74-LIM-3B (REPORT NUMBER) AIR POLLUTION EMISSION TES WOODVILLE LIME AND (PLANT NAME; CHEMICAL COMPANY WOODVILLE, OHIO (PLANT ADDRESS) U. S. ENVIRONMENTAL PROTECTION AGENCY Office of Air and Water Programs Office of Air Quality Planning and Standards Emission Standards and Engineering Division Emission Measurement Branch Research Triangle Park, N. C. 27711 ------- PEDCo-EN VI RON MENTAL SUITE13 ATKINSON SQUARE CINCINNATI, OHIO 45246 513 1-7-7 1-433O EMISSION TESTING REPORT EPA REPORT 74-LIM-3-B WOODVILLE LIME AND CHEMICAL CO, WOODVILLE, OHIO Contract No. 68-02-0237 Task 26 Submitted by: PEDCo-Environmental Specialists, Inc, 13 Atkdnson Square Cincinnati, Ohio 45246 Prepared by: W. G. DeWees Richard W. Gerstle, P. E, September 16, 1974 ------- 1. TABLE OF CONTENTS Page II. 'INTRODUCTION 1 III. SUMMARY OF RESULTS 3 IV. PROCESS DESCRIPTION 9 V. LOCATION OF SAMPLING POINTS 12 VI. PROCESS OPERATION & TEST CONDITIONS 14 VII. SAMPLING AND ANALYTICAL PROCEDURES 19 A. PARTICULATE RESULTS AND EXAMPLE CALCULATIONS B. GASEOUS RESULTS AND EXAMPLE CALCULATIONS C. VISIBLE EMISSIONS RESULTS D. OPERATING RESULTS E. FIELD DATA F. SAMPLE IDENTIFICATION LOG G. LABORATORY REPORT H. SAMPLING EMTHODS I. TEST LOG J. RELATED REPORTS K. PROJECT PARTICIPANTS L. SUMMARY OF TESTING COSTS ------- II. INTRODUCTION Under the Clean Air Act of 1970, as amended, the Environ- mental Protection Agency is charged with the establishment of performance standards for stationary sources which may contri- bute significantly to air pollution. A performance standard is based, on the best emission reduction systems which have been shown to be technically and economically feasible. In order to set realistic performance standards, accurate data on pollutant emissions must be gathered from the stationary source category under consideration. Woodville Lime and Chemical Co. in Woodville, Ohio, was designated as a possible representative well-controlled stationary source in the lime production industry and therefore was selected for an emission testing program. The process under investigation in this test series was operation of the No. 1 lime kiln at the Woodville plant, from which emissions are controlled by a cyclone in series with a Buell electrostatic precipitator. Preliminary tests were performed during the week of May 20, 1974, to ascertain composition and velocity of the gas stream and to observe visible emissions. The emission test program was conducted from July 8 to 10, 1974; on three test runs. Sampling was done at the kiln stack to determine concentrations of filterable and total particulate, ------- oxides of nitrogen, and sulfur dioxide. Determinations of moisture content and dry molecular weight were performed simultaneously. Samples of the kiln feed, kiln product, kiln fuel, and effluent dust from the ESP unit were collected for calculation of a sulfur balance. In addition, visible emissions were recorded by two certified observers during this time. Because of difficulties with process operation and above-normal production rates, further tests were scheduled for August 5, 1974. In the interim between test periods the kiln was shut down, at which time.the ESP was cleaned and inspected. ------- III. SUMMARY OF RESULTS Data on particulate emissions from the lime kiln are summarized in Table 1. Emissions of filterable particulate, as measured by the probe and filter catch, averaged 9.77 pounds per hour at a concentration of 0.041 grain per DSCF. Total particulate emissions averaged 18.3 pounds per hour at a concentration of 0.077 grain per DSCF. Emissions of filterable particulate were higher in the first two tests than in the third. This can probably be attributed to discon- tinuity in process operations and to problems with control equipment, described in Section IV, "Process Operation". Because of these difficulties, the emissions data reported in this report are considered questionable with respect to being representative of a well-controlled lime-producing process. Data on oxides of nitrogen emissions are summarized in Table 2. These data show an average concentration of 339 ppm by volume and an hourly emission rate of 67.7 pounds per hour of N02. Data on sulfur dioxide emissions are summarized in Table 3. These data show an average concentration of 44.5 ppm by volume and an hourly emission rate of 12.0 pounds per ------- Table 1. SUMMARY OF PARTICULATE DATA Run Number Date Volume of Gas Sampled , DSCFa Average Stack Temperature , °F Percent Moisture by. Volume , % Stack Volumetric Flow Rate, DSCFM Stack Volumetric Flow Rate , ACFMC Percent Isokinetic Unit Production Rate, ton/hr Particulates - probe, bypass, and filter catch mg gr/DSCF gr/ACF Ib/hr Ib/ton Particulates - total mg gr/DSCF gr/ACF Ib/hr Ib/ton 1 7/8/74 237.923 621 11.3 27619 64393 102.9 781.1 0.051 . 0.022 12.0 1704.6 0.111 0.047 26.2 3_ 7/9/74 239.642 669 12.1 27390 67296 104.5 718.9 0.046 0.019 10.9 989.9 0.064 0.026 15.0 5_ 7/10/74 248.641 674 11.4 28658 70330 103.6 417.0 0.026 0.011 6.4 Vs 889.3 0.055 0.022 13.6 Avg'. 242.07 655 11.6. 27889 67340 140 639 0.041 0.017 9.77 ; 1194.6 0.077 0.032 18.3 Dry standard cubic feet at 70°F, 29.92 in Hg. b Dry standard cubic feet per minute at 70°F, 29.92 in. Hg. Actual.cubic feet per minute. ------- Table 2. SUMMARY OF OXIDES OF NITROGEN DATA NOx Test No. Date, 1974 Time, 24 hour clock Flow Rate, DSCFM3 Sample Volume , ml Milligrams of NO- NOX Concentration, N0x Ib/hr Average ppm Ib/hr A 7/8 1748 27619 1457 0.83 ppm 299 58.9 B 7/8 1848 27619 1521 0.672 232 45.6 C 7/8 1951 27619 1519 0.953 329 64.8 299 D 7/8 2048 27619 1495 0.957 336 66.1 58.85 E 7/9 915 27390 1554 0.976 330 64.4 F G 7/9 7/9 1015 1115. 27390 27390 1549 1487 0.934 1.034 316 364 61.8 . 71.3 339.75 66.45 H 7/9 1215 27390 1522 1.014 349 68.3 I 7/10 920 28658 1602 1.093 358 . 73.2 J K 7/10 7/10 1033 1130 28658 28658 1938 1616 1.169 1.349 316 438 64.7 89.5 380 77.67 L 7/10 1230 28658 1660 1.290 408 83.3 Average 339.58 67.66 (jt a) Dry standard cubic feet per minute, corrected to 70° and 29.92" Hg as obtained during particulate test runs. ------- Table 3. SUMMARY OF SULFUR DIOXIDE DATA Test No. Date, 1974 Flow rate,DSCFMa Sample volume, DSCFa S02 in sample, grams SO- emissions, Ib/hr S02 concentration, ppm by volume 2 7/8 27619 166.917 0.867 19.1 70.-2 4 7/9 27390 165.549 0.130 2.42 10.6 6 Avg. 7/10 28658 166.705 0.649 14.4 12.0 52.6 44.5 a) Dry standard cubic feet at 70°F 29.92 in. Hg. ------- hour of sulfur dioxide. Visual determination o-f the opacity of emissions from the lime kiln exit stack was performed independently by two PEDCo personnel. Data on opacity measurements are summarized in Table 4. The average opacity was less than 5 percent in all tests. A period of high emissions occurred, however, for about 1 minute in the first test, during which opacity levels exceeded 20 percent. Failure of a field in the electro- static precipitator caused the discontinuity,.with the result that the opacity values are not considered typical of those occuring with well-controlled lime-production operations. During sample recovery on test 1, the probe glass liner tip was found to be broken. This test was therefore not representative of true emissions. Because of the higher than expected opacity and various process problems, this test series was terminated before enough measurements were obtained to provide representative results. ------- No. Date Table 4. SUMMARY OF VISIBLE EMISSION DATA ' ! 1 7/8/74 ' 7/9/74 Obs. 1 . Obs. 2 . Obs. 1 . Obs. 2 Interval of Observations start -. -End Duration of Observation, min Total No. of Readings No. of Readings Unobservable No. of Readings @ 0% Opacity 5% .10% ' 15% 20% 25%. 30% ' . 35% 40% 45% . 50% Percent Readings Unobservable Percent Readings @ 0% Opacity 5% 10% 15% 20% Percent Readings Exceeding 20% 24-hour clock start and end times b Excluding the time that readings were not recorded'for period of observation. c Readings recorded at 15-second intervals unless otherwise noted. Observer 1 - R. S. Amick Observer 2. - w. G. DeWees 8 5. 7/10/74 Obs..1 , Obs. ? 1715 2124 247 988 0 986 2 ^^ _ » ^ _ _ _ _ 0 99.8 0.2 - _ 1713 2112 228 912 . 10 711 184 7 _ _ __ M _ 0.8 78.0 20.2 - . _ 840 1245 245 980 0 . 914 34 26 3 3 _ _ _ . 0 93.3 3.5 2.6 0.3 0.3 . 843 .1235 233 932 154 174 597 7 _ » » ^ , _ _ _ M 16 . 5 18.7 64.1 0.7 - _ 820 1252 272 1088 0 1061 21 5 1 H _ «. _ 0 97.5 1.9 0.5 0.1 _ 838 1239 212.5 850 0 782 66 1 1 ^ mu , ^^ ^ _ _ 0 92.0 7.8 0.1 0.1 _ ------- .IV. PROCESS DESCRIPTION . Limestone consisting primarily of calcium carbonate or combina- tions of calcium and magnesium carbonate with varying amounts of impurities is quarried at the Woodville Plant. The limestone is calcined or burned to form lime, commonly divided into two basic pro- ductsquicklime and hydrated lime. Calcination expels carbon dioxide from the raw limestone, leaving calcium oxide (quicklime). With the addition of water, calcium hydroxide (hydrated lime) is formed. The basic processes in production are: (1) quarrying the lime- stone raw material, (2) preparing the limestone for kilns by crushing and sizing, (3) calcining the limestone, and (4) optionally processing the quicklime further by additional crushing and sizing followed by hydration. The majority of lime is produced, in rotary kilns which can be fired by coal, oil, or gas. Rotary kilns have the advantage of producing high production per man-hour and a more uniform product. However, they do require higher capital investment and unit fuel costs than most vertical kilns. The Woodville Lime and Chemical plant has two rotary kilns each equipped with a Buell electrostatic precipitator. The kilns are almost identical. The feed for both is a dolomitic stone, quarried on the site and fed in sizes ranging from 1 inch to 2 1/4.inches at a rate of about 700 tons per day. There is no ------- preheater. Normally the kiln is fueled with a mixture of 95 percent Number 6 fuel oil .and 5 percent natural gas. Both kilns have two heat transfer sections, each 20 feet long. The product, about 350 tons per day, is,cooled in a Neims cooler before storage. There is no product crushing, but undersize material is separated and returned to the kiln. The majority of the product.is used in the steel industry, mostly in basic oxygen furnaces; none of the product is hydrated. The electrostatic precipitator on kiln Number 1 was put in operation in July 1971. In this kiln the main process fan is located before the ESP, with a cyclone before the fan to reduce fan blade erosion. The precipitator on kiln Number 2 was put in operation in December 1973. The main process fan is after the ESP and there is no cyclone. In both systems the inlet gas to the precipitators is cooled to about 600°F with a combination of water injection and/or tempering air. Each precipitator has 28,800 square feet of collecting surface area, which includes one cell and two fields; design gas velocity is 1.5 feet per second and treatment time, 10.0 seconds. The plant manager reported that an earlier emission test showed exit loadings of less than 0.005 grain per dry standard cubic foot. At present the dust collected from the precipitators is disposed of in the quarry... It is expected that in the future the 10 ------- dust will be granulated and used as a component of dry mix fertilizers that are blended in another part of the complex. At the time of the initial plant inspection (February 8, 1974) the precipitators were working satisfactorily and had been very well maintained. The plant is representative of modern design; raw materials and products are typical of those in the industry. 11 ------- V. LOCATION OF SAMPLING POINTS Figure 1 shows the sampling ports and sampling points used in the No. 1 lime kiln exit stack. The sampling ports were located in a 63.5-inch inside-diameter vertical stack, 4 feet (0.75 diameter) from the stack exit, and 12 feet (2.26 diameters) from the nearest downstream disturbance. In order to meet the sampling requirements of Methods 1 and 5 of the Federal Register, Vol. 36, No. 247, it was necessary to install a stack extension on the ESP exhaust outlet. Forty-eight traverse points (24 along each of two perpendicular diameters) were used as described in the Federal Register Method 1. Additional sampling points in the existing stack at a lower site were used for some of the gas sampling.. 12 ------- TOP VIEW A. 45' 24'- ScoffolcJing Edge ol roof w'l 1 1 CROSS SECTION I S All Dimensions in Fool Aro Approximate ELEVATION Figure 1. Test Site-No. 1 Kiln Precipitator Outlet. 13 ------- VI. PROCESS OPERATION & TEST CONDITIONS Before the test series began, EPA engineers had decided to conduct tests at the Woodville plant only during periods in. which opacity of visible emissions from the kiln stack was in the range of 0 to 5 percent. This range had been described as typical of opacities during operation of the No. 1 kiln and was judged to be typical of those occurring in a well-controlled lime-producing plant. Although plant operations appeared to be normal and preliminary readings indicated 0 to 5 percent opacity values, several problems developed during the first day of testing, July 8,1974. After about 3 hours of testing, PEDCo's team of opacity readers stopped the tests at 8:22 p.m. because opacity values were exceeding the 5 percent limit. Testing was resumed at 8:27 p.m. and continued until 9:13 p.m., when the "A" field of the kiln's electrostatic precipitator malfunctioned, probably because of overload. Sampling was resumed at 9:16 p.m., when the opacity values again dropped to the 0 to 5 percent range. The first test was completed at 9:29 p.m. The second test was started on July 9 at 8:41 a.m. Opacities of visible emissions ranged between 0 and 5 percent 14 ------- throughout the entire test sequence. The test was completed at 12:48 p.m., and because no problems were encountered in sampling or process operation the emissions were considered representative of those occurring normally. After completion of the second test, plant operators performed a routine cleaning operation, shutting down a fan on the inlet to the ESP for removal of adhering dust. The fan was not re-started after cleaning, however, and opacity readings during the afternoon ranged between 10 and 15 percent. The third test, therefore, was not begun until the following day. Testing was resumed at 8:24 a.m. on July 10. Operations appeared normal except for a heavy load in the kiln, as evidenced by the .ampere meter on the kiln-drive motor.. Opacity readings ranged from 0 to 5 percent. Sampling was hampered, however, by blockage in the silica gel impinger, which was replaced several times. As testing progressed, the opacity readers reported an increasing number of 5 percent readings, with occasional 'puffs' as high as 10 percent. Observations .of the plume were difficult because of cloudy skies. Test No. 3 was completed at 12:55 p.m. Operating variables for the three test runs are summarized in Table 5,. and sulfur contents of the various process streams are shown in Table 6. A fourth test, intended to provide values to replace those obtained in Test No. 1, was started at 3:00 p.m. July 15 ------- Table 5. SUMMARY OF OPERATING VARIABLES Date Particulate Test No. Stone Feed Rate, ton/hra Oil Rate, gal/hr Firing Zone Temp, °F Mid Kiln, Temp, °F Kiln Feed End Temp, °F Before ESP Temp, °F Stack Temp, °F ELECTROSTATIC PRECIPITATOR DATA "A" Field Primary current, amps Primary voltage, volts Precipitator current, amps "B" Field Primary current, amps Primary voltage, volts Precipitator current, amps 7/8/74 322 2620-2650 1460-1465 1020-1040 683-700 660-675 39-50 250-275 0.20-0.30 41-55 240-260 0.27-0.35 7/9/74 3 f ' ' ^ I 356 2600-2650 1450-1475 10'00-1035 685-700 660-690 37-46 250-265 0.19-0.23 50-54 240-250 0.28-0.30 7/10/74 5 375 2590-2620 1470-1520 1050-1080 700-725 670-700 48-61 250-270 0.20-0.32 53-61 240-250 0.32-0.37 a) Obtained by multiplying indicated tonnage by (see Appendix D). 16 ------- Table 6. SULFUR CONTENT OF KILN, FUEL OIL, FEED ROCK, PRODUCT AND EFFLUENT. DUST. Sample #1 ESP Col. Dust #1 ESP Col. Dust #1 ESP Col. Dust #2 ESP Col. Dust #2 ESP Col. Dust #2 ESP Col. Dust #1 Stone Feed #1 Rock Feed #1 Rock Feed #1 Rock Feed #2 Stone Feed #2 Rock Feed #2 Rock Feed #2 Kiln Product #1 Lime Product #1 Lime Product #1 Lime Product #2 Lime Product #2 Lime Product #1 Fuel Oil #1 Fuel Oil #2 Fuel Oil #2 Fuel Oil #2 Fuel Oil #1 Fuel Oil Date 7/8/74 7/9/74 7/10/74 7/8/74 7/9/74 7/10/74 7/8/74 7/9/74 7/10/74 7/10/74 7/8/74 7/9/74 7/10/74 7/9/74 7/8/74 7/9/74 7/10/74 7/8/74 7/10/74 7/9/74 7/8/74 7/9/74 7/10/74 7/8/74 7/10/74 Time 1830 1015 0800 2030 1255 1030 1750 1100 1700 1000 2036 1230 1300 1300 1720 0930 1000 2030 1230 0930 1900 1230 1230 2030 1100 Sulfur Content % by weight 0.9 1.32 1.28 0.78 1.16 .1.64 0.02 0.07 0.06 0.07 0.14 0.04 0.04 0.01 0.07 0.04 0.02 0.06 0.07 1.75 2.26 1.7 0.875 3.22 2.26 17 ------- 10. Except for the heavily loaded kiln, process operations appeared normal. Because opacity readings rose to the 15 to 20 percent.range, testing was stopped at 4:30 p.m. Cleanup operations later revealed that the sampling probe was broken. The values obtained in this test were therefore discarded, and further sampling was scheduled for the following day. On-the morning of July 11, however, stack opacity values were again ranging between 5 and 10 percent. Although plant personnel tried several variations in kiln operation, the high opacity readings persisted throughout the day and evening. A reading at 10:30 p.m. gave values between 20 and 25 percent. At 6:00 a.m. on July 12, opacity readings still ranged between 5 and 10 percent. Personnel of the Woodville plant, EPA, and PEDCo agreed that the kiln should be shutdown briefly for inspection. Examination of the ESP revealed that several charge plates were covered with about 1 inch of a sticky substance, which prevented the dust particles in the effluent from receiving the positive charge and thus reduced collection efficiency. It was estimated that cleaning of the plates would require shutdown of the kiln for a week or so. A shutdown was scheduled for the week of July 15 to allow cleaning of the ESP, rebricking of certain kiln sections, and routine periodic maintenance. Further emissions testing was to be conducted shortly after resumption of kiln operation. 18 ------- VII. .SAMPLING AND ANALYTICAL PROCEDURES Sampling procedures were designated by EPA. Analyses of collected samples were performed by PEDCo. Appendix H presents detailed.sampling and analytical procedures. Velocity and Gas Temperature Gas velocities were measured with a calibrated type S pitot tube and inclined draft gage. Velocities were measured at each sampling point across the stack diameter to determine an average value according to procedures described in the Federal Register - Method 2. Temperatures were measured with the use of a thermocouple. Molecular Weight A 4-hour integrated sample of the stack gases was collected during test 1 by pumping the gas into a Tedlar plastic bag at the rate of approximately 0.005 CFM. This bag sample was then analyzed with an Orsat analyzer for C02, 02, and CO as described in the Federal Register, Method 3. Particulates Concentrations of particulate matter in stack gases were 2 measured by Method 5 as described in Federal Register. A rigid train consisting of a heated glass-lined probe, a 3-inch diameter 1) Federal Register, Vol. 36, No. 247, December 23, 1971. 2) Federal Register, Vol. 36,. No. 159, August 17, 1971. 19 ------- glass-fiber filter, and a series of Greenburg-Smith impingers was used for particulate sampling, as shown in Figure 2. Sampling was conducted under isokinetic conditions by monitoring stack-gas velocity with a pitot tube and adjusting the sampling rate accordingly. The particulate sample was recovered by triple-rinsing the nozzle, probe, cyclone by-pass, and front half of the filter holder with acetone into a glass container. The back half of the filter holder, impingers, and connecting tubes were rinsed with distilled water and the washings placed in a glass container with. the impinger contents. These components were then triple-rinsed with acetone into another glass container. The filter was placed in a separate container. Blank samples of water and acetone were also taken. NO x Nitrogen oxides were collected in evacuated 2-liter flasks containing 25 ml of a dilute sulfuric acid/hydrogen peroxide absorbing solution. The sampling and analytical procedure was as described in Method 7 of the Federal Register except that the final flask vacuum was read immediately after sampling. S02 Sulfur dioxide sampling procedures followed those described in Method 6. However, due to the low expected concentrations, 1) Federal Register, Vol. 36, No. 247, December 23, 1971. 20 ------- FILTER NJ HEATED GLASS PROBE THERMOMETER STACK WALL HEATED I SECTION - MANOMETER I | ' / SILICA GEL-^I | I_LOO_FLL_ 0£_ WAT ER j THERMOMETERS UMBILICAL CORD CALIBRATED ORIFICE CONTROL VALVES VACUUM GAUGE Hh MANOMETER- I Figure 2. Particulate Sample Train ------- larger sampling .equipment was used. Flue gas was passed through a set of Greenburg-Smith impingers at a rate of approximately 0.8 cubic foot per minute. The first impinger contained 150 ml of 80 percent isopropanol; the second and third impingers contained 100 ml each of 3 percent hydrogen per6xide/water solution. After sampling, ambient air was passed through1the train for 10 to 15 minutes. The isopropanol solution was discarded,, and the peroxide solution rinsed into a glass container. The hydrogen peroxide solution was titrated with barium chloride, using a Thorin indicator as described in Method 6. Visible Emissions <» Visible emissions were determined according to procedure in Method 9. Readings were difficult to determine at times due - to trucks loading and unloading ESP dust and quarry rock in the vicinity of either the ESP unit or the observer and the light colored plume against an overcast and partly cloudy sky caused poor distinction. In addition, certain ESP rappers set up a visible emission condition (puffs) that read approximately 5 to 10 percent opacity for about 2 to 3 seconds every cycle. Sulfur Analysis Solid samples were analyzed using Standard Methods of Chemical Analysis of Limestone, Quicklime and Hydraded Lime, C25-67, A.S.T.M. Standards, Part 9, Cement; Lime; Gypsum, 1972, American Society for Testing and Materials, Philadelphia, Pa. 22 ------- Fuel oil samples, were analyzed using Standard Method of Test for Sulfur in Petroleum Products by the Bomb Method/ D 129-64, A.S.T.M. Standards, Part '17, Petroleum Products - Fuels, Solvents, Burner Fuel Oils, Lubricating Oils, Cutting Oils, Lubricating Greases, Hydraulic Fluids, 1972, American Society for Testing Materials, Philadelphia, Pa. 23 ------- |