi- tion B11), Hg removals were 97 to 98%. At similar carbon feed rates, but an ESP inlet temperature of 177°C (350°F) [Con- dition B7], Hg removals were 89 to 96% and stack gas Hg concentrations were 22 to 107 u.g/dscm. These data suggest that the ability of carbon to absorb Hg is di- rectly related to flue gas temperature, but that, even at a relatively high ESP inlet temperature of 177°C (350°F), activated carbon injection results in high Hg reduc- tions. Impact of PM Control Efficiency. The PM control efficiency of the ESP aver- aged 99.8% or more for all test condi- tions. The PM concentrations in the stack ranged from 1.1 to 8.9 mg/dscm (0.0005 to 0.004 gr/dscf). These levels of PM con trol and emission did not exhibit any ap- parent relationship between PM control and Hg removal efficiency for the tests conducted at the Camden facility. Multlvariate Regression Analysis of Hg Control A stepwise multivariate regression analy sis was used to assess the statistical sig- nificance of individual process variables and to develop predictive equations for Hg removal efficiency and stack gas Hg concentration. These analyses identified three statistically significant process vari- ables influencing Hg control efficiency: car- bon feed rate, ESP inlet temperature, and carbon injection method. The analyses also identified four statistically significant pro- cess variables affecting stack gas Hg con centration: carbon feed rate, carbon injection method, ESP inlet temperature and inlet Hg concentration. Figure 6 shows the predicted stack gas Hg concentrations for the injected carbon concentrations for the best regression model based on an ESP operating tern perature of 132°C (270°F) and inlet Hg concentrations of 200, 500, 800, and 1,100 |ig/dscm. Note that most of the reduction in stack Hg concentration occurs at in jected carbon concentrations below about 100 mg/dscm. At injected carbon concen trations above this level, the stack Hg concentration decreases, but the reduc tion is much more gradual. Considering the degree of control by inherent fly ash carbon, the variations in the inlet flue gas Hg concentration, and the variation in re duction efficiency of the carbon injection process, complying with an Hg emission limit of 100 u,m/dscm at the Camden f acil ity would probably require injected carbon concentrations in the range of 150 to 200 mg/dscm. The absence of inlet Hg concentration as a statistically significant variable for predicting Hg removal efficiency is in con trast to the OMSS data and is believed tc reflect the difference in control capability ------- Mercury Reduction (%) 100 90 80 70 60 60 40 ~ 30 ~ 20 10 - n -•*!"• •m — J • * m * 100 200 300 400 Total Carbon (mg/dscm) 500 600 Dry Carbon @ 270F * Dry Carbon <§> 350F | Figun 5. Mercury reduction as a function of total carbon concentration at 132°C (270°F) and 177°C (350°F). 450 400 Inlet Mercury Concentration 1100\ig/dscm 800 \i.g/dscm 500 \jig/dscm . 200\ig/dscm 100 200 300 Injected Carbon (mg/dscm) 400 500 Figure 6. Regression lines for stack mercury concentration as a function of inlet mercury concentration and dry carbon injection rate at 132°C (270°F). of systems equipped with a FF versus an ESP. With a FF, carbon will adsorb Hg both while entrained in the flue gas and after it is collected in the filter cake. When inlet Hg levels vary (e.g., due to a short- duration spike in Hg concentration), the unsaturated carbon on the filter cake is able to adsorb additional Hg and to mod- erate the spike at the FF outlet. In this situation, the efficiency of the control sys tem (i.e., entrained carbon and filter cake) can increase for short periods. During these periods the outlet concentration is not strongly dependent on inlet concen tration until there is "breakthrough" of the filter cake carbon. The ability of the filter cake to buffer outlet Hg spikes in inlet Hg levels is similar to the ability of the excess sorbent in the filter cake to moderate fluc- tuations in inlet acid gas levels. With an ESP, most of the Hg reduction occurs while the carbon is entrained in the flue gas and is controlled by the likelihood of contact between carbon particles and Hg prior to the collection of carbon with the fly ash on the ESP plates. Once a carbon particle is collected on an ESP plate, the potential for contact with Hg is greatly reduced, because of both the removal of carbon from flue gas and the limited op- portunity for Hg in flue gas to contact carbon collected on plates of the ESP. In this case the Hg capture is limited by the total concentration of suspended "free stream" carbon, and the outlet Hg con centrations for a given carbon loading are highly dependent on inlet concentrations. Other Metals Flue gas concentrations of the 16 other metals in addition to Hg were determined during six test conditions (see Table 1) Five of these test conditions were con ducted at 132°C (270°F): no carbon injec- tion (B10), dry carbon injection at a low and a high feed rate (B2 and 611, respec tively), and slurry injection of carbon at a medium and a high feed rate (B13 and B12, respectively). The sixth test condi tion was conducted at 177°C (350°F) with dry carbon injection (B7). For Cd, Pb, As, Ba, and Cu, metals removal efficiencies exceeded 99% dur ing all test conditions. For Cr and Mn removal efficiencies exceeded 99% ex cept during the high temperature run (B7) and for Mn during the medium feed rate carbon-in-slurry test condition (B13). For Mo and Ni, removal efficiencies showed significant variability, ranging from a low of 72% for Mo during the high tempera- ture test condition up to 98%. Removal efficiencies for Sb, Be, Co, and V could not be precisely determined because their concentrations in the stack were below ------- their analytical detection limits. Removal efficiencies for Ag and Tl could not be estimated because concentrations of these metals were below their analytical detec- tion limits at both the inlet and outlet sam- pling locations. Considering the poor recovery of matrix spikes used for analyti- cal quality assurance, the data for Se were unacceptable and are not reported here. These data indicate that the 13 detected metals, with the possible exception of Mo, are emitted from the combustor primarily as PM and that emissions of these metals are controlled predominantly by the PM control device. There also appears to be an effect of ESP temperature on the con- trol of Cr, Mn, and Ni but, given the small size of the data set, this relationship may be due to random chance. Injection of activated carbon did not have a quantifi- able impact on emissions of any of the 13 detected metals, which were generally re- moved at high levels. Organic Compounds Economizer outlet and stack gas con- centrations of CDD/CDF were measured during Conditions B10 (no carbon injec- tion), B11 (dry carbon at 132°C [270°F]), and B12 (slurry carbon at 132°C [270°F]). During Condition B10 without carbon in- jection, the total CDD/CDF removal effi- ciency across the SD/ESP was 78 to 80%. During Condition B11 with a high injection concentration of dry carbon (360 mg/ dscm), the removal efficiency was 95 to 98%. During Condition B12 with a high injection concentration of carbon in slur- ried lime (330 mg/dscm), the removal effi- ciency was 96 to 97%. These data suggest that, unlike Hg, the CDD/CDF removal efficiency of dry and slurried carbon injec- tion was similar. As shown in Figure 7, stack gas con- centration of CDD/CDF was reduced from 40 to 60 ng/dscm without carbon injection to less than 7 ng/dscm for dry carbon injection and less than 13 ng/dscm for slurry injection. The higher stack CDD/ CDF levels during slurry injection of car- bon reflect the higher concentration of CDD/CDF measured at the economizer outlet during two of the Condition B12 runs of approximately 375 ng/dscm, com- pared to 130 to 220 ng/dscm for the other seven runs. The carbon injection concen- tration into slurry also averaged nearly 10% below that for dry carbon injection. The reduction of CDD/CDF emissions by carbon injection is consistent with Euro- pean field test results. Sampling for VOCs was conducted dur- ing Conditions B10 (no carbon injection) and B11 (dry carbon injection). There ap- CDD/CDF Concentration (ng/dscm) ou 50 40 30 20 10 0 ' ' * 1 1 1 1 No Carbon Dry Carbon Wet Carbon (II-B10) (II-B11) (II-B12) Figure 7. Stack CDD/CDF concentration with and without carbon injection into flue gas at 132°C (270°F). peared to be a reduction in the level of some compounds (carbon disulfide, benzene, chlorobenzene) across the SD/ESP and an increase in others (trichloro-fluoromethane, methylene chloride, toluene). Of significance to this study, there was no apparent impact of carbon injection on reduction of any of these compounds in the SD/ESP system. Acid Gases As noted in Description of Facility, above, various gaseous components in the flue gas were monitored during each test condition. Emissions of SO2, HCI, and NOx were monitored using the plant CEM system. The SCX data displayed a general in- crease in SO2 removal with increasing car- bon injection rate. However, the size of the data set and the scatter in the data are such that this apparent relationship may be due to random chance. No rela- tionship between carbon feed rate and HCI or NOX emissions was apparent. Impact of Carbon Injection on ESP Performance ESP performance test results from Unit A were evaluated using average PM, Cd, and Pb removal efficiencies and the per- cent of total PM less than 2 u.m during each test condition. There was no consis- tent change in any of these parameters during the first four test conditions, indi- cating that carbon injection did not alter ESP performance. During Condition A5, with the fourth ESP field out of service, there was no apparent change in PM re- moval efficiency. However, the removal efficiency for Cd and Pb decreased, and the percent of emitted PM less than 2 jim increased. These changes are consistent with the expected enrichment of volatile metals onto fine paniculate and the re- duced ability of the ESP to collect fine particulate when the fourth ESP field was out of service. Stack opacity, ESP volt- age, and ESP current remained within nor- mal operating ranges during the entire Unit A test period. Conclusions The collected data and results calcu- lated for the Camden County tests led to several conclusions: Hg reductions in excess of 90% were achieved by injection of dry carbon at both of the ESP operat- ing temperatures examined (132°C [270°F]and 177°C [350°F]). The most important process vari- ables affecting Hg emissions were carbon feed rate, carbon injection method, and ESP operating tem- perature. • The amount of unburned carbon present in fly ash played a signifi- cant beneficial role in controlling Hg emissions. The two carbons tested (Darco FGD and Darco PC-100) were similarly effective in controlling Hg emissions when injected as a dry powder. (No slurry tests were conducted with the coal-based PC-100.) • Injecting carbon (the lignite-based Darco FGD) with lime slurry was 10 ------- less effective in reducing Hg emis- sions than dry injection. This con- trasts with the results of the OMSS tests and may be due to the perfor- mance characteristics of an ESP versus a FF or to differences in carbon properties (Darco PC-100 was used in the OMSS tests). Multivariate regression analyses identified three statistically signifi- cant process variables influencing Hg control efficiency: carbon feed concentration, ESP inlet tempera- ture, and carbon injection method. The four significant process vari- ables which influence stack gas Hg concentrations are: carbon feed concentration, ESP inlet tempera- ture, carbon feed method, and inlet flue gas Hg concentration. Injecting carbon reduced stack emissions of CDD/CDF by over 75% so that CDD/CDF removals increased to 95% or more. How- ever, there was no apparent effect of carbon injection on emissions of VOCs. Emissions of metals other than Hg were primarily associated with PM, and their control was determined mainly by the efficiency of PM re- moval. A possible exception to this relationship was Mo. Carbon injec- tion had no apparent benefit on the emission control of these metals. Carbon injection had no discernible impact on the ESP efficiency in con- trolling PM. 11 &U.S. GOVERNMENT PRINTING OFFICE: 1994 - 550-0«7/80137 ------- D. White, W. Kelly, M. Stocky, J. Swift, and M. Palazzolo are with Radian Corp., Research Triangle Park, NC 27709. James D. Kilgore is the EPA Project Officer (see below). The complete report, entitled "Emission Test Report, Field Test of Carbon Injection for Mercury Control, Camden County Municipal Waste Combustor," (Order No. PB94-101540; Cost: $27.00; 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 Environmental Protection Agency Center for Environmental Research Information Cincinnati, OH 45268 Official Business Penalty for Private Use $300 BULK RATE POSTAGE & FEES PAID EPA PERMIT No. G-35 EPA/600/SR-93/181 ------- |