Background of the Invention 1. Field of the Invention The present invention relates generally to a method for reducing byproducts emissions from combustion reactions, and, more particularly, to a method for reducing flue gas acidity in combustion furnaces.

2. Description of the Prior Art Acidity decrease The flue gas of power generation plants has long been recognized as a source of atmospheric pollution. In the combustion of fossil fuels, some of the naturally present elements are oxidized to form acids, such as S03, NOx, HCI, HF, and the like. These acids, especially S03, can become a problem if their concentrations exceed certain thresholds. For example, as the S03 concentration increases, the acid dewpoint temperature of the flue gas increases. If the temperature of the flue gas is less than the acid dewpoint temperature of the flue gas, the S03 in the gas will condense and react with water to form H2S04, causing corrosion problems inside the furnace. Also, flue gases exiting a furnace cool immediately and S03 and other acids in the gas condense, creating localized acid rain, which is the condensation and precipitation of S03 and other acids onto the surrounding land with

subsequent corrosion. Excessive S03 will condense into small droplets, creating a visible plume as it exits the furnace, which becomes an esthetic and local political problem. If NH3- like compounds are present in the flue gas, they can react with S03 to form ammonium bisulfate (NH3HS04) which then fouls the air heater.

Thus, a need exists to decrease the acid dewpoint temperature of the flue gases such that the acid dewpoint temperature is lower than the flue-gas temperature in the coolest parts of the furnace, such as the ducts and stack. A further need exists to lower the acid content of the flue gases such that the localized acid rain and other problems associated with high-acid flue gas are minimized.

SO3 increase The particulate matter carried in the flue gas can be removed by electrostatic precipitators that cause the individual particles to accept an electrical charge and then use that charge to attract them to collector plates for disposal. The efficiency of such electrostatic precipitators is dependent upon the ability of the individual particles to take a charge, that is, the resistivity of the particles. It has been found that the presence of S03 in the flue gas effectively reduces the resistivity of the particles, making them easier to charge electrostatically.

In the combustion of coal, some of the naturally present sulfur is converted to S03.

On the other hand, the effectiveness of S03 in reducing the resistivity of the particulate matter in the flue gas depends upon the concentration of the S03, with about 15 to 20 parts per million (ppm) giving optimal results. Therefore, precipitator efficiency is affected by the ability to adjust the amount of S03 in the flue gas, regardless of the sulfur content of the coal being burned, to provide an overall S03 concentration in the optimal range.

S03 is also produced in SCR (catalyst) installations by the oxidation of SOz and often exceeds the optimal 15 to 20 ppm optimal concentrations. The catalyst blends typically used in the SCR to reduce NOx to N2 (in the presence of ammonia) also oxidize SO2 to S03. The rate of this reaction is strongly temperature dependent and, at higher temperatures, can convert more than 1 percent of SO2 to S03. High sulfur U. S. coal generates anywhere from 2,000 to 3,000 ppm of SO2 in the boiler, and therefore can result in 20 to 30 ppm of S03 out of the SCR. The problem is that as much as 50 percent, or 10 to 15 ppm, of the S03 coming out of the SCR will make it past the scrubber and out of the stack. At about 8 to 10 ppm, depending upon the particulate concentration, S03 becomes visible as a blue plume.

Furthermore, S03 can also be produced catalytically on other boiler surfaces through interaction with elements/chemicals such as Vanadium Therefore, because any S03 formed prior to the SCR adds to the effluent S03, reducing the S03 formed prior to the SCR is important for reducing the effluent S03 and permits the use of SCR for the reduction of NOx for gases without generating excessive amounts of S03.

S03 control If the S03 concentration is too low, the precipitator will operate at less than optimal efficiency. On the other hand, if the S03 concentration is too high, the flue gas becomes highly acidic, creating a"blue plume"and contributing to acid rain. In addition, acidic flue gases contribute to corrosion of the pipes carrying the flue gas, and, when combined with NH3-type chemicals, can clog the air heater.

Furthermore, an SCR is often only intended to be used for six months per year (during the summer ozone control season), and are bypassed during the winter. This creates seasonal variability in the S03 concentrations at the precipitator, in the duct work, and out of the exhaust stack.

It is therefore desirable to control the concentrations of S03 in the flue gas depending upon whether the SCR is in use or not. SO3 concentrations approaching 40 ppm produce severe adverse local acid problems that are not necessarily regulated, but create local political problems for the facility. The U. S. EPA has indicated that future regulations on S03 emissions are to be expected.

It is desirable, therefore, to have an S03 flue gas system that is capable of adjusting the concentrations of S03 in a flue gas with or without an SCR installed to maintain the S03 concentration at an optimal level for increased ESP performance, without increased localized S03 emissions.

Staging Combustion staging is the process of burning a fuel, i. e. , coal, in two or more stages.

A fuel-rich stage, or simply, rich stage, is one in which not enough air is available to fully burn the fuel. A fuel-lean stage is one in which there is sufficient or extra air to fully burn the fuel. Staging is used in the prior art to reduce NOx by a) reducing peak temperatures (thermal NOx) and b) providing a reducing environment (NOx reduction). Macro-staging is the dividing of whole sections of a furnace into rich and lean stages and is accomplished through the use of such techniques as Over-Fired Air (OFA). Micro-staging is the creation of proximal microenvironments with functionally different characteristics, such as reduction potential, temperature, and the like. Micro-staging in a furnace can be achieved, for

example, in the first stage of the furnace through the use of Low-NOx burners with adjustment of spin-vane settings and registers. Increased staging increases the residence time in a reducing atmosphere and increases the effect of the reducing atmosphere.

Prior art has used micro-staging to reduce NOx emissions in combustion furnaces.

Low-NOx burners (LNB) stage by delivering high-fuel-content primary air into the furnace that mixes with secondary air flowing through one or more secondary air registers. LNB primarily use micro-staging. The flow through a LNB is designed such that the volatile components of the coal mix with the available near-field air at a stoichiometric ratio near unity (1.0), thus anchoring the flame. The net combustion in the central core near the burners is overall fuel rich and does not produce much thermal NOx, as the temperatures are low.

The coal is eventually consumed over the depth of the furnace as more and more air slowly mixes into the central core. The majority of the NOx created in this region is from the fuel- bound nitrogen reacting to NO through the intermediate HCN. The rate at which the outer secondary air mixes into the core flow is set by the dampers and the spin vanes, as well as the spin vane in the coal pipe. LNB systems decrease NOx by staging since there is a continuous mixing of the rich products of combustion and secondary air throughout the combustion zone. Staging is increased by decreasing the mixing rate between the rich core flow and the outer secondary air flow.

Prior art has used macro-staging to reduce emissions in combustion furnaces. Macro- staging consists of highly mixed fuel and air in the lower furnace, mixed to a stoichiometric ratio below unity for a large part of the flow. Excess oxygen is ultimately required to assure that all of the fuel has burned and to reduce explosion risks. In a macro-staged furnace, excess air is introduced downstream of the burners. Increased staging is achieved by

increasing the residence time, temperature, or reducing quality of the combustion products in the absence of oxygen.

Prior art used both micro-staging (LNB) and macro-staging (OFA) to reduce NOx emissions in combustion furnaces. In the case of both micro-staging and macro-staging, components of each of the above are used and adjusted to achieve NOx emissions reduction.

Staging has nowhere been taught in the prior art for flue gas acidity reduction, acid dewpoint temperature control or S03 concentration control in combustion gases.

Summary of the Invention The present invention is directed to a method for reducing the acidity of flue gases in combustion systems and methods.

The present invention is further directed to a method for reducing the acid dewpoint temperature of flue gases in combustion systems and methods.

It is therefore an aspect of the present invention to provide a method for reducing the acidity of flue gases in combustion systems and methods, including the steps of : a) partially combusting the fuel in a first stage to create a reducing environment; b) maintaining the reducing environment for a sufficient time period such that reducible acids are reduced to achieve a desirable acidity concentration in the flue gas; c) combusting the remainder of the fuel and combustion intermediates in a second stage with oxidizing environment ; thereby decreasing the acidity of the flue gas by reducing the acid concentration of the gas.

Another aspect of the present invention provides a method for reducing the acid dewpoint temperature of flue gases in combustion systems and methods with staging.

Still another aspect of the present invention provides a method of lowering the acid dewpoint temperature of flue gas, including the steps of: a) partially combusting the fuel in a first stage to create a reducing environment ; b) combusting the remainder of the fuel and combustion intermediates in a second stage with oxidizing environment; c) measuring the acid dewpoint of the flue gas; d) adjusting the reducing environment for a sufficient time period such that the flue gas acid Still another aspect of the present invention provides a combustion furnace operated with a method for reducing the acidity of the flue gas, the method steps including: a) partially combusting the fuel in a first stage to create a reducing environment; b) maintaining the reducing environment for a sufficient time period such that reducible acids are reduced to achieve a desirable acidity concentration in the flue gas; c) combusting the remainder of the fuel and combustion intermediates in a second stage with oxidizing environment; thereby decreasing the acidity of the flue gas by reducing the acid concentration of the gas.

These and other aspects of the present invention will become apparent to those skilled in the art after a reading of the following description of preferred embodiment (s) when considered with the drawings.

Detailed Description of the Invention In the following description, like reference characters designate like or corresponding parts throughout the several views. Also in the following description, it is to be understood that such terms as"forward,""rearward,""front,""back,""right,""left,""upward ly," "downwardly, "and the like are words of convenience and are not to be construed as limiting

terms. In the present invention, "reducible acid"refers to acids in which the acidity can be reduced or eliminated by the electrochemical reduction of the acid.

The present invention is directed to a method for in-furnace decrease and control of the acid dewpoint temperature using combustion staging. The present invention is further directed to a method for in-furnace reduction and control of S03 using combustion staging.

Increased staging is advantageously used to simultaneously decrease the acidity, decrease the acid dewpoint temperature and reduce the S03 levels of the flue gas.

Acidity, acid dewpoint temperature and SO reduction through micro-staging Similar to how NOx is reduced back to N2 in a rich"reducing"environment, S03 is reduced back to SOx in a reducing environment. With macro-staging, the center of the furnace below the OFA ports is largely fuel-rich. This staged environment can be adjusted to be even less mixed to create reducing micro-stages within the first stage of the furnace. The mixing can be reduced by reducing the spin vane velocity settings of the primary air and coal flow, or additionally or otherwise, the secondary air spin vane and register settings, thus creating reducing micro-stages, or additionally or otherwise, the relative exit velocities between the primary air and coal flow and the secondary air flow can be changed.

While the majority of fuel-bound sulfur forms SO2, some forms S03 directly during combustion of the fuel-bound sulfur. SO2 can react to form more S03 through the following oxidative reaction: SO2 + O (+M)- S03 (+M) However, this three-body reaction is very slow. An additional source for S03 production in an oxidative environment is through the reaction:

S02 + 02- SOs + 0 This reaction does not require three bodies to simultaneously collide; however, it is very sensitive to temperature, requiring high temperatures, and it is susceptible to reverse reaction: SO3 + O # SO2 + O2 None of the above three reactions occur in any significant quantity in a reducing environment due to the lack of O and 02 species. In a reducing environment, the direct conversion of S03 to SO2 takes place through the following general"reducing"reaction: SO3 + R # SO2 + RO Where R is any reducing radical species. The primary radical in fossil fuel combustion is the H radical.

SO3+HoSO2+0H Many radicals and molecules can be functional in a reducing environment; e. g. , H, OH, C, CO, CH, CH2 C2H, CH3, CnHm, N, NHi, and many others.

The above S03 reducing reactions are very fast when there are significant concentrations of the reducing radicals ("R"). Sufficient concentrations exist primarily in reducing environments within the first (fuel-rich) stage of the furnace.

In a fuel-rich staged, reducing environment, oxidative chemistry terminates due to greatly decreased (extinguished) concentrations of oxidative combustion species; e. g. , OH, 0, 02, HO2, H202, and many others. In this environment, species are very competitive for any available oxygen species. Molecules with oxygen atoms that exist in relatively small

1) The distance between stages can be lengthened 2) The mixing can be increased for macro-staging applications 203) The mixing can be decreased for micro-staging applications 4) The mass flow between stages can be reduced (deeper staging) 5) The volumetric utilization between stages can be increased (e. g. , swirl) 6) The pressure can be increased concentrations are consumed by oxygen-wanting species that exist in high concentration; e. g. , the oxygen in NO is consumed by other species like C, CO, H, and CH. Molecules that have multiple oxygen atoms are particularly at risk; i. e., S03 will quickly revert to SO2 through oxygen abstraction by just about anything around, most notably H atoms.

Thus, in a reducing environment, the S03 reduction reaction is very fast virtually irreversible while the reducing environment is maintained.

Surprisingly and importantly, with the present invention methods and systems, the net effect is that any S03 that is formed during combustion is quickly reduced to S02 in the first stage and S03 is not reformed by oxidation to S02 because there is not enough residence time at sufficiently high temperature in the furnace in the latter, fuel-lean stages. Thus, the present invention advantageously uses the differences in reaction rates to reduce and maintain the S03 levels in the flue gas.

Increased staging increases the residence time in a reducing atmosphere, or increases the reducing potential of the atmosphere, to decrease S03 concentration and thereby lower the dewpoint temperature. Therefore, to increase the reduction of S03, the residence time can be increased or the reducing potential in the flue gases can be increased.

To increase residence time, several methods are available.

7) The density can be increased To increase the reducing potential in the flue gases, several methods are available.

1) The temperature can be increased 2) The stoichiometric ratio (i. e. , the air-to-fuel ratio) can be decreased.

53) The local fuel flow can be increased (for fixed air flow) 4) The local air flow can be decreased (for fixed fuel flow)

Mixing within a stage also influences the reduction process. A perfectly mixed stage with a stoichiometric mixture is the best, since these reaction conditions will give the highest temperature, while still maintaining the reducing environment; i. e., minimizing oxidation radicals like O radicals. But, since perfect mixing is impractical, in practice a stoichiometric ratio less than one is used, which minimizes the occurrence of localities with a stoichiometric ratio greater than one. However, as mixing is reduced, a longer residence time and/or higher temperature is needed to achieve a similar reduction of the total acidity, acid dewpoint temperature, and/or S03 concentration. However, the temperature of the combustion gases is dependent to a certain extent on the level of mixing, going down if mixing is decreased.

Therefore, if an increased temperature is desired for a given degree of mixing, temperature must be increased by other means, such as preheating air, changing heat transfer characteristics of furnace, and the like. Alternatively or additionally, the residence time in the reducing environment can be increased by delaying lean stage air introduction, such as OFA injection.

Note that S03 is formed by the oxidation of SO2 in a catalyst because a catalyst enables the oxidation of S02 though the following reaction: S02 + 02- S03

Production of S03 in a catalyst is independent of the S03 concentration in the gas, since the catalyzed reaction is only dependent on the SO2 and °2 concentration. Therefore, any S03 that is reduced by the present invention independently reduces the exit S03 and is not affected by and does not affect S03 production in a catalyst.

The present invention thus provides a method for controlling and reducing flue gas acidity, specifically the flue gas concentrations of S03, in order to beneficially (1) affect the efficiency of an electrostatic precipitator, and more particularly, (2) to reduce the concentration of S03 and other reducible acids in the flue gas in order to reduce the flue gas acidity and acid dewpoint, thereby reducing air heater pluggage, duct corrosion, and S03 emissions to the environment, which can be a source of visible plumes and localized acid rain.

In a preferred embodiment of the present invention, macro-staging to regulate furnace acidity and S03 levels is achieved through the use of OFA. In another preferred embodiment, micro-staging to regulate furnace acidity and S03 levels is achieved through the use of low-NOx burners. In yet another preferred embodiment, macro-staging and micro- staging through the use of OFA and low-NOx burners in combination are used to regulate furnace acidity and S03 levels. For furnaces with SCRs in operation, the acidity is preferably regulated to reduce total flue gas acidity. For furnaces without SCRs or with by-passed SCRs, the S03 is preferably regulated such that the S03 levels going to the ESP enhance or favor precipitation. For current ESPs, S03 levels between about 10 to about 15 ppm (by volume) in the exhaust is desirable for best ESP efficiency.

The dewpoint temperature is a convenient parameter for estimating and/or adjusting the reducing environment variables in order to achieve adequate reduction of acidity and/or

desired S03 levels. For a desired level of S03 and operating relative humidity, the dewpoint can be determined and the reducing environment variable adjusted accordingly to achieve the desired dewpoint. Other methods of determining acidity and/or S03 level can be used for the same purpose without departing from the scope of the invention.

In a preferred embodiment of the present invention, a power plant is operated to provide a deeply-staged, micro-stage or macro-stage reducing environment in the lower furnace. The OFA in the upper furnace provides the necessary oxygen to ensure an acceptable level of burnout of the remaining unburned fuel, combustion intermediates, and CO. Additionally, an SCR can be used to reduce NOx. Thus, an embodiment of the present invention includes a combustion furnace with OFA and low NOx burners for use with sulfur containing fuels to lower the dewpoint temperature and to reduce the S03 concentration..

Additionally, an SCR can be provided to reduce NOx. The low NOx burners are preferably of a grade that provides adequate mixing in the primary stage to provide adequate acid dewpoint temperature reducing and S03 concentration reduction, thus permitting the use of an SCR, if necessary. Thus, an embodiment of the present invention includes a combustion furnace with high-grade low NOx burners for the purpose of reducing the flue gas acidity, lowering the acid dewpoint temperature and reducing the flue gas S03 concentration. This embodiment can further include an SCR.

An adequate reducing environment according to the present invention is one that will reduce S03 to S02 in less than about 2 seconds, more preferably, in less than about 0.5 seconds. In the present invention, such a reducing environment can be achieved when the first stage flue gas temperature is greater than or equal to 900 Kelvin (1160 degrees F), more preferably greater than about 1255 K (1800 degrees F), even more preferably greater than

about 1650 K (2500 degrees F). A reducing environment is one where the ratio of the concentrations of reducing radicals to oxidizing radicals is greater than about 1; more specifically, the ratio of the concentrations of H radicals to O radicals is greater than about 1.

A better reducing environment is one where the ratio of the concentrations of reducing radicals to oxidizing radicals is greater than about 10; more specifically, the ratio of the concentrations of H radicals to O radicals is greater than about 10.

Thus, a method for operating a furnace according to the present invention involves the steps of: a) partially combusting the fuel in a first stage to create a reducing environment; b) maintaining the reducing environment for a sufficient time period such that S03 is reduced to SO2 to achieve a desirable level of S03 ; c) combusting the remainder of the fuel and combustion intermediates in a second stage with oxidizing environment; thereby controlling the levels of S03 in the flue gases.

Alternatively, in another embodiment according to the present invention, a method of lowering the acid dewpoint temperature of flue gas includes the steps of: a) partially combusting the fuel in a first stage to create a reducing environment; b) combusting the remainder of the fuel and combustion intermediates in a second stage with oxidizing environment; c) measuring the acid dewpoint of the flue gas;

d) adjusting the reducing environment for a sufficient time period such that the flue gas acid dewpoint is lowered to a desirable level; thereby decreasing the acid dewpoint temperature of the flue gas by reducing the reducible acid concentration of the gas.

Examples The following examples illustrate the results that can be achieved using methods according to the present invention. Methods according to the present invention were used to reduce flue gas acidity and lower acid dewpoint at 3 different power plants. Because S03 is the predominant acid in coal furnace emissions, S03 emissions were measured and used as an indicator of acidity and dewpoint. The experimental data shown in Tables 1 and 2 were achieved through the use of high-velocity over-fired air and were measured by third-party companies.

Table 1. Effects of Staging Depth on S03 levels at 2 different plants. Plant 1 Plant 2 Staging Depth Parameters Shallow Deep Shallow Deep Load (MW net) 182 179 154 154 NOx (lb/MWtu) 0.64 0.36 0. 63 0. 28 Coal % S (%) 1.22 1.22 0. 87 0. 87 Outlets SO2 (ppm) 1100 1100 720 720 Outlet S03 (ppm) 19 5.7 11* 0. 5 S03/S02 (%) 1.7 0.52 1. 5* 0. 07 S03 Reduction 70% 95%

N/A-Data Not Available; *-Estimated based on assumption that 98.5% of the sulfur in coal goes to S02 and 1.5% of the sulfur in coal goes to S03.

For the"shallow"staging cases, the over-fired air ports were nearly closed, but still contained cooling flow (around 10% of the total air). For the"mid"staging case, the

over-fired air ports made up nearly 20% of the total air flow. For the"deep"staging cases, the over-fired air ports made up nearly 30% of the total air flow. All three units were corner-fired units and the OFA system was located well above the burner zone.

Table 2. Effect of three levels of staging at a single plant (Plant 3, different from Table 1). Staging depth Parameters Shallow Mid Deep Load (MW net) 72 72 72 NOx (lb/MMBtu) 0. 56 0. 48 0.34 Coal % S (%) 2. 85 2. 85 2. 85 Outlets S02 (ppm) 1856 1855 1856 Outlet S03 (ppm) 5. 9 1. 9 1.1 S03/S02 (%) 0. 32 0. 1 0.06 S03 Reduction (vs Shallow) 68% 81%

Thus, the experimental data demonstrate the ability to regulate the S03 level, which is the predominant acid in coal furnace emissions and an indicator of flue gas acidity and acid dewpoint, using methods according to the present invention.

Certain modifications and improvements will occur to those skilled in the art upon a reading of the foregoing description. All modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.