United States Environmental Protection Agency Air and Energy Engineering Research Laboratory Research Triangle Park NC 2771 Research and Development EPA/600/S7-87/019 Sept. 1987 Project Summary Pilot-Scale Evaluation of LIMB Technology R. S. Dahlin, R. Beittel, and J. P. Gooch In support of EPA's LIMB (Limestone Injection Multistage Burner) develop- ment program. Southern Research In- stitute (SoRI) performed pilot-scale studies of sulfur capture in the LIMB process and the effect of LIMB on particulate properties and electrostatic precipitator (ESP) performance. The sulfur capture studies showed that hydrated lime was generally superior to limestone as a sorbent for in-furnace sulfur removal. For both sorbents, downstream injection was found to be preferable over near-flame injection. With hydrated lime, the optimum in- jection temperature was found to be about 1200°C, where utilizations as high as 30% were achieved. The injec- tion of either sorbent resulted in a large increase in the electrical resistivity of the ash, which could severely impact ESP performance. Laboratory and pilot- scale studies showed that the resistivity increase could be offset by flue gas conditioning using sulfur trioxide (SO3) or water vapor. With limestone injection, acceptable resistivity levels were re- stored by the injection of 30 ppm of S03. This Project Summary was developed by EPA's Air and Energy Engineering Research Laboratory, Research Triangle Park, NC, to announce key findings of the research project that Is fully docu- mented In a separate report of the same title (see Project Report ordering In- formation at back). Introduction EPA's Air and Energy Engineering Research Laboratory (AEERL) is develop- ing the Limestone Injection Multistage Burner (LIMB) process as a low-capital- cost control option for compliance with possible acid rain legislation. The purpose of the LIMB process is to achieve a 50% reduction in emissions of sulfur oxides (SOX) at a calcium-to-sulf ur (Ca/S) molar ratio of 2. This would make the process applicable to a significant number of existing coal-fired boilers that would probably be impacted by acid rain legis- lation. In a retrofit application of LIMB, the sorbent (limestone or hydrated lime) is injected downstream of the burner zone using a retrofitted system for sorbent handling and injection. The re- sulting particulate (calcium sulfate, un- reacted calcium oxide, and fly ash) is collected in the existing ESP or baghouse. Since sorbent utilization is generally low (~ 12-15% for limestone and 25-30% for hydrated lime), it is necessary to use more than (typically twice) the stoichio- metric requirement of the sorbent. This results in a significant increase in the particulate loading that must be handled in the boiler system and particulate col- lector. The particle size and electrical resistivity of the particulate are also af- fected by the sorbent injection, and these effects can severely impact particulate collection efficiency. Objectives and Scope The original goal of this research pro- gram was to study the effect of the LIMB process on particulate properties and ESP performance. As part of this work, it was necessary to evaluate the effectiveness of various sorbents in terms of sulfur capture. The latter evaluations prompted an expansion of the project scope to include a study of sulfur capture in the LIMB process. Thus, the project report covers two areas of LIMB-related re- search: (1) Studies of sulfur capture in ------- the LIMB process, and (2) Studies of the effect of LIMB on participate properties and ESP performance. The goal of the sulfur capture studies was to investigate the effects of sorbent type, injection conditions, particle size, and promoters on sulfur capture. The goal of the par- ticulate and ESP work was to examine the effects of LIMB on paniculate loading, particle size distribution, and electrical resistivity (three of the major factors in- fluencing ESP performance). Prior to the sulfur capture or particulate work, how- ever, it was necessary to verify the ability of the SoRI pilot-scale coal combustor to simulate utility boiler conditions and ash characteristics. This was necessary to ensure that the LIMB-related testing done in this unit could be applied to full-scale utility boilers. The goal of the verification effort was to show that the ash produced by the SoRI combustor was similar to full-scale ash from the same coal in terms of particle size distribution, morphology, electrical resistivity, and chemical com- position. These comparisons showed ex- cellent correspondence between the combustor ash and ash produced from the same coal in a full-scale unit. Results and Discussion Sulfur-capture screening studies of sorbent type and injection location were conducted with three sorbents: Vicron 45-3 calcitic limestone (V), Longview calcitic hydrated lime (L), and Corson pressure-hydrated dolomitic lime (C). Tests were performed with both coal firing and S02-doped natural gas firing. The injection location was varied from the burner (B) to furnace section 4 (S-4), which is near the furnace outlet. The corresponding gas temperatures and sulfur captures (at Ca/S = 2) are: Coal Firing Injection Location B S-3 S-4 Temperature °C ND 1237 1132 Capture, % V L C 35 37 ND 40 61 81 32 S3 ND Natural Gas Firing Injection Temperature Capture, % Location °C V L C B S-3 S-4 1477 1332 1126 30 29 ND 24 40 80 28 45 ND At equivalent Ca/S ratios, the sorbents are ranked in performance: pressure- hydrated dolomitic lime > calcitic hydrated lime > limestone. This may be misleading, however, since the dolomitic lime also contains 1 mole of magnesium per mole of calcium. Thus, a much greater weight of dolomitic lime is required to achieve the same Ca/S ratio. When compared at equivalent mass injection rates, the calcitic and dolomitic hydrated limes give virtually identical performance, despite the fact that the magnesium is inert and does not react with S02 under furnace conditions. This suggests that the magnesium acts to facilitate the reaction between the CaO and SO2. For both the limestone and the hydrated lime, the optimum injection temperature was about 1237°C with coal firing. Since this was optimum for both the limestone and hydrated lime, the other injection loca- tions were not tested with the pressure- hydrated dolomitic lime. The dependence of sulfur capture on the sorbent particle size was investigated using size-fractionated samples of ash/ sorbent mixtures collected isokinetically at the exit of the combustor system. Chemical analyses of these fractions showed that sorbent utilization was a strong function of particle size for both the limestone and the hydrated lime. The data obtained with both sorbents injected atS-4(~1132°C)are: Particle size, fim 0.5 1.0 2.0 5.0 10 20 Utilization, % Vicron limestone 35 32 22 15 14 ND Longview hydrate 25 26 25 18 15 13 Sorbent utilization decreases with in- creasing particle size for both sorbents. This points out one advantage of hydrated lime over limestone: the mass median particle size is much smaller (~2 vs. 15 Mm). It also illustrates the potential per- formance gains from ultrafine grinding of the limestone, to the extent it is practical. The promotion of sulfur capture by the use of a sodium-based additive was in- vestigated using 5 wt% of sodium bi- carbonate premixed with the Vicron limestone. With natural gas firing and sorbent injected through the burner, the sulfur capture (at Ca/S = 2) was almost doubled by the promoter (32% vs. 60% capture). However, this effect was largely eliminated when fly ash was added to the system to simulate coal firing and when similar tests were conducted during coal firing. This suggests that the volatilized sodium is being lost to the fine fly ash particles, so that it is not available for promotion with coal firing. The effect of sorbent injection on the electrical resistivity of the ash was deter- mined through in situ resistivity measure- ments in the pilot-scale combustion system and through IEEE laboratory tests in controlled environments. The baseline ( (without sorbent injection) resistivity values ranged from 2x10s to 1010 ohm- cm in the presence of 22 to 40 ppm of naturally occurring S03. When limestone was injected, and virtually all of the S03 was removed « 0.2 ppm remaining), the in situ resistivity was increased to about 1012 ohm-cm. In laboratory tests per- formed at the same temperature (~ 150°C), the resistivity was 9x1012 ohm- cm in the absence of any S03. With 5 ppm of S03 in the laboratory test cell, the resistivity was reduced to 5x108 ohm-cm, illustrating the extreme sensitivity to residual S03 levels. Higher levels of S03 are required to produce this effect in the combustor system due to the much shorter exposure time (days in the labora- tory vs. seconds in the combustor system). The ability to restore acceptable SO3 levels and resistivity values was demonstrated using a catalytic S03 generator and in- jection system. The results of these studies are: SO3 injected, ppm 0 10 Resistivity, ohm-cm I.SxIO'2 2x10" 20 30 40 3x10'° 3x10* 2x10s These results indicate that resistivity can be restored to acceptable levels at rea- sonable S03 injection rates. This was also true with hydrated lime injection, although more SO3 was required, and the amenability of the ash to conditioning was much more sensitive to sorbent injection location. With injection at S-3 (~ 1237°C), 120 ppm of SO3 was required to reduce resistivity to 1010 ohm-cm. Despite this large injection rate, less than 8 ppm of SO3 remained in the gas phase at the exit of the system, suggesting that almost all of the SO3 was adsorbed on the particulate. The effect of sorbent injection on the particulate size distribution was evaluated through in situ measurements made in the pilot-scale system using cascade impactors, an optical counter, and an electrical mobility analyzer. With lime- stone as the sorbent, burner injection produced fine (0.1-1.0 /im) particle con- centrations that were an order of magni- tude higher than with downstream injection at S-4. This suggests that the limestone decrepitates at the higher temperatures associated with burner injection. With downstream injection at ------- IS-4, the particle size distributions ob- tained with limestone and hydrated lime were similar, despite the much finer size of the original hydrated lime. The effect of sorbent injection on ESP performance was predicted using the resistivity values and the particle size data in the EPA/SoRI model of electro- static precipitation. The results for the baseline (no sorbent) and the limestone injection cases are: from the burner, away from the flame zone. This study suggests that the opti- mum injection temperature is about 1237°C, although a higher injection temperature may be needed in a full- scale boiler to allow for mixing effects. A retrofit application of LIMB tech- nology can have a devastating impact on ESP performance, especially for older plants with undersized ESPs. In these Total paniculate loading, mg/m3 (gr/ft3) Mass median panicle size, p.m Resistivity, ohm-cm SCA, nf/rrf/sec (ft'/kacfm) Average applied voltage, kV Current density, nA/crrf Predicted collection efficiency, % Baseline 6,876(3.00) 14 2x10 10 44.3(225) 41.7 26.3 99 Limestone 15,586(6.8) 16 2x10 12 44.3(225) 29.7 1.50 93 The predicted degradation in ESP per- formance corresponds to a factor of 16 increase in emissions. If the original resistivity and electrical operating condi- tions are restored by flue gas condition- ing, the collection efficiency can be brought back to about 99%, but the emis- sions would still be higher by a factor of 2.3 due to the higher inlet loading. Further improvements to the ESP in- ternals would be required to restore original emission levels with such a small ESP. Larger units may have excess capacity that would allow emissions to be controlled at a comparable level with- out further modifications. Conclusions and Recommendations Based on the sulfur capture data from this study, it appears that hydrated lime must be used in lieu of limestone to meet the performance objective of 50% SO2 control at Ca/S = 2. The studies of size- fractionated samples suggest that further improvements in hydrated lime per- formance may be possible by fractionating out the smallest particles. The practicality of this concept has not yet been evaluated. Although limestone performance im- proves with decreasing particle size, it does not seem feasible to attain 50% removal by ultrafine grinding due to the power requirements and cost. Improve- ment of sorbent performance by the use of a sodium-based additive does not appear feasible due to the apparent loss of the volatilized sodium on the fly ash particles. Additives that enhance the specific surface area of the sorbent may be advantageous. Whatever sorbent is selected, it should be injected downstream plants, it appears likely that flue gas conditioning and modification of the ESP internals will be necessary to restore acceptable performance. The use of water sprays may be advantageous to gain the benefits of cooling, conditioning, and reducing the gas flow. This would provide an increase in the effective specific col- lection area (SCA) to complement the reduction in resistivity. Other potential remedial measures would include the installation of a cold-pipe precharger section, conversion of the ESP to an ESOX process, or even the use of a wet ESP. Enlargement of the SCA is not feasible unless it is accompanied by the use of conditioning or other modifications. Space limitations also make this difficult at many older plants. Pilot testing of various ESP modifications is required to select the optimum remedial measures for a LIMB retrofit. Such pilot test should include an evaluation of electrode de- posits and rapping requirements. /?. S. Dahlin R. Beittel, and J. P. Gooch are with Southern Research Institute, Birmingham. AL 35255-5305. Samuel L, Rakes is the EPA Project Officer (see below). The complete report, entitled "Pilot-Scale Evaluation of LIMB Technology," (Order No. PB 87-224 630/AS; Cost: $18.95. subject to change) will be available only from: National Technical Information Service 5285 Port Royal Road Springfield, VA 22161 Telephone: 703-487-4650 The EPA 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 29 8/ I Official Business Penalty for Private Use S300 EPA/600/S7-87/019 0000329 PS ------- |