Technical Paper

BR-1835

Determination of Wet FGD Limestone Reactivity

Authors: S.R. Brown R.F. DeVault P.J. Williams Babcock & Wilcox Power Generation Group, Inc. Barberton, Ohio, U.S.A. Presented to: Electric Power 2010 Date: May 18-20, 2010 Location: Baltimore, Maryland U.S.A.

Determination of Wet FGD Limestone Reactivity

S.R. Brown R.F. DeVault P.J. Williams Babcock & Wilcox Power Generation Group, Inc. Barberton, Ohio, U.S.A. Presented to: Electric Power 2010 May 18-20, 2010 Baltimore, Maryland, U.S.A. BR-1835

Abstract
Limestone reactivity is a determinant of limestone based wet flue gas desulfurization (FGD) system performance. Accurate estimation of this parameter is necessary for absorber performance modeling and absorber design. Reactivity is a direct measure of how readily a given limestone will provide alkalinity and react with the acid resulting from the dissolution of sulfur dioxide into water. This term is used in estimation of the amount of limestone that must be fed into the absorber to maintain a given pH for a given Ca/S stoichiometry and solids residence time. When a limestone possessing lower than design reactivity is used, reaction tanks designed for more reactive limestones may be inadequate to fully dissolve the limestone, feed rates may increase and gypsum purity would decrease due to increased inerts and unreacted CaCO3 and MgCO3 fed to the dewatering system. Due to natural variation occurring in crystal structure among limestones, this parameter has to be empirically determined, rather than predicted from the results of compositional analysis. The most common method used to determine reactivity is through bench-scale experimentation. Ideally, limestone reactivity test methods would provide an absolute reactivity constant that could be directly used to evaluate a limestone and determine the performance of a specific absorber design. However, development of a method to determine absolute reactivity in terms of reaction rate constant is very difficult. Most methods determine the relative reactivity, which provides a measure of reactivity as compared to a reference limestone of known performance. Presently, an industry standard is not available and a number of different procedures exist for conducting such measurements. Herein is discussed methodology for determination of limestone reactivity.
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Introduction
Accurate determination of limestone composition and reactivity are crucial in selection of reagents for wet flue gas desulfurization (FGD) applications, especially for systems producing commercial grade gypsum products. Engineering design of wet FGD systems are based upon many factors including assumptions of the composition and reactivity. While systems can be constructed to utilize a wide range of limestone composition and reactivity, limestone quality must be agreed upon early during system design because this parameter affects unit sizing, product quality, wastewater treatment, limestone consumption rate and system performance. Though lower quality limestone may provide an advantage in system operating cost, the benefit of these savings should be weighed against impacts on system performance. Limestone of acceptable quality is necessary for achieving design level performance. Reactivity is a direct measure of how readily a limestone will provide alkalinity and react with the acid resulting from the dissolution of sulfur dioxide into water. This parameter is important because the liquid to gas ratios (L/G) and pressure drop of contacting devices increases with decreasing reactivity. In addition, higher limestone consumption rates and larger reaction tanks would be needed to achieve comparable levels of SO2 removal than would be needed with more reactive limestones. Higher limestone consumption, in turn, may cause decreased gypsum purity or an increase in purge and waste streams. Larger reaction tanks required to improve utilization of limestones of lesser reactivity incur greater capital expense. Due to natural variation occurring in limestone mineralogical structure, reactivity is empirically determined, rather than predicted from the results of compositional analysis. The most common method used to
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determine reactivity is through bench-scale experimentation. Ideally, limestone reactivity test methods would provide an absolute reactivity constant that could be directly used to evaluate a limestone and determine the performance of a specific absorber design. However, development of a method to determine absolute reactivity in terms of reaction rate constant is very difficult. Most methods determine the relative reactivity, which provides a measure of reactivity as compared to a reference limestone of known performance.

wet FGD absorber. Sulfur dioxide in flue gas enters in the absorber, where it dissolves into the aqueous phase of the absorber slurry and dissociates to produce sulfurous acid. The acid acts in a heterogeneous reaction at the surface of limestone particles, yielding calcium cations and hydrogen carbonate anions within the slurry. The hydrogen carbonate then undergoes acid-base neutralization, producing carbon dioxide and water. These reactions are provided in Equation 1 through Equation 5. Equation 1: Equation 2: Equation 3: Equation 4: Equation 5: SO2 (g) SO2 (aq) SO2 (aq) + H2O HSO3- + H+ CaCO3 (s) + H+ Ca2+ + HCO3- HCO3- + H+ + CO2 (aq) + H2O CO2 (aq) CO2 (g)

Background
Determination of limestone reactivity is essential for accurate modeling and design of wet FGD systems. As reactivity is a measure of the rate at which a limestone will provide alkalinity to react with the acid created during SO2 dissolution and hydrolysis, this term is used in estimation of the amount of limestone that must be fed into the absorber to maintain a given pH for a given Ca/S stoichiometry and solids residence time (tank size). This can be accounted for in the initial design of the wet FGD system. However, when a limestone possessing lower than design reactivity is used, reaction tanks designed for more reactive limestones may be inadequate to fully dissolve the limestone. Further, feed rates would increase over those developed for the reactive limestone in order to maintain pH and SO2 removal. Therefore, gypsum purity would decrease due to increased inerts and unreacted CaCO3 and MgCO3 fed to the dewatering system. The flow rates of waste streams may also be increased. Presently, an industry standard is not available and a number of different procedures exist for conducting such measurements. A test method is presently under development by ASTM. Babcock & Wilcox Power Generation Group, Inc. (B&W PGG), utilities, limestone suppliers and other OEM providers are supporting this effort by serving on the task group. The methodology discussed herein was developed by and is presently used by B&W PGG to conduct limestone analysis.

The overall reaction between limestone and acid is summarized in Equation 6. Equation 6: 2H+ + CaCO3 (s) Ca+2 + CO2 (aq) + H2O Limestone dissolution, acid neutralization and CO2 stripping continues to occur within the absorber reaction tank. Additional reactions occur within the reaction tank, including sulfite oxidation (Equation 7) and gypsum formation (Equation 8). Equation 7: O2 (g) + 2HSO3- 2SO4-2 + 2H+ Equation 8: Ca2+ + SO4-2 + 2H2O CaSO4 2H2O Limestone reactivity is used during system design to determine the amount of limestone that must be fed into the absorber to maintain a given pH for a given Ca/S stoichiometry and solids residence time. When a limestone possessing lower than design reactivity is used, reaction tanks designed for more reactive limestones may be inadequate to fully dissolve the limestone. Limestone feed rates would need to increase to maintain design levels of SO2 removal efficiency. Unreacted limestone exits the absorber tower and is fed to the dewatering system. Levels of calcium and magnesium carbonate within the gypsum cake will increase, decreasing gypsum product quality.

Nomenclature
NIST Reactivity National Institute of Standards and Technology A measure of the rate at which a limestone will provide alkalinity to react with the acid created during SO2 dissolution and hydrolysis Standard Reference Material Flue Gas Desulfurization Argillaceous limestone control Dolomitic limestone control

Limestone Reactivity Testing

Key parameters for relative reactivity measurement
Critical parameters for methodologies aimed at relative measurement of limestone reactivity include, but are not limited to the following: Sample preparation pH and automatic titrator control settings Acid used for titration Common ion concentration Use of and type of wetting agent Electrode type
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SRM FGD 1d 88b

Wet FGD system chemistry

As limestone is mostly composed of carbonate species and as it is a prolific and readily available quarried stone, it is used to provide the alkalinity for reaction with SO2 within the wet FGD absorption process. The limestone is pulverized and mixed with water to form slurry that is fed into the
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 Selection of a control limestone Correction for initial PSD, to account for the bias introduced by deviances in sample PSD. Repeatable sample preparation is essential, as differences in limestone grind will produce different initial particle size distributions. Sample preparation methods should be as similar as possible, using the same grind and sieve settings and techniques for all samples. Due to differences in bond work index between different mineral structures within limestone, use of a double-screened fraction is not necessarily a solution, as this may introduce error in results due to differences in the limestone composition within each screened range as compared to that of the bulk limestone. Therefore, all of the sample to be tested should pass through the specified mesh. The pH used should be representative of a wet FGD absorber, and a tight control system should be employed to ensure constant pH and controlled acid addition. Control of the pH is necessary because limestone dissolution is a function of pH. The controller must be tuned such that undershoot and overshoot of pH is minimized. Limestone undergoes a heterogeneous reaction with aqueous H+ during titration; the comparative rate of this reaction as compared to a control stone is the relative reactivity of a limestone. Swings in pH will change the rate of this reaction, rendering results inconclusive. B&W PGG uses an automatic titrator to provide system control, though other methods may be possible. The acid used during titration affects various aspects of the method, especially PSD measurement. Limestone undergoes a reaction with the aqueous hydrogen ion; therefore, any acid may be selected for use in limestone titration. Commonly, HCl or H2SO4 are selected. Use of H2SO4 may provide a more accurate basis for modeling of an entire wet FGD system, but is not thought to offer an advantage when determining reaction rate. When H2SO4 is used as the titrant, gypsum product is produced, precluding measurement of limestone particle size after the start of reaction because of gypsum particle interference. Further, electrode scaling and fouling may become issues when using H2SO4. Since direct

reaction between limestone and the anion species does not occur once the acid has dissociated, HCl may be used for limestone titration. The resulting products remain soluble, leaving unreacted limestone and inert species as the only particulate within the CaCl2 solution. Consideration should also be given to the effect of common ion concentration on CaCO3 reactivity. Due to the principles of chemical equilibrium, the rate of the reaction between limestone and H+ is affected by the relative concentrations of products and reactants within solution. As reactivity tests methods are aimed at measurement of this reaction rate, even relative test methods should seek to keep the concentration of Ca+2 within the solution relatively constant. For the B&W PGG method, which uses HCl as the titrant, the concentration of the calcium ion will impact limestone dissolution. Initial calcium ion concentration of the solution should be set such that change in this ion concentration over the test duration is negligible. To explore the effect of initial Ca+2 ion concentration on reactivity, testing was performed using various molar concentrations of CaCl2 for the starting solution. Results are provided in Figure 1. A decrease in the measured reactivity is observed as initial CaCl2 concentration increases. The effect of common ion concentration may be less of a factor when H2SO4 is used as a titrant, as a solid product would be formed. Some limestones will float when added to solution, and a wetting agent may be needed to provide accurate results for such samples. If the sample is not fully wetted, less limestone surface area would be available to react within the system per unit mass of sample. In effect, the sample would be expected to perform as if less sample were initially added. Use of a wetting agent ensures that all of the sample surface area is available for heterogeneous reaction. If a wetting agent is selected, it should be used for all samples. Methanol and Triton X-100 are two possible wetting agents. B&W PGG used to perform reactivity testing using methanol, but concerns over agglomeration have resulted in switching to use of Triton X-100 (Figure 2). B&W PGG uses Triton

Fig. 1 Relative reactivity of the B&W PGG control limestone tested with different starting concentrations of CaCl2 as compared to the standard test conditions. Babcock & Wilcox Power Generation Group

Fig. 2 Sample Sauter mean diameter for the control limestone, NIST argillaceous limestone standard reference material 1d and reagent grade calcium carbonate, measured after 60% reaction of sample alkalinity, tested using either methanol or Triton X-100 as a wetting agent. 3

X-100, as this chemical acts as a dispersant in addition to a wetting agent, reducing possible error from sample agglomeration. A non-fouling electrode with fast response is to be used. B&W PGG recommends the DGi-114-SC electrode in combination with an automatic titrator. B&W PGG compares limestone reactivity test results to results from limestone of known field performance to provide a relative comparison of reactivity while perfecting our method for determination of an absolute constant. Selection of a proper control material is considered essential for valid results. The control material should provide repeatable results and be widely available. B&W PGGs experience is that naturally occurring limestones perform differently in reactivity tests as compared to synthetic blends. Some would propose use of reagent grade CaCO3 as a standard control. However, B&W PGG feels that since the control limestone is meant to serve as a basis for relative comparison of reactivity, that this would not be adequate. One reason for this is that the particle size distribution of the reagent grade CaCO3 is not representative of a ground limestone. In addition, there were indications that even when correcting for PSD, the reagent grade CaCO3 reactivity was higher than naturally occurring limestones of high alkalinity. This could be related to the crystal structure and composition of reagent grade CaCO3 as compared to natural limestone. B&W PGG has tested the same limestone that has been ground to different degrees of fineness. Results indicate that the empirically determined value for the reaction rate will not be constant unless corrected for PSD. Therefore, a correction for initial PSD will likely be necessary, even for relative techniques, to account for the bias introduced by deviances in sample PSD.

Titration endpoint Percentage of limestone reacted at titration endpoint Effect of inerts The stat titration curve should produce a region wherein the derivative of the natural log of the fraction of limestone remaining with respect to time is constant; one should ensure that the titration endpoint occurs within this region of constant slope. To obtain a reaction rate constant for limestone dissolution, the surface area available for reaction must be known. Unfortunately, the PSD of a limestone sample is not constant over time. During the course of reaction, smaller particles will be preferentially exhausted, causing the SMD of the limestone sample to change during partial reaction of a limestones alkalinity. Therefore, the particle size distribution must be measured at the point in titration where the reaction rate constant is to be calculated. This is necessary in order to obtain the value for surface area used in calculation of the heterogeneous rate constant. The concentration of inert species relative to the limestone increases as limestone dissolves. Limestone particles breaking down during reaction may also release inert particles. Therefore, the contribution of inert species is to be considered.

Methodology
The B&W PGG limestone reactivity test method is used to ascertain the rate constant of a limestone sample and to qualify candidate limestones for suitability as wet FGD reagents with regard to this parameter. This method uses an automatic titrator to add HCl to a fixed amount of limestone sample. The automatic titrator includes an agitator and provides precise control over the titration, which is necessary when determining the rate of reaction. Particle size distribution (PSD) measurements are taken to provide an estimate of the limestone surface area available for reaction. Results from titration and PSD measurements are used to estimate the reactivity constant of a given limestone. As

Additional parameters for absolute reactivity measurement

Additional parameters needed for empirical quantification of a limestone reactivity reaction rate constant include:

Fig. 3 Volume of acid added as a function of time for 60% titration of one run of a wet FGD reagent limestone alkalinity using HCl. 4

Fig. 4 Natural log of the fraction of limestone remaining as a function of time for 60% titration of one run of a wet FGD reagent limestones total alkalinity using HCl. Babcock & Wilcox Power Generation Group

method refinement towards an absolute measure of limestone reactivity continues, results are presently compared to a limestone of known field performance. To prepare the sample, the limestone is pulverized in a disk mill and screened such that 100% passes through 325-mesh (45 m). By using a constant mill setting during grinding and by screening the sample, some control over PSD is afforded. However, obtaining two samples with the same PSD is highly unlikely, even from the same screening. This is primarily due to differences in the BWI of the different limestone samples. Double screening is not used due to concern that error may be induced through such activity as, theoretically, fractions of differing composition may result above and below the smallest screen. Additional testing of this sample preparation protocol is required. Within a wet FGD system, limestone is thought to react with the hydrogen ions in solution resulting from SO2 dissolution and its subsequent hydrolysis in water. As limestone does not react directly with SO2, but, rather, reacts with the protons released from its absorption, any acid may be used to model the reaction of limestone and acid. This becomes apparent from review of Equation 1 through Equation 6. B&W PGG chooses to use HCl for limestone reactivity testing because the products of this reaction remain soluble in water, unlike the gypsum that would be produced during reaction with H2SO4. The presence of gypsum within the system precludes limestone PSD measurement after reaction initiation, as one would not be able to differentiate between limestone and gypsum particles during PSD analysis. Through the use of HCl, PSD measurements may be taken at later stages in the reaction. A one-gram sample of the prepared limestone is titrated with HCl in an automatic titrator until complete reaction at a pH of 3.85. Use of a compatible wetting agent is critical to allow wetting of the limestone sample and to ensure complete suspension of the limestone sample particles. The volume of acid added is recorded and this result is used to determine total alkalinity of the limestone sample. From analysis of the titration results, the amount of HCl required to titrate 60% of the total alkalinity is calculated. A second one-gram sample from the same screening is prepared and titrated at a pH of 5.0 until the calculated volume of acid required to react 60% of the total alkalinity has been added. Results are recorded as volume of acid added as a function of time (Figure 3). During data analysis, the 60% titration data, original sample mass and total alkalinity of the sample are used to construct a curve for the natural log of the limestone fraction remaining as a function of time. The instantaneous slope of this curve at the endpoint of titration is used in calculation of the reaction rate constant. PSD measurements for the sample are obtained at the titration endpoint to correspond with this slope (Figure 4). This sample is quantitatively transferred and diluted to 1-L in a volumetric flask with 0.6 M CaCl2 solution. A PSD reading is taken on an aliquot of this diluted sample using a spectrophotometer or Microtrac particle size analyzer.
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Next, an excess of HCl is added to this sample, reacting the remainder of the samples alkalinity. Another PSD reading is made to measure the inerts. The two PSD readings are used to determine the specific surface area, expressed as the Sauter Mean Diameter (SMD), of the alkaline species in the sample when 60% of the alkalinity has been reacted. The alkaline particles are assumed to be spherical. The Sauter Mean Diameter and the rate of acid addition are used to determine a reaction rate constant with units of microns of alkaline particles reacted per minute. The rate constant is independent of the actual particle size.

Results and discussion

Finding appropriate control limestones for reactivity testing can be complicated. Unlike controls for compositional analysis, synthetic blends cannot be created from spiking known materials, because such blends may not behave in the same manner as a cohesive natural stone, with each species in the blend likely reacting independently during the course of titration. Therefore, four known materials were tested. These include a field limestone of known performance (the B&W PGG laboratory control limestone), NIST argillaceous limestone SRM 1d, NIST dolomitic limestone SRM 88b and reagent grade calcium carbonate. Results of the B&W PGG reactivity test method are exhibited in Figure 5, as compared to the reactivity of the B&W PGG control limestone. The reagent grade calcium carbonate, being a purely reactive species, had the highest reaction rate. The dolomite control barely reacted within the system, requiring 13.5 hours to react to 60% of the total sample alkalinity. NIST SRM 1d provided acceptable results. From these, one finds that the test method is able to accurately differentiate limestone with varied reactivity. These same limestones were tested using the B&W PGG 5-minute test method. Results are presented in Figure 6. This test measures the amount of limestone reacted over the course of five minutes. One observes a similar ranking by this test method, supporting the value of such measure-

Fig. 5 Reactivity of reagent grade calcium carbonate, NIST SRM 1d argillaceous limestone and NIST SRM 88b dolomitic limestone relative to the B&W PGG control. 5

Fig. 6 Five-minute relative titration test results for reagent grade calcium carbonate, the B&W PGG control limestone, NIST SRM 1d argillaceous limestone and NIST SRM 88b dolomitic limestone.

Fig. 8 Reactivity of the control limestone taken at different titration endpoints, relative to the reactivity of the control limestone at standard test conditions.

ment. However, this method does have a known bias for some samples because it does not correct for particle size distribution. R&D is presently underway to provide a factor for initial particle size distribution for use with this relative method. Some OEM reactivity test procedures define the titration endpoint differently. The endpoint for the full B&W PGG reactivity test method is 60% reaction of a limestones original alkalinity, as determined by the full titration performed as the first stage of testing. To ascertain the effect, if any, that changing the titration endpoint could have on reactivity, testing was performed during which the limestone control was reacted to 40%, 50%, 60%, 70% and 80% of its original alkalinity. Results in the form of the derivative of the natural log of limestone remaining as a function of time taken at the titration endpoint are shown in Figure 7, plotted as a function of the fraction of alkalinity reacted. From these results, one observes that the slope is not constant as titration progresses, which is as expected. After correction for particle size, one finds that reactivity cannot be said to change at a value equal to or greater than 60% reacted (Figure 8).

Limestone is thought to be less reactive as dolomite fraction increases. The magnesium within the dolomite crystal matrix causes a stronger and more cohesive crystal matrix than the calcite phase, rendering it less reactive. One measure of the dolomite content of limestone is magnesium content. This is not, however, an exact measure because magnesium could exist in other phases within the limestone, such as magnesian calcite. A wide variety of field limestones were tested. Relative reactivity results are plotted as a function of magnesium content in Figure 9. Figure 10 re-presents this data, with the outlying data point from NIST SRM 88b omitted. Though wide scatter exists in the data, one finds an overall trend of decreasing reactivity with increasing magnesium content. The data scatter may be attributed to other variations within the field limestones, such as inert content. Dolomite content may be directly measured by Thermogravimetric Analysis (TGA). Results from reactivity testing of a wide range of field limestones are presented in Figure 11, as a function of dolomite content. This data is presented again in Figure 12, excluding the dolomite control NIST

Fig. 7 Slope of the natural log of the fraction of limestone remaining as a function of time, taken at the titration endpoint, for the control limestone, determined at different titration endpoints. 6

Fig. 9 Reactivity of various limestone samples, shown as a function of magnesium content, relative to the control limestone.

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Fig. 10 Reactivity of various limestone samples, shown as a function of magnesium content, relative to the control limestone results from NIST SRM 88b omitted.

Fig. 12 Reactivity of various limestone samples, shown as a function of dolomite content, relative to the control limestone results from NIST SRM 88b omitted.

SRM 88b. Again, one observes that limestone reactivity decreases with increasing dolomite content supporting the validity of this test method. The data does exhibit a wide berth of scatter. Since these samples are from naturally occurring limestone, such deviations are likely due to differences in chemical and/or mineralogical composition other than magnesium content. Inert content also affects limestone reactivity because the presence of inerts at the limestone surface decreases the active surface area of each limestone particle. If no inerts were present, the entirety of the limestone particles surface area would be available for heterogeneous reaction with acid. Since inert areas are present in the stone, they would be expected to decrease reactivity. Figure 13 displays the reactivity of various field limestones, normalized to the control, as a function of percent inerts as determined by modified ASTM Method C 25-06. As anticipated, one observes a decrease in reactivity with increasing inert content, lending validity to the test method. One of the most prevalent elemental inert species in limestone is silicon. The silicon usually exists as quartz, SiO2, or is

bound to various clays in the inerts. Limestone reactivity as a function of silicon content is plotted in Figure 14 for a number of naturally occurring limestone samples. A trend is observed such that measured reactivity decreases with increasing silicon content. However, there is a wide degree of scatter among the data points. This scatter could be due to other factors that were not held constant, such as dolomite content.

Summary
Accurate measurement of limestone reactivity is needed to qualify limestones for use in wet FGD application. Reactivity is one of the bases used during system design when sizing absorber reaction tanks and determining residence time, calculating limestone feed rates, gypsum purity and SO2 removal efficiency. When limestone with lesser reactivity than design is fed into the system, one or all of these factors are affected. Limestone feed rates would be increased to achieve design SO2 removal, sending more unreacted limestone to the dewatering system and increasing the Ca/S stoichiometry. This unreacted CaCO3 and MgCO3,

Fig. 11 Reactivity of various limestone samples, shown as a function of dolomite content, relative to the control limestone.

Fig. 13 Reactivity of various limestone samples, shown as a function of acid insoluble content, relative to the control limestone.

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Fig. 14 Reactivity of various limestone samples, shown as a function of silicon content, relative to the control limestone.

along with the additional associated inerts, have downstream ramifications. Their concentration in the gypsum product is increased, decreasing gypsum product quality. To improve gypsum quality with less reactive limestone, a higher fraction of purge may be used, sending greater material to wastewater treatment. Method resolution is important, as limestones that will not readily provide alkalinity need to be identified to prevent poor system performance. The reactivity procedure discussed in this paper is able to distinguish between wet FGD reagent quality limestones and dolomitic limestones. As the dolomitic content of a limestone increases, reactivity is expected to decrease this trend was observed with the B&W PGG test method. Similarly, reactivity was also shown to decrease as inert content increased within a variety of field limestones. These trends support the assertion that the B&W PGG method is accurate and useful for determination of wet FGD limestone reactivity.

At present, an industry standard is not available. Though ASTM is actively working towards a standard method, it is unclear when that method would be released and what the scope would entail. EPRI had also developed a method, B7, aimed at mimicking wet FGD conditions, but this method is rather cumbersome for general use. Thus, many OEM suppliers and customers have their own methods to perform such testing; this paper documents one such method. Various parameters would be considered essential for any test method adopted by industry. Foremost, the method should include a correction for particle size distribution. B&W PGG has ongoing R&D for an improved method of correction. Further, tight system control must be maintained, preferably through the use of automatic titration, to ensure that the rate measured is accurate. An inert correction is necessary to account for the presence of acid insoluble constituents within the limestone bulk. The pH at which testing is performed should represent system conditions. Use of a wetting agent that functions as a dispersant is recommended to avoid potential errors from particle agglomeration. The B&W PGG reactivity test method is an established method for determination of limestone reactivity, which aims to determine a rate for limestone reaction within a wet FGD system. This method requires an automatic titrator and experienced technicians to perform properly. Though aspects of the method are proprietary, B&W PGG is working to develop a version that could be performed in a third-party laboratory. At present, results are compared to a control limestone of known performance while method improvement is ongoing. B&W PGG also utilizes a short, relative 5-minute test method for approximation of limestone reactivity. However, as this method has no correction for particle size distribution, and thus, has an inherent bias.

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