EPA-650/2-73-031 October 1973 ENVIRONMENTAL PROTECTION TECHNOLOGY SERIESEPA-650/2-73-031 EFFECTIVENESS OF SELECTED FUEL ADDITIVES IN CONTROLLING POLLUTION EMISSIONS FROM RESIDUAL-OIL-FIRED BOILERS by D.W. Pershing, G.B. Martin, E.E. Berkau, and R.E. Hall Control Systems Laboratory National Environmental Research Center Research Triangle Park, North Carolina 27711 ROAP No. 21ADG Program Element No. 142014 Prepared for NATIONAL ENVIRONMENTAL RESEARCH CENTER OFFICE OF RESEARCH AND DEVELOPMENT U.S. ENVIRONMENTAL PROTECTION AGENCY RESEARCH TRIANGLE PARK, NORTH CAROLINA 27711 October 1973This report has been reviewed by the Environmental Protection Agency and approved for publication. Approval does not signify that the contents necessarily reflect the views and policies of the Agency, nor does mention of trade names or commercial products constitute endorsement or recommendation for use. iiCONTENTS Acknowledgements Summary Introduction The Additives Trimex PACE KAP Glo-Klen Sodium Carbonate Test Facility The Boiler Injection System Standard Fuel Analytical Procedures Test Plan Trimex PACE, KAP, Glo-klen Sodium Carbonate Discussion of Results: SO, Baseline Characterization Trimex PACE itiCONTENTS (Cont. ) KAP. Glo-Klen Sodium Carbonate Discussion of Results: Other Emissions Unburned Hydrocarbons Carbon Monoxide Nitric Oxide Metallic Conclusions Bibliography iv 27 27 32 35 35 36 35 39 41Table No. LIST OF TABLES Title Chemical Analysis of Additives Chemical Analysis of Standard Test Fuels Trimex Test Plan Test Plan for PACE, KAP, and Glo-Klen Results of Trimex Testing Results of Particulate Analysis--Trimex Analysis of Boiler Deposits (Trimex) Results of PACE Testing Results of Particulate Analysis--PACE Results of KAP Testing Results of Particulate Analysis--KAP Results of Glo-Klen Testing Results of Particulate Analysis--Glo-klen Additional Uncontrolled Metallic Emissions Resulting from the Use of Trimex in a 1000-MW Boiler LIST OF FIGURES tle Schematic of Test System Analytical System Sulfur Oxides Sampling Apparatus (Wet Chemical) Photographs of Test Boiler After Trimex Testing Page 12 4ACKNOWLEDGEMENTS The authors wish to gratefully acknowledge the help of Messrs. Nelson L. Butts and Daniel S. Watkins in carrying out the experimental aspects of this program and of John H. Wasser in conducting the boiler characterization. vi‘SUMMARY The purpose of this study was to experimentally evaluate the effectiveness of four additive materials in controlling pollutant emissions from fossil fuel combustion. The additives considered were Trimex, PACE, KAP, and Glo-Klen. Each material was carefully examined in a highly instrumented package boiler over the range of typical operating conditions (e.g., combustion intensity and residence time) for industrial and utility systems. The test results show that Trimex, PACE, KAP, and Glo-Klen do not reduce emissions of S0,, NO, CO, or UHC under any condition tested. Based on these test results, the boiler operating problems, and the possibility that use of these materials might create potentially harmful new emissions, none of the additives can be recommended as a means of controlling pollutant emissions.INTRODUCTION For many years numerous companies have marketed a variety of fossil-fuel additives purported to be able to improve or change the combustion of oi] and/or coal in some beneficial fashion. In an effort to determine the effect of these compounds on pollutant emissions, the U. S. Environmental Protection Agency* has undertaken a detailed evaluation. The work began several years ago with a literature survey and a series of contacts with individuals knowledgeable in the use of fuel additives for specific situations. A distillate oi] testing program followed: some 200 different materials were evaluated for their effect on light oi] emissions. The results of the work showed that although a few proprietary metallic additives substantially reduced soot emissions, in no case did any additive reduce the emissions of carbon monoxide, unburned hydrocarbons, or nitrogen oxides from distillate oi] combustion. To evaluate the effect of these materials on SO, emissions and to establish the potential of other new materials, a continuing residual oi] and coal program was initiated. While the bulk of the detailed testing will be conducted by an outside contractor, the Combustion Research Section has conducted an initial in-house evaluation of the most widely publicized materials: Trimex, PACE, KAP, and Glo-Klen. *Combustion Research Section, Clean Fuels & Energy Branch, Control Systems Laboratory, Office of Research and Development, National Environmental Research Center/RTPThis document is a report of the effectiveness of these new materials in controlling pollution emissions from residual oi1 combustion. Mention of company and product names herein does not constitute endorsement by the U. S. Environmental Protection Agency. Environmental Protection Agency policy is to express all measurements in Agency documents in metric units. When implementing this practice will result in undue costs or lack of clarity, conversion factors are provided for the non-metric units used in a report. Generally, this report uses British units of measure. For conversion to the metric system, use the following conversions: To convert from To Multiply by °F °% 5/9 (°F-32) ft meters 0.304 rt? meters? 0.0929 Ft meters? 0.0283 gal. 1 3.79 Btu cal 252 Ibs 9 453.6 1bs/10° Btu 9/10 cal 1.80 grains/ft? g/m? 2.29 tons kg 907THE ADDITIVES Pollutant reduction additives can be divided into two categories: those that catalyze reactions which convert the pollutant to a non-toxic state (e.9., catalytic reduction of NO to Np and 0») and those that chemically react with the pollutant to form specie which can be easily collected (e.9., reaction of CaCO, with SO, to form calcium sulfate). Catalytic additives are most desirable because of the small amount of material required. The four proprietary additives tested in this work are of the catalytic type according to their manufacturers. The last additive tested, sodium carbonate, is of the latter type because it reacts chemically with SO, to form sodium sulfates. Table 1 gives the detailed chemical analyses of each proprietary material tested. These data were determined for EPA by an independent laboratory* using atomic adsorption, neutron activation, etc. as indicated. In each case x-ray diffraction was also used to determine the chemical Compound(s) predominant in each additive. The final additive, sodium carbonate, was a single compound (commercial grade) and was therefore not analyzed. All of the materials are dry powders that are blown into the primary combustion zone where they are reported to cause reductions in pollutant emissions. TRIMEX Trimex is a fine, dry powder fuel additive manufactured by Trimex Corporation, 495 Mandalay Avenue, Clearwater, Florida. It is available *She11 Development Company, Emeryville, California 3Table 1. CHEMICAL ANALYSIS OF ADDITIVES Element Weight percent Analysis method Trimex I Trimex IL PACE KAP Glo-Klen al Atomic absorption 7.9 6.0 a 0.3 6.5 B Flame emission 0.5 0.3 - — -- ca Atomic ausorption 1.0 MW ad 44 0.6 c Combustion > 0.5 6.1 -- a Ag-titration _ = 21.2 30.1 --- cr Atomic absorption -- a 0.4 -- --- cu Atomic absorption a -- 0.5 - - Fe Atomic absorption 2.8 7 7.8 3.6 14 Mg Atomic absorption 1.9 ww 4.3 2.5 0.8 Mn Atomic absorption a --- 6.2 2.2 - Ha Flame emission 1.9 3.6 1.5 19.6 4.6 Ni Atomic absorption = — 0.2 - --- 0 Neutron activation 55.5 53.1 24.3 23.3 60.0 si Neutron activation 27.6 23.1 0.1 5.6 19.3 Ti Atomic absorption 0.2 0.2 + + Zn Atomic absorption - os 0.7 os a Total 99.3 90.8 98.8 97.7 93.2in two formulations, botn of which are mixtures of clays. The x-ray diffraction patterns indicated that Trimex I is mostly montmorillonite, while Trimex II is a mixture of 2.Na,O . A120, . 2Si0, and gismondite, Ca(A1,Si,0g) . 4 H,0. The material is recommended for both coal and oi1 and is reported('"3) by the manufacturer to substantially reduce CO, UHC, and $0, emissions. The manufacturer's recommended feed rate is about 1 1b of Trimex per 25 Ibs of sulfur in the fuel. (This is equivalent to about 1 1b of additive for 300 gallons of a I-percent residual oi1, or to about 2.5 Ibs of additive per ton of 3-percent sulfur coal.) Trimex sells for about $360 per ton F.0.B. in 50-ton lots. PACE PACE (Pure Air and Clean Environment) is a fine, red-powder fuel additive, manufactured by Takayuki Oishi, Japan. X-ray diffraction indicates that it is probably a mixture of NaCl, MgO, Ca0, and alpha Fe,0,. The manufacturer reports it is effective in reducing emissions of smoke and SO,. The manufacturer's reconmended minimum feed rate is 1 1b of PACE to 1000 Ibs of fuel. (This is equivalent to about 1 Ib of additive for 125 gallons of residual oi] or to about 2 Ibs per ton of coal.) No firm cost data are available because PACE is not widely marketed in the United States. KAP KAP is a dry-powder fuel additive marketed by Kleen-Aire Products, Inc. , 3930 Newhall Road, Columbus, Ohio. Based on the results of x-ray diffraction and KBr pressed plate infrared spectral analysis, KAP appears to be 50 percent salt (NaCl), 13 percent talc (tg 58140) 9H), 10 percent CaCO,, andan iron manganese silicate. KAP is reconmended for use in coal, oi1, and smelting furnaces and is reported(*) by the manufacturer to eliminate or reduce the emission of black smoke, S0,, CO, NO, and chlorine gas while increasing the combustion temperature, cleaning the combustor walls, and increasing the burning efficiency by at least 10 percent. The recomended feed rate is about 1 1b of additive per 1000 Ibs of fuel. (This is equivalent to about 1 Ib of additive for 125 gallons of residual of1 or to about 2 Tbs per ton of coal.) KAP sells for about $1200 per ton. GLO-KLEN Glo-Klen is also a dry-powder fuel additive manufactured by Glo-klen, Inc. , 3705 Morse Avenue, Lincolnwood, Illinois. X-ray diffraction indicates that it is a mixture of clays, probably montmorillonite and eriomite. The manufacturer reports that Glo-Klen is effective with anything burnable including gas, oi1, wood, and coal, and that it reduces or eliminates emissions of smoke, SO,, NO, CO, UHC, etc. In contrast to the other materials, it is only necessary to spread or blow Glo-Klen into the firebox once or twice a day according to the manufacturer. The recommended dosage is 2 Ibs per 1000 sq ft of heating surface. (This is equivalent to a continuous feed rate of about 1 Ib of additive for 300 gallons of residual oi] or about 0.75 Ibs per ton of coal.) Glo-Klen retails for about $1100 per ton. SODIUM CARBONATE At the conclusion of the testing with the proprietary materials, a single very brief test was conducted with sodium carbonate since it has been repeatedly shown to be effectivel®) in reducing $0, enissions. The test sample of sodium carbonate was commercial grade and was obtained from a local supplier at a cost of $4.95 per 100 1b delivered. No attemptwas made to determine the absolute purity of the material. Previously, workers(®) have utilized feed rates between 0.80 and 4.8 Ibs Na,C0, per Tb of sulfur in the fuel. (The latter is equivalent to about 1 1b of additive per 2.5 gallons of 1-percent sulfur residual oi1 or about 290 Tbs of additive per ton of 3-percent sulfur coal.) Sodium carbonate was included in this program to provide a "control" on the test system; that is, to show that SO, reductions are possible with the use of an additive.LAMINAR FLUE GAS OUT FLOW ELEMENT AIR BLOWE! A a ‘TO ANALYTICAL SYSTEM PRE-CALIBRATED VIBRA-SCREW FEEDER ADDITIVE INJECTION LINE, OBSERVATION PORT TT — COMBUSTION AIR IN = FIREBOX-FIRETUBE SL BOILER (3-PASS) OBSERVATION PORT OIL FLOW METER RESIDUAL OIL, SUPPLY TANK ELECTRO-COIL, ‘THERMO-CONTROLLER OIL PUMP Figure 1. Schematic of test system.TEST FACILITY The test system used in this program is shown in Figure 1. Basically it consisted of a highly instrumented commercial boiler which had been modified for addition of solid fuel additives in the combustion zone and a complete set of analytical instrumentation for emissions characterization. Each component is described in detail below. THE BOILER The experimental portion of this evaluation was conducted on a 54-HP (1.8 miltion Btu/hr input), firebox-firetube package boiler firing residual oil. With the exception of the additive injection system, the unit was a typical commercial boiler with a 20-gallon per hour air atomizing gun burner capable of modulation. The inlet oi] temperature was maintained constant at 220°F by a thermal controller. The oi1 flow was metered continuously, and the flow rate was checked by calculations using excess air and stack velocity. INJECTION SYSTEM The injection system used throughout the testing was designed to conform to the recommendations of the respective additive manufacturers and to simulate those currently in use in industrial systems. The dry- powder additives were continuously metered into the primary combustion zone by means of a pre-calibrated, variable-speed, vibrating screw feeder above the burner. Periodic timing of the displacement rate for known quantities of additive was also used to provide a check on the feeder calibration. The powder was conveyed from the feeder to the injector bymeans of fluidizing air (less than 1 percent of the total combustion air). Significant plugging problems were not encountered due to the close proximity Of the feeder and the injector. The injector was a stainless steel tube and in nearly a1] cases was positioned inside the wind box of the burner so that Suspended ponder was injected into the highly turbulent region of the burner throat just before the oi1 nozzle. This was done to ensure maximum contact between the additive and the combusting fuel. Observation ports were utilized to verify that settling did not occur. During two of the Trimex tests the injector was moved forward approximately 12 inches so that the additive powder was blown in directly above the flame zone. STANDARD FUEL To provide a uniform test fuel, a large quantity of typical No. 6 oil was obtained before the test series began. However, unfortunately the Trimex testing extended so long that it was necessary to obtain a new oil supply prior to the other testing. While both of these oils were obtained from the same supplier there was a slight variation in composition as shown by Table 2. These residual oi1s were used throughout the testing with the exception of one special Trimex test in which a small quantity of high (1.74 percent) sulfur oil was used to evaluate the effect of sulfur content on performance of this additive. ANALYTICAL PROCEDURES Sampling and analytical systems (Figure 2) were similar to those used in earlier studies by Martin et a1:(6) paramagnetic oxygen analysis, flame Yonization detection for UHC, and non-dispersive infrared for CO, CO), and NO. $0, emissions were monitored continuously with a non-dispersive infrared analyzer. Total So, was also determined using the So, version of the standard 10Table 2. CHEMICAL ANALYSIS OF STANDARD TEST FUELS Weight percent PACE, KAP, Glo-Klen, and Specie Trimex testing NapC0, testing c 88.4 87.9 H 10.2 10.18 N 0.27 0.25 s 0.9 0.88 0 0.28 0.38 Ash 0.04 0.04A FLUE GAS TO WET SO, VELOCITY PROBE WATER TRAP ALL STAINLESS STEEL LINES HEATED MOLECULAR SIEVE - 3 A'CLAY BASE HEATED PARTICULATE FILTER WATER TRAP HEATED STAINLESS PROBE FLOW CONTROL Teelon FI | FIBREGLAS oe INDUSTRIAL FILTER vacuum PUMP SILICA GEL TRAP SILICA GEL TRAP GLASS WOOL FILTER NDIR 50, PARA- MAGNETIC 0% ANALYZER NDIR co ANALYZER IONIZATION H/C ANALYZER 2 ANALYZER | ANALYZER ANALYZER Figure 2. Analytical system. 12EPA wet chemical SO, sampling technique. (7) In the SO, version (Figure 3) the contents of the isopropanol bubbler and the probe washings were titrated and the resulting concentration in ppm was added to the total. The entire technique was verified by analyzing certified span gases. Since the purpose of this investigation was to determine the effect of the additive on total SO, emissions, no attempt was made to separate the S0,/S0, components. Filterable particulate matter was collected isokinetically on woven silver filters capable of 2 0.8 micron collection. Each sample was then analyzed for chemical composition by an independent laboratory. 13tL GREENSBURG-SHITH BUBBLERS, & REQUIRED SILICA GEL ORYING TUBE ‘3% HQ SOLUTION ROTANETER (0.10 CFM) SEN SN Ss NEEDLE 60-mm MED POROSITY FRITTED DISK CONDENSER, GRAHAM COIL TYPE, 300-nm, CORNING 2500 80% ISOPROPANOL SOLUTION VACUUM PUMP DRY GAS METER Figure 3. Sulfur oxides sampling apparatus (wet chemical). FLUE GAS OUT GLASS WOOL, FILTERTEST PLAN The experimental phase of the evaluation was directed at characterizing the effectiveness of the additives over a wide range of conditions represen- tative of actual boiler operations. While the additive materials were being analyzed, the test facility was constructed, instrumented, and operated to establish baseline performance over the range of conditions to be investigated. The additive testing was then begun. Since each additive was tested as nearly as possible according to the manufacturer's suggestions, test plans were not identical. TRIMEX Trimex was injected continuously for 11 days before any detailed testing was begun because the manufacturer stresses that the material must be allowed to acclimate the boiler before it is effective. After the acclimation period continuous testing was begun and the following variables were examined: Air/fuel ratio (excess air) (20-40 percent) Firing rate (load) (8-20 gal./hr) Additive feed rate (1 1b additive/200 Ibs fuel to 1 1b additive/25 lbs fuel) Additive injector location Fuel composition (sulfur level) (0.9 - 1.8 percent) Additive formulation (Trimex I and IT) Due to the limited time available, it was not possible to conduct a complete factorial experiment evaluating all 64 variable combinations. Table 3 shows the actual test plan used. Blank runs (no additive) wereTable 3. TRIMEX TEST PLAN Condition No. Operating variables Addi tive/blank 1 High fire Normal excess air Blank 2 High fire Normal excess air Additive - Nominal injection rate 3 Low fire Normal excess air Additive - Nominal injection rate 4 High fire Low excess air Additive - Nominal injection rate 5 High fire Normal excess air Additive - 10 times nominal ‘injection rate 6 High fire a Normal excess air Additive? - 10 times nominal injection rate 7 High fire Normal excess air Blank "Additive injected above flame zone. 16not conducted before each test condition, because the manufacturer claims that Trimex must be used continuously to be effective. Four complete blank tests were conducted, however, before and after the Trimex testing. PACE, KAP, GLO-KLEN During the testing of PACE, KAP, and Glo-Klen, the following variables were considered: Air/fuel ratio (excess air) (20-40 percent) Firing rate (load) (8-20 gal./hr) Additive injection rate (dose) Again it was not possible to do a complete factorial experiment. Fuel composition (sulfur level) was not considered because the 1.8-percent sulfur of] was no longer available (due to a local ordinance). Injector location was not included as a variable because injection above the flame zone led to boiler operating problems during the Trimex testing. Table 4 shows the detailed plan used with PACE, KAP, and Glo-Klen. As the table ‘indicates, a blank test (no additive) was conducted before each additive test. In no case were data taken until after the test unit had been operating at equilibrium condition (additive or blank) for at least 1 hour. SODIUM CARBONATE During the sodium carbonate testing it was only possible to briefly examine the high fire, normal excess air condition before the test facility was shut down for relocation of the laboratory.Table 4, TEST PLAN FOR PACE, KAP, AND GLO-KLEN Condition No. Operating variables Addi tive/b1 ank 1 Low fire Normal excess air Blank Low fire Normal excess air Additive - Nominal injection rate 2 High fire Normal excess air Blank High fire Normal excess air Additive - Nominal injection rate 3 High fire Low excess air Blank High fire Low excess air Additive - Nominal injection rate 4 High fire Normal excess air Blank 5 High fire Normal excess air Additive - 3 times nominal injection rate 18DISCUSSION OF RESULTS: SO, In order to facilitate comparison, all data throughout the paper are reported as ppm by volume, dry, and reduced to stoichiometric (zero percent excess air). Due to the duration of the Trimex testing, it was necessary to procure a second supply of standard fuel before starting the next testing. Although both supplies were from the same producer, they were not identical in composition and, therefore, gave slightly different baseline S0,. Finally, each material was tested primarily at a "nominal" feed rate of about 10 grams per minute (depending upon additive density). This rate exceeds most of the manufacturer's reconmended minimum dosages; however, it was selected to ensure that claimed S0, reductions would be observed. Once the materials were shown to be effective, the dosage would be reduced to determine the most cost effective feed rate. BASELINE CHARACTERIZATION Characterization work had established the "normal" commercial operating condition for this type of unit as full load (a firing rate of 20 gallons per hour) and 40 percent excess air. The reduced-load condition was defined to be 8 gallons per hour (40 percent excess air) and was included ‘in the testing to investigate the effect of residence time on additive performance. (At this low-fire condition, the gas/additive contact time is ‘increased by a factor of about 2.5.) The low excess air condition was defined to be 20 percent excess air (just above the flame-out limit of the unit). This condition was included to determine if limiting the availability of oxygen would enhance the effectiveness of the material.Testing before and after the Trimex injection confirmed the Trimex baseline (no additive) to be 625 ppm SO,; this agrees with the theoretical SO, concentration calculated from the analysis of the fuel. The 625 ppm baseline level is the average of many tests and has a standard deviation of 7 percent. Therefore, any change of more than 88 ppm (2a) from the baseline level can be considered statistically significant. During the PACE, KAP, and Glo-Klen tests, baseline runs were conducted before and after each additive test at a particular condition. A total of eight baseline determinations were conducted during the complete testing of each of these additives; the average results were: 613 t 25 ppm (PACE) 614 £ 29 ppm (KAP) 614 16 ppm (Glo-Klen) + These values agree with the 615 ppm SO, predicted from the analysis for this fuel. ‘TRIMEX The bulk of the Trimex trialswere conducted using Trimex II as requested by the manufacturer. The initial testing (after the acclimation period) was conducted at the high fire boiler condition and the nominal additive ‘injection rate of 7 grams per minute (1 1b additive/200 1b fuel). As Table 5 indicates, Trimex had no effect under these conditions. (All results are from at least 4 hours of testing at the specified condition and are the average of at least two sets of complete emissions measurements. ) In the next test, the firing rate was reduced to 8 gallons per hour, thus increasing the additive/combustion gas contact time by a factor of 2.5. Again, no significant change over the baseline (no additive case) was observed. 20ir4 Table 5. | RESULTS OF TRIMEX TESTING? emission? Additive/ $0 c Test Condition blank (ppm dry, reduéed to 0% excess air) Effect ——eren Dank (ppm drysreduted to OF excess air) Effect aut Blank 652 t 45 None High fire (full load) Trimex 667 None Normal excess air 7 g/min Low fire (reduced load) Trimex 642 None Normal excess air 7 g/min High fire (full load) Trimex 665 None Low excess air 7 g/min High fire (full load) Trimex 657 None Normal excess air 60 g/min High fire (full load) Trimex® 656 None Normal excess air 60 g/min ail test results were obtained using Trimex II and the standard fuel after the acclimation period. These results are the average of at least two separate emission determinations. Variations of less than 45 ppm from the baseline are not statistically significant. average of all blank runs. Sadditive injected above flame zone.In the third series of tests, the boiler was operated at high fire but at a low excess air level (20 percent) just above the flame-out limit of the unit. The purpose of these tests was to determine if limiting the availability. of oxygen would enhance the effectiveness of the material. Again, the results were negative. During the fourth series of tests, the additive injection rate was increased to 60 grams per minute (maximum output of feeder) to investigate possible effects of increased feed rate. None were observed. In the final tests, the additive injector was positioned so that it sprayed the Trimex powder above the flame zone. No reduction was observed. The average SO, emission during all the Trimex testing (after the acclimation period) was 657 ppm with a standard deviation of only 18 ppm. The average baseline level was 652 ppm. Thus, there is little doubt that Trimex was wholly ineffective throughout the actual testing. During the 11-day acclimation period, tests were run under several other conditions. While the detailed results are not reported herein, in deference to the manufacturer's claim regarding an acclimation period, the trends are worth noting. Before the supply of Trimex II arrived for testing, Trimex I was evaluated at both the low and high fire normal excess air conditions. No reductions were observed. The unit was also switched to a high sulfur residual oi1 (1.74 percent); again, no reduction was observed. Throughout the actual Trimex testing, particulate samples were chemically analyzed. Table 6 presents these results. In no case did the 22Table 6. RESULTS OF PARTICUIATE ANALYSIS - TRIMEX Percent of entering Test Additive/ Particulate logding® Percent sulfur® Particulate sulfur Fuel sylfur? § leaving bgiler as condition blank (grains/#t3) in particulate (16/108 Btu) (1b/10? Btu) solid Low fire (reduced load) Blank 0.056 0.4 0.0003 0.51 0.06 High fire (full load) Blank 0.074 15 0.0014 0.51 0.3 High fire (full load) Trimex 0.081 f - 0.51 -- Normal excess air 7 g/min Low fire (reduced load) Trimex 0.113 2.4 0.0035 0.51 0.7 Normal excess air 7 g/min High fire (full load) — Trimex g - - 0.51 -- Low excess air 7 g/min yjligh fire (full load) —_Trimex 1.25 2.0 0.0325 0.51 6.4 Normal excess air 60 g/min High fire (full load) —_Trimex" 1.32 2.4 0.0415 0.51 8.1 Normal excess air 60 g/min “pry, at 32°F, and reduced to zero percent excess air. Pas determined for EPA by an independent laboratory. “This column shows the total sulfur contained in the particulate based on the firing rate, particulate loading, and chemical analysis of the particulate. eased on the chemical analysis of the oi1. “This column shows the percent of the fuel sulfur which left the boiler as part of the particulate. finsufficient sample. SNot determined. Nadditive injected above flame zone.sulfur content of the flue gas particulate exceed 0.04 Ibs per million Btu which is less than 9 percent of the total sulfur entering the boiler (0.51 Tbs/10® Btu). Thus, these data give no indication that Trimex was forming any significant amount of solid phase complex. At the conclusion of the Trimex testing the boiler was shut down and samples of various deposits taken. Table 7 shows the analysis of these samples. The deposits in the front-tube cross section contained 1.8 percent sulfur--the highest concentration found anywhere in the boiler. However, even if the average deposit level was assumed to be 1.8 percent sulfur, this would represent less than 0.3 percent of the total sulfur input during the measured period based on a total sulfur balance on the system. Hence, no significant amount of sulfur was being converted to solid deposits. Thus, there can be little doubt that Trimex was wholly ineffective in reducing So, emissions: no reduction in flue gas $0, concentration was observed, no significant sulfur was found in the particulate, and no sulfur was found deposited inside the boiler. PACE, The results of the PACE testing are shown in Table 8. Under no Conditions did PACE significantly reduce SO, emissions. The slight reductions in the low fire and high fire/increased rate tests, while not statistically significant, may be real since both occurred at increased additive-to-fuel ratio (above 1 1b PACE/80 1b fuel). Since PACE contains substantial amounts of NaCl, MgO, and CaO, these slight reductions would be expected due to stoichiometric chemical effects such as the formation of CaSO,. 24Table 7, ANALYSIS OF BOILER DEPOSITS (TRIMEX) Location Percent sulfur Burner quarrel Firebox floor Firebox lower wall Firebox upper wall Second tube pass Front-tube cross section Back-tube cross section 2592 Table 8. RESULTS OF PACE TESTING Additive/ $0, emission® b Test condition blank (ppm drysreduted to 0% excess air) Effect! Theoretical emissions ¢ Based on fuel analysis Blank 615 - Baseline measurements! Blank 613 t 25 = Low fire (reduced load) PACE 567 None Normal excess air 6 g/min High fire (full load) PACE 609 None Normal excess air 6 g/min High fire (full toad) PACE 597 None Low excess air 6 g/min High fire (full load) PACE 565 None Normal excess air 15 g/min These results are the average of at least two separate emission determinations. variations of less than 50 ppm are not statistically significant. “The residual of] used throughout this testing contained 0.88 percent sulfur. Upon oxidation, this level would result in 615 ppm of SO, dry at stoichiometric. “this result is the average of the eight separate emission determinations conducted throughout the testing (before and after each additive test).Table 9 shows the results of the particulate sampling and analysis conducted during the PACE testing. Unfortunately, it was not possible to take a particulate sample at every condition due to time limitations. The data confirm that no significant amount of the entering sulfur leaves the combustor in the solid phase. KAP The results of the KAP testing are shown in Table 10. As the table indicates, under no condition tested did KAP have a statistically significant effect on SO, emissions. A slight possible reduction was observed at the high feed rate condition: this is probably due to a stoichionetric reaction between the active metal components and SO, to form sulfates. Regardless of the mechanism, however, the dose rate is economically unfeasible. The possible 7-percent reduction was achieved at 1 1b additive/40 Ibs of1 which is equivalent to 11 cents per gallon of oi] treated. Table 11 shows the results of the particulate analysis at four of the test conditions. Again, the flue gas particulate contains no signi- ficant amount of sulfur. GLO-KLEN The detailed results of the Glo-Klen testing are shown in Table 12. In summary, the average SO, emission with Glo-Klen was 611 ppm. The average SO, emission without Glo-Klen was 614 + 16 ppm; the theoretical SO, was 615 ppm. Glo-Klen had absolutely no effect on SO, emissions under any condition tested. (Its composition is very similar to that of Trimex and it would, therefore, not be expected to affect S0,.) 27Table 9. RESULTS OF PARTICULATE ANALYSIS - PACE Test Additive/ Particulate logding® Percent. sul fur? Particulate sulfur® Fuel splfurd Percent of entering condition blank (grains/#t3) in particulate (1b/10° Btu) (1b/10° Btu) S$ leaving as solid High fire (full load) Blank 0.079 5.4 0.0056 0.50 wl Normal excess air High fire (full load) PACE 0.105 12.3 0.0169 0.50 3.4 Normal excess air 6 g/min High fire (full load) Blank 0.114 4.1 0.0061 0.50 1.2 Low excess air High fire (full load) PACE 0.100 8.8 0.0115 0.50 2.3 Low excess air 6 g/min 8 “bry, at 32°F, and reduced to zero percent excess air. Sas determined for EPA by an independent laboratory. “This column shows the total sulfur contained in the particulate based on the firing rate, particulate loading, and chemical analysis of the particulate. 4gased on the chemical analysis of the oil. *This column shows the percent of the fuel sulfur which left the boiler as part of the particulate.62 Table 10. RESULTS OF KAP TESTING Additive/ SO, emissions® b Test condition blank (ppm dry, reduéed to 0% excess air) Effect Theoretical emissions® Blank 615 - Baseline measurements? Blank 614 t 29 oi Low fire (reduced load) KAP 597 None Normal excess air 13 g/min High fire (full load) KAP 597 None Normal excess air 13 g/min High fire (full load) KAP 597 None Low excess air 13 g/min High fire (full load) KAP 572 None Normal excess air 34 g/min *These results are the average of at least two separate emission determinations. variations of less than 50 ppm are not statistically significant. “The residual of] used throughout this testing contained 0.88 percent sulfur. Upon oxidation this level would result in 615 ppm of SO,. “this result is the average of the eight separate emission determinations conducted throughout the testing (before and after each additive test condition).Table 11. RESULTS OF PARTICULATE ANALYSES - KAP Percent of entering Test Additive/ Particulate logding™ Percent sulfur? Particulage sulfur Fuel sylfurd S leaving boiler as condition blank (grains/ft3) in particulate (bs10° Btu) (110° Btu) solid® High fire (full load) Blank 0.062 f --- 0.50 aod Normal excess air High fire (full load) KAP 0.124 6.2 0.0100 0.50 2.0 Normal excess air 13 g/min High fire (full load) Blank 0.094 5.0 0.0061 0.50 1.2 Low excess air High fire (full load) KAP 0.140 10.2 0.0186 0.50 3.7 Low excess air 13 g/min 38 pry, at 32°F, and reduced to zero percent excess air. Pas determined for EPA by an independent laboratory. “This column shows the total sulfur contained in the particulate based on the firing rate, particulate loading, and chemical analysis of the particulate. based on the chemical analysis of the oil. this colum shows the percent of the fuel sulfur which left the boiler as part of the particulate. finsufficient sample.le Table 12. RESULTS OF GLO-KLEN TESTING Addi tive/ SO, emissions® b Test condition blank (ppm dry, reduéed to 0% excess air) Effect’ Theoretical emissions® Blank 615 - d + Baseline measurements: Blank 614. 16 - Low fire (reduced load) Glo-Klen 610 None Normal excess air 7 g/min High fire (full load) Glo-Klen 620 None Normal excess air 7 g/min High fire (full load) Glo-Klen 607 None Low excess air 7 g/min High fire (full load) Glo-Klen 606 None Normal excess air 18 g/min These results are the average of at least two separate emission determinations. variations of less than 32 ppm are not statistically significant. “The residual oi1 used throughout this testing contained 0.88 percent sulfur. Upon oxidation this level would result in 615 ppm of SO, dry at stoichiometric. “This result is the average of the ei (before and after each additive test). ght separate emission determinations conducted throughout the testingTable 13 shows the results of the particulate analyses conducted during the Glo-Klen testing. In no case does the total particulate sulfur exceed 0.006 Tbs/10® Btu which is less than 2 percent of the total fuel sulfur. SODIUM CARBONATE At the end of the proprietary additive testing, one brief test was conducted with sodium carbonate (Na,CO,) to denonstrate that dry materials do exist, capable of S0, control. The feed rate was 1 1b of Na,C0y per 30 Ibs of fuel. This corresponds with 1.3 times the sodium carbonate required to react with all the SO, to form Na,S0,. The NayC0,, injected dry at the high fire, normal excess air condition, reduced the SO, emissions from 614 ppm to 393 ppm. This generally agrees with previously reported NapC0, work(®) and represents about a 36-percent SO, reduction. This result is also strengthened by the particulate analysis which revealed a sulfur content in excess of 20 weight percent. Unfortunately, it was not possible to total material balance as in Tables 6, 9, 11, and 13 because the extremely high solid loading prevented isokinetic sampling for more than 1 minute. No attempt to optimize the utilization of sodium carbonate was made because of the boiler operating problems (e.g., tube fouling and ESP overloading) associated with the long-term feeding of large amounts of the material. 32ee Table 13. RESULTS OF PARTICULATE ANALYSIS - GLO-KLEN Percent of entering Test Additive/ Particulate logding® Percent sulfur? Particulage sulfur‘ Fuel sulfur? S$ leaving boiler as condition blank (grains/ft?) in particulate (1b/10° Btu) (1b/10° Btu) solid’ High fire (full load) Blank 0.048 5.0 0.0032 0.50 0.6 Normal excess air High fire (full load) Glo-Klen 0.076 4.6 0.0046 0.50 0.9 Normal excess air 7 g/min High fire (full load) Blank 0.091 4.9 0.0058 0.50 Ww Low excess air High fire (full load) — Glo-klen 0.136 3.0 0.0053 0.50 Ww Low excess air 7 g/min “ory, at 32°F, and reduced to zero percent excess air. Pas determined for EPA by an independent laboratory. “This colum shows the total sulfur contained in the particulate based on the firing rate, particulate loading, and chemical analysis of the particulate. gased on the chemical analysis of the oi1. “This colum shows the percent of the fuel sulfur which left the boiler as part of the particulate.DISCUSSION OF RESULTS: OTHER EMISSIONS UNBURNED HYDROCARBONS Unburned hydrocarbon emissions from commercial boilers are typically very low if the unit and burner are maintained properly. The average baseline hydrocarbon emission for the test boiler was 0.3 ppm calibrated as propane. No additive had any effect on this level. CARBON MONOXIDE The average baseline carbon monoxide emission was 29 ppm; no additive had any effect on this level. (It should be cautioned, however, that injecting a dry additive in such a way that it changes the combustion aerodynamics can substantially increase carbon monoxide emissions. This was experimentally observed during initial location of the injection system.) NITRIC OXIDE No additive had any effect on the measured NO emissions from the test unit; this agrees with the general results found during previous additive testing, (6) Emissions of NO from residual oi! combustion are attributable to two sources: thermal fixation of atmospheric nitrogen at high temperatures, and oxidation of nitrogen in either the oil or the additive. However, none of the additives were effective in reducing NO formation via either mechanism. NO emissions did not increase since none of the materials contained significant nitrogen. 35METALLIC Use of any metal-containing additive is also undesirable from an air pollution viewpoint because of the new emissions its use would create, For example, if one uncontrolled 1000-MW utility boiler were to use Trimex at the manufacturer's recommended dosage for a year, it would emit almost 300 tons of new metallic pollutants (assuming none of the additive collected in the boiler). Table 14 gives a more detailed breakdown of these emissions. (Since it is not clear in what form these metals would be emitted, their toxicity cannot be established.) Each of the other materials would result in similar emissions. If the metallic emissions are avoided by collecting the solid emissions Prior to the stack with a baghouse or other particulate removal system, then a potential water-pollution/solid-waste problem results. For example, disposal of the solids from PACE or KAP utilization would be difficult because both additives contain large quantities of sodium. This would almost certainly result in sodium compounds in the solid waste that were water soluble and would contaminate the run-off from any disposal site. In practice part of any dry, metallic additive always collects inside the boiler and can create serious boiler operating problems. For example, at the end of the Trimex testing the test boiler had to be taken off line for complete cleaning due to deposits in the boiler tubes and firebox as shown in Figure 4. Admittedly, the high-additive doses used during the testing greatly accelerated the formation of deposits; however, there is little doubt that extended additive injection at lower rates would result in similar deposits. 36Table 14. ADDITIONAL UNCONTROLLED METALLIC EMISSIONS RESULTING FROM THE USE OF TRIMEX IN A 1000-MW BOILER Elenent_ Additonal bs/yr Al 231 ,000 8 12,000 Ca 42,000 Fe 66,000 Mg 66,000 Na 139,000CLOSE-UP OF BOILER TUBES -- RIGHT-HALF HAS BEEN CLEANED. phs of test boiler after Trimex testingCONCLUSIONS This testing, as in any experimental program, has certain limitations; it is pertinent to consider these before any conclusions regarding the data are reached. First, the program was conducted on a 20-gallon per hour (0.3 MM) package boiler, not a 1000-MW utility unit. There are recognized differences in the operating characteristics of each; the tests were designed to cover a broad range of conditions, including those typical of larger utility systens. For example, combustion zone residence times typically range between 1.0 and 1.5 seconds and combustion intensities between 10,000 and 100,000 Btu/hr/ft?, During the testing the combustion zone residence time was varied from 0.7 to 1.8 seconds and the combustion intensity from 36,000 Btu/hr/ft? (high fire) to 15,000 Btu/hr/ft? (1ow fire). These changes did not significantly affect additive performance. Further, in the case of Trimex, recent independent testing’®) on a 1-¥W size unit found material of the same composition to be completely ineffective. Thus, there is no reason to think that the effectiveness of any of the materials would change markedly as a function of unit size. Second, since the test fuel was residual of] no absolute conclusions can be reached regarding the effectiveness of the additives with other fuels, such as coal or wood. However, in the Trimex case, literature data on coal testing show no effectiveness; (>) doubling the sulfur content of the ofl in the present study gave no change in performance. KAP has been evaluated with coat; (8) however, unfortunately the conclusions were "not firm." Thus, it appears that the data can at Teast be considered a guide to performance with other fuels. 39Each additive test was started at a dose rate of 10 grams per minute (relatively high) to ensure that the claimed reductions would be observed. The authors had planned to then reduce the dose rate to determine the most cost effective rate. However, in every case the additive was ineffective at this "nominal" rate, so further reductions were useless. Unfortunately, increasing the dosage was also ineffective in producing performance. With these considerations in mind the following conclusions can be drawn from this program. 1, Trimex, PACE, KAP, and Glo-Klen were injected under a wide variety of operating conditions; under no circumstances was there any significant reduction in SO, emissions. Further, based on the results of this and other work, there is no reason to believe that the material would be effective in controlling SO, emissions from any boiler or furnace burning oi1 or coal. 2, The additives had no effect on UHC, CO, or NO emissions at any condition investigated. 3. Widespread use of any of the additives tested could result in tons of new emissions with unknown toxicity. 4. Potential operating problems, such as tube clogging and corrosion, need further investigation before major use of any “pollution control" additive is considered. 40BIBLIOGRAPHY Milner, M. R. and F. B. Johnston. Combustion Adjuvant. U. S. Patent 3,630,696, December 28, 1971. Milner, M. R. Combustion Adjuvant. U. S. Patent 3,628,925, December 21, 1971. Pratt, R. Emissions Level Reduced in Tests. Savannah Morning News, p 1, March 26, 1972. Air Pollution . . . What is the Answer? Kleen-Aire Products, Inc. Bulletin on KAP. Brancaccio, J. and C. V. Flash. Use of Dry Fuel Additives to Reduce SO, Emissions from a Full Size Industrial Coal-Fired Boiler. Presented at 65th Annual APCA Meeting, Miami Beach, Florida, June 1972. Martin, G. B., D. W. Pershing, and £. E. Berkau. Effects of Fuel Additives on Air Pollutant Emissions from Distillate Oi1-Fired Furnaces. EPA Office of Air Programs Publication No. AP-87, June 1971. Determination of Sulfur Dioxide Emissions from Stationary Sources, Federal Register, Vol. 36, No. 159, pp. 15717-15718, August 17, 1971. Siltala, C. A. Emission Testing at City of Columbus Power Plant During Addition of KAP. Environment Control Corp. Final Report, July 1971. 4BIBLIOGRAPHIC DATA SHEET T Rei fa Tale aod Sobel Effectiveness of Selected Fuel Additives in Controlling 3: Recipient's Accession No. |5. Report Date] October 1973- Pollution Emissions from Residual-Oil-Fired Boilers e 7. Raahor(sy D. W. Pershing, G. B. Martin, E. E. Berkau, R.E, Hall 19. Performing Organization Name and Address EPA, Office of Research and Development NERC-RTP, Control Systems Laboratory 1s. Performing Organization Rep Rerlorming Ore Pe 10. Project/Task/Work Unit No. Ti. Contract/Grant No. Research Triangle Park, North Carolina 27711 In-House 12 Sponsoring Organization Name and Address 13. Type of Report & Penod Final NA Te TS. Supplementary Notes * The report gives results of a study to experimentally evaluate the effect- iveness of four additive materials in controlling pollutant emissions from fossil fuel combustion: Trimex, PACE, KAP, and Glo-Klen. Each was carefully examined in a highly instrumented package boiler over the range of typical operating conditions (e.g. , combustion intensity and residence time) for industrial and utility systems. Results show that none of the four reduce emissions of SOx, NO, CO, or UHC under any condition tested. Based on these results, the boiler operating problems, and the possibility that their use might create potentially harmful new emissions, none of the additives can be recommended as a means of controlling pollutant emissions. V7. Key Words and Dacument Analysia- Air Pollution Fuel Additives Residual Oil Combustion Sodium Carbonates Sulfur Oxides Hydrocarbons Carbon Monoxide Nitrogen Oxide (NO) 17b. Identsfsces/Open-Ended Terms Air Pollution Control Stationary Sources Wa. Descriprors Boilers Glo-Klen Unburned Hydrocarbons Trimex Metallic Emissions PACE Particulates KAP We. COSATI Field /Group 13B, 13A, 21B [essay se 9 Seca Case hs [ATW a Page oar 7G Unlimited Security Class (The ] 20. 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