METHOD FOR PREVENTING FORMATION OF AMMONIUM BISULFATE, SULFURIC ACID, AND RELATED PRODUCTS IN COMBUSTION EFFLUENTS

Abstract: The present invention is related to a method for preventing the formation of NH₄HSO₄ during the noncatalytic reduction of nitric oxide by ammonia or ammonia precursors in combustion effluents. The present invention is also related to a method for preventing the formation of H₂SO₄ in the absence of ammonia or its precursors. The formation of these corrosive substances is extremely detrimental. NH₄HSO₄ formation is a limitation upon the usefulness of nitric oxide reduction processes, particularly in boilers, furnaces, and other combustion devices. The formation of H₂SO₄ limits effective heat recovery in combustion equipment. The present invention specifically teaches the use of methanol to reduce SO₃ in the effluent stream to SO₂. The noncatalytic reduction of SO₃ by methanol is selective in that a large fraction of the SO₃ is converted to SO₂, while on a percentage basis very little oxygen is consumed. In addition, the process of the present invention allows the amount of methanol to be limited such that significant amounts of carbon monoxide are not produced and emitted with the effluent stream. By eliminating SO₃, the formation of NH₄HSO₄ and H₂SO₄ can be blocked. The present invention teaches contacting the methanol with the combustion effluent at a temperature ranging from approximately 500°C to about 950°C in order to assure proper operation of the process. It is also important to limit the reaction time used so that the carbon monoxide produced by the methanol oxidation is not itself oxidized to carbon dioxide.

Description: BACKGROUND 1. The Field of the Invention The present invention is related to methods for preventing corrosion and fouling of boilers, furnaces, and other burner equipment through preventing the formation of ammonium bisulfate (NH₄HSO₄) and sulfuric acid (H₂SO₄) in the effluent stream from said boilers, furnaces and other burner equipment. More particularly, the present invention relates to preventing the formation of ammonium bisulfate and sulfuric acid by the selective, noncatalytic reduction of sulfur trioxide (SO₃) to sulfur dioxide (SO₂), thereby making the SO₃ unavailable to react with water vapor or water vapor and ammonia to form those undesirable products. 2. The Background of the Invention A. General Background One of the major problems in modern industrialized society is the production of air pollution from numerous sources. Air pollution can take various forms. Some of the different types of air pollutants include particulate emissions such as dust, coal particles and the like, sulfur compounds such as SO₂ and SO₃, ozone, carbon monoxide emissions, volatile hydrocarbon emissions, and the emission of nitrogen compounds commonly referred to collectively as "NO x ." Pollution sources include automobiles, industrial plants, small commercial establishments (such as dry cleaners and service stations), and even nature itself. Combustion effluents and waste products from particular types of sources have proven to be major contributors to damaging air pollution when the effluents are discharged into the atmosphere. Unless these waste products are treated before their release into the atmosphere, serious smog and other air pollution problems are encountered. It will be readily appreciated that high concentrations of air pollutants can have serious deleterious impacts on the health and the general welfare of society. Air pollution is known to aggravate certain medical conditions (such as heart and lung problems) and is known to cause problems in the environment ranging from corrosion to acid rain. One of the most common components found in polluted air is nitrogen dioxide ("NO₂"), which is known to be an extremely poisonous material. Nitrogen dioxide, which is brown in color, undergoes a series of reactions known generally as "photochemical smog formation" in the presence of sunlight and airborne hydrocarbons. These reactions result in a marked decline in overall air quality. While NO₂ is produced from a wide variety of pollution sources, its primary source is from NO released into the air. NO is commonly formed during combustion processes, including internal combustion engines in automobiles, hydrocarbon fueled power plants, process furnaces, incinerators, coal fired utility boilers, glass furnaces, cement kilns, oil field steam generators, gas turbines, and other similar installations. In these combustion processes, part of the ambient oxygen combines with atmospheric nitrogen (rather than with the fuel) in the flame by a process generally known as "nitrogen fixation." Nitrogen fixation is primarily limited to processes where a flame is employed in the combustion process, as opposed to catalytic processes. However, if there are organic nitrogen compounds in the fuel, they may also form NO when the fuel is burned either by a flame or catalytically. Since NO is the only oxide of nitrogen which is stable at the high temperatures encountered in these types of combustion processes, NO is the predominant product. At normal atmospheric temperatures, however, the equilibrium between NO and NO₂ favors NO₂. Hence, NO formed by combustion is generally discharged into the atmosphere as NO, and only subsequently is converted to NO₂. In order to control NO₂ emissions, therefore, it is necessary to deal to a large extent with NO before it enters the ambient air. B. Nitrogen Removal Processes and Ammonium Bisulfate Formation There have been considerable efforts in the art to find effective ways to remove oxides of nitrogen from waste gases so that these waste gases may be discharged to the atmosphere without harm to the environment. It has been found in the art that the removal of NO₂ is relatively easy since it reacts with water and air to form nitric acid. NO₂, therefore, is commonly removed by aqueous scrubbing. If a base, such as ammonia, is added to the scrub water, the nitrogen scrubbing process is facilitated and ammonium nitrate is produced. If limited amounts of NO are present along with the NO₂, the NO may be co-scrubbed, thereby yielding ammonium nitrate. These processes, however, are subject to the limitation that they are only effective for mixtures of nitrogen oxides which are predominantly NO₂, rather than predominantly NO. This is a problem because NO is the predominate species at the temperatures generally encountered in flue gases. As a result, various processes have been developed in the art for oxidizing NO to NO₂ so that the relative inexpensive and convenient scrubbing processes may take place. For example, methods have been developed for oxidizing and removing NO x exhausted from boilers, cinder furnaces, nitric acid factories, automobiles, and the like. Several processes known in the prior art involve contacting the gaseous flow which includes NO, with various organic compounds (such as aldehydes, alcohols, ketones, organic acids, and the like) in the presence of oxygen. By such processes, the NO is oxidized to NO₂ which can then be removed by the scrubbing processes described above. Similar processes have been developed whereby NO is oxidized to NO₂ by contacting the NO with other types of oxygen-containing hydrocarbons such as methanol and ethanol. An alternative approach for removing NO from flue gases and other streams of pollutants is to reduce NO to nitrogen and water, which may then be discharged to the atmosphere. These processes generally teach the removal of NO x from flue gas by reduction of the NO by the addition of ammonia, or an ammonia precursor, alone or in combination with a second combustible material while the waste gas is at a relatively high temperature (generally from about 700°C to about 1200°C). An example of such an NO reduction process is described in US-A-3,900,554 to Lyon, issued August 19, 1975 (hereinafter referred to as the "'554 patent"). The process disclosed in the '554 patent teaches the reduction of NO to N₂ by injecting ammonia into the combustion effluent stream at a temperature from about 870°C to about 1100°C. If the NH₃ is injected along with a second reducing agent, such as hydrogen, NO will be reduced to N₂ at temperatures as low as 700°C. The method described in the '554 patent for controlling the emission of NO to the atmosphere has a number of advantages. The NO in the emission stream is converted to molecular nitrogen and water. This conversion is accomplished without the use of any catalyst and hence without the substantial expense and difficulties inherent in catalytic processing of combustion effluents. Moreover, according to the process of the '554 patent, the conversion of NO to N₂ is selective and specific. Combustion effluents typically contain NO at concentrations of from about 100 to about 2,000 ppm, while oxygen concentrations are generally in the range from about 2% to about 10%. Thus, the concentration of oxygen is orders of magnitude greater than the concentration of NO. If the reduction of NO were nonselective ( i.e. , if to reduce one percent of the NO, one had to reduce one percent of the oxygen), the amount of reducing agent required would be prohibitive. In the process described in the '554 patent, however, the reduction of NO is achieved with nearly equimolar quantities of NH₃. The reaction is highly selective; reducing a large fraction of the NO while leaving the oxygen largely untouched. Notwithstanding the foregoing advantages, the process described in the '554 patent, and other processes which employ a nitrogen oxide reduction technique, encounter a severe disadvantage in most applications. Many of the sources of the coal and oil commercially used in furnaces, boilers, and other burners, contain some amount of sulfur. In most instances, it is quite expensive and technically difficult to remove the sulfur before burning the fuel. It has been a common practice, therefore, to burn fuels which still contain a portion of the native sulfur. Sulfur compounds, including SO₂ and SO₃, are then produced during combustion and must be removed from the effluent gas stream by separate expensive technologies. Combustion of a sulfur-containing fuel in a boiler, furnace, or other burner typically produces combustion effluents in which 98% to 99% of the sulfur exist in the form of SO₂, and only 1% to 2% of the sulfur exists in the form of SO₃. In processes such as that described in the '554 patent where NO is reduced by injecting ammonia into the gas stream, some of the ammonia or ammonia precursors injected into the process will be left unreacted. Under certain conditions NH₃ will react with the sulfur gases, i.e. , as the combustion effluents cool, the remaining NH₃ will react with SO₃ and water vapor present in the effluent stream to form NH₄HSO₄ according to reaction equation (1): NH₃ + SO₃ + H₂O → NH₄HSO₄ (1) Unfortunately, NH₄HSO₄ is an extremely sticky and corrosive liquid and is known to damage the equipment used in combustion processes. The temperature at which the formation of NH₄HSO₄ occurs is such that in a typical boiler or furnace of the type generally encountered in combustion processes, formation of NH₄HSO₄ occurs within the air heater. Thus, fouling, corrosion, and plugging of the air heater has been commonly encountered. As a result, the nitric oxide reduction technologies which use ammonia and ammonia precursors have had severe limitations and their commercial acceptance has been correspondingly limited. The operators of boilers and furnaces are often extremely reluctant to accept any technology which can cause fouling, plugging, and corrosion such as that expected from NH₄HSO₄. It will be noted that in the event that there are no sulfur oxides in the effluent stream, the formation of NH₄HSO₄ is not a problem. In many combustion applications, however, there will be at least a small quantity of sulfur oxides in the effluent stream and, thus, some SO₃. The ammonia or ammonia precursors which are used in the nitric oxide reduction reactions can then react with the SO₃ present to form NH₄HSO₄, which even in small quantities can cause severe problems over time. It is apparent that one important need in the art is a method for the prevention of the formation of NH₄HSO₄ during the reduction of NO x in the presence of ammonia, or ammonia precursors, when sulfur is present in the effluent stream. It would be an advancement in the art to provide such a method which was operable during the noncatalytic reduction of NO. It would be a further advancement in the art to provide for the removal of SO₃ from the effluent stream so that formation of NH₄HSO₄ was prevented. It would be a further advancement in the art if SO₃ could be selectively and noncatalytically reduced to SO₂, which can be readily removed by conventional techniques. C. Sulfuric Acid Production As mentioned above, the combustion of coal, fuel oil, or other sulfur containing fuel in a normal boiler or furnace produces a flue gas which contains some sulfur oxides. Generally 98-99 percent of the sulfur is oxide gas in the form of SO₂ and 1-2 percent is SO₃. From an air pollution control viewpoint, the major concern is the total emission of sulfur oxides to the atmosphere. In terms of boiler or furnace operation, however, the production of this small amount of SO₃ is a major problem even in environments which are essentially free of ammonia. When the flue gas cools, the SO₃ reacts with water to form a mist of sulfuric acid. If the back end of the boiler or furnace is cool enough so that this acid mist forms inside the unit, severe corrosion problems result. Alternatively, if the back end is warm enough to prevent acid mist formation but the stack is not, the acid mist tends to incorporate any soot that the flue gas may contain. This mixture falling in the immediate vicinity of a smoke stack can cause severe local problems ( i.e. , the "acid smut" problem encountered with fuel oil firing). In the past, the accepted cure for this problem was to keep the temperature of the flue gas throughout the boiler and the stack well above the acid mist point. That is, the problem was solved by deliberately wasting some of the heat produced by burning the fuel. This deliberate waste was always troublesome in that inefficiency was assumed in the operation. This energy waste is especially unsatisfactory now that energy conservation is a matter of priority. Thus, it will be appreciated that in processes which do not employ ammonium compounds to control NO x , production of SO₃ is still a very significant problem. Instead of producing sticky and corrosive ammonium bisulfate, sulfuric acid is produced. Depending on the specific temperature conditions, sulfuric acid may occur within the combustion equipment or in the ambient environment. In either case, undesirable results follow. Accordingly, an inexpensive gas phase homogeneous reaction in which SO₃ was reduced to SO₂ would be an ideal solution to both sets of problems. It would be a further advancement in the art to reduce SO₃ and thereby avoid sulfuric acid formation using a noncatalytic reaction. It would be a related advancement in the art to remove SO₃ during the combustion process such that subsequent removal of SO₃ was not necessary. Such methods and apparatus are disclosed and claimed below. BRIEF SUMMARY AND OBJECTS OF THE INVENTION One embodiment of the present invention is related to a method for preventing the formation of NH₄HSO₄ during the noncatalytic reduction of nitrogen oxides by ammonia or ammonia precursors. As was discussed above, when NO x (primarily NO) is reduced using ammonia or ammonia precursors to form nitrogen, in the presence of some SO₃, the formation of NH₄HSO₄ often occurs. The formation of this sticky and corrosive substance inside the combustion unit downstream of the NO reduction zone is an extreme limitation upon the usefulness of nitrogen oxide reduction processes, including specifically the nitrogen oxide reduction process of the '554 patent. In another embodiment, the present invention is related to methods for preventing the formation of sulfuric acid. As discussed above, when SO₃ and water vapor are both present in a hot effluent stream, a reaction of the two to form sulfuric acid is expected. It will be appreciated that this reaction is particularly prevalent where ammonia is not being used to reduce NO x emissions. The present invention teaches the use of methanol to reduce SO₃ in the effluent stream to SO₂ in order to prevent formation of sulfuric acid or ammonium bisulfate. The methanol is oxidized in the process, with the chief product of that oxidation being carbon monoxide ("CO"). It will readily be appreciated that the emission of more than a small amount of CO to the atmosphere can be an undesirable condition. Accordingly, the present invention also teaches a method whereby the amount of CO emitted to the atmosphere is limited to acceptably small values by limiting the amount of CO initially produced. This is accomplished by using methanol in only limited amounts. Since the process of the reduction of SO₃ with methanol is extremely selective, it is possible to limit the amount of methanol which is used. As a result, when employing the present invention, only limited amounts of carbon monoxide are emitted to the atmosphere. The noncatalytic reduction of SO₃ by methanol is selective in that a large fraction of the SO₃ is converted to SO₂, while very little oxygen is consumed on a percentage basis. During the process, it is also found that NO tends to be oxidized to NO₂. The amount of methanol which must be used, therefore, is related to the total amount of NO and SO₃ present in the combustion effluents. Accordingly, it is preferred that in order to provide enough methanol for a substantial reduction of SO₃, but not enough to cause unnecessary emissions of CO, the amount of methanol contacted into the combustion effluents should be in the approximate mole ratio of from about 0.8 to about 2.0, with respect to the sum of NO and SO₃. In most applications, it is expected that the preferable range will be from about 0.9 to about 1.5. In order to keep the absolute amount of carbon monoxide emitted to the atmosphere to acceptably low levels, it is also a teaching of the present invention that the amount of methanol injected into the combustion effluent stream should be less than about 1000 ppm, and preferably less than about 500 ppm. According to the present invention, there is provided a method for minimising the formation of H₂SO₄ or NH₄HSO₄ in a combustion effluent having NO, at least 1 ppm SO₃, water vapour, and in the case of NH₄HSO₄ formation, ammonia, the method being characterised by the step of contacting the combustion effluents with methanol, in an amount such that the mole ratio of the methanol to the sum of the NO and SO₃ is in the range of from about 0.8 to about 2.0, at a temperature in the range from about 500°C to about 950°C and for a reaction time in the range 0.01 to 5 seconds, such that the methanol reduces SO₃ in the combustion effluent to SO₂, thereby minimising the formation of H₂SO₄ and NH₄HSO₄. The limitation of the reaction time to be in the range 0.01 to 5 seconds is important, so that the carbon monoxide produced by methanol oxidation is not itself oxidised to carbon dioxide. It is well known that the oxidation of CO produces concentrations of oxygen atoms and OH radicals which can again oxidise SO₂ to SO₃. Thus, if the CO is allowed to oxidise to CO₂ the process will be defeated in that SO₃ will again enter the environment and produce the possibility of forming additional NH₄HSO₄ or H₂SO₄. It is important, therefore, to minimise the reoxidation of SO₂ to SO₃ by limiting the reaction time as referred to above, so as in turn to minimise the oxidation of CO. It is, therefore, a primary object of the present invention to provide methods for preventing the formation of NH₄HSO₄ during the reduction of NO x . It is a related object of the present invention to prevent the formation of NH₄HSO₄ during the reduction of NO x where ammonia and ammonia precursors, along with SO₃, are present in the effluent environment. It is another primary object of the present invention to provide methods for preventing the formation of sulfuric acid in effluent streams. It is a related object of the invention to prevent sulfuric acid formation in emissions streams containing SO₃ and water. It is also an object of the present invention to remove SO₃ from the effluent stream by converting the SO₃ to SO₂, in order to prevent the above-mentioned reactions. It is more specifically an object of the present invention to selectively and noncatalytically reduce SO₃ to SO₂ using methanol, while also limiting the amount of methanol used in order to correspondingly limit the amount of carbon monoxide produced. These and other objects of the invention will become apparent upon reading the following detailed description and appended claims. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS I. General Discussion As described above, the present invention relates to the prevention of the formation of NH₄HSO₄ or H₂SO₄ in boilers, furnaces, and other burners. Particularly, the present invention relates to the removal of SO₃ from the stream of exhaust gases from certain types of pollution emitting facilities so that it is unavailable to react to form NH₄HSO₄ when ammonia and ammonia precursors are used to remove NO x from the exhaust gases of such facilities, or H₂SO₄ in the absence of ammonia but in the presence of water. As briefly discussed above, the formation of NH₄HSO₄ becomes a problem when the SO₃ and ammonia (or ammonia precursors) are present in the effluent gas stream within the critical temperature range. Ammonia and its precursors are widely used in the conversion of NO to nitrogen in such effluent gas streams. This reduction reaction is performed in order to remove the NO, thereby minimizing eventual NO₂ pollution in the ambient atmosphere. In order for NH₄HSO₄ to be formed, SO₃ must be present. The SO₃ reacts with the ammonia and water to form the fouling and corrosive NH₄HSO₄ compound. While SO₃ comprises only a relatively small percentage of the total sulfur generally emitted, its presence, even in small quantities, can result in the formation of sufficient NH₄HSO₄ to cause damage to combustion facilities. Although the present invention will likely only find use where significant amounts of sulfur are emitted, such facilities are numerous. Generally NH₄HSO₄ at levels below 1 ppm (the term "ppm" is used herein to signify moles per million moles of combustion effluents) is not a serious problem. Thus, the embodiment of the invention related to preventing NH₄HSO₄ formation is primarily useful in facilities where combustion effluents contain at least 1 ppm NH₃ and at least 1 ppm SO₃. Since SO₃ generally comprises 1% to 2% of the total SO x , the present invention will find its primary application in effluents containing more than 50 ppm SO x . The present invention is also useful in facilities that do not use ammonia to reduce NO x . In such facilities the reaction of SO₃ and water to produce sulfuric acid becomes a serious problem. Therefore, the present invention can also be employed to prevent this undesirable chemical reaction. II. The Process of the Preferred Embodiment The processes of the present invention involve contacting the combustion effluents with methanol. Since methanol will produce CO in the course of the process, it is necessary to limit both the relative and absolute amounts of methanol used. The present invention teaches the selective, noncatalytic, reduction of SO₃ by methanol, such that a large percentage of SO₃ is converted to SO₂. While, on a percentage basis, very little oxygen is consumed during this reaction process, some NO is converted to NO₂. Thus, the amount of methanol which must be used is directly related to the total amount of NO and SO₃ present in the combustion effluents. Accordingly, it is important to the present invention to provide enough methanol to accomplish substantial reduction of SO₃, but not enough methanol to cause unnecessary emissions of CO. The amount of methanol used in combination with the combustion effluents will generally be in the mole ratio with respect to NO and SO₃ in the range of from about 0.8 to about 2.0. In most applications, that ratio will preferably be in the range of from about 0.9 to about 1.5 of NO and SO₃. NO concentrations are much more easily measured than SO₃ concentrations and the amount of NO in the effluent gases is much larger than the amount of SO₃. Hence, in most situations, it is both acceptably accurate and more convenient to control the amount of methanol used with relationship to the relatively larger and more readily measured NO concentration, rather than SO₃ concentration. In any commercially viable effluent gas treatment process, it is important to limit the absolute amount of carbon monoxide emitted to the atmosphere to acceptably small levels; generally, the amount of CO emitted to the atmosphere should not exceed about 1000 ppm. In order to achieve this level of CO, it is important to the present invention that the amount of methanol injected into the combustion effluent gas generally be less than approximately 1000 ppm and preferably less than approximately 500 ppm. If more methanol is injected, additional pollution problems are encountered with respect to CO. When the present invention is used in combination with NO x reduction, the contacting of the methanol and the combustion effluents is done downstream of the zone in which the combustion effluents are contacted with an NO reducing agent. That is, the methanol is contacted with the combustion effluents downstream from the point that ammonia or ammonia precursors are introduced into the effluent stream. It will be appreciated that it would be wasteful to introduce methanol into the stream until after the reduction of NO with NH₃ or its precursors since the amount of CH₃OH needed to reduce SO₃ to SO₂ is related to the sum of NO and SO₃ at the point at which the methanol is contacted into the combustion effluents. The temperature at which methanol is introduced into the combustion effluents must be carefully controlled in order to produce the desired results. It is presently preferred that the temperature be within the range of approximately 500°C to about 950°C. When the temperature is significantly below 500°C, it has been found that the methanol will not react with the SO₃ to prevent the formation of H₂SO₄ or NH₄HSO₄ as the case may be. For example, methanol may be injected into a stream of combustion effluents having the following composition: The effluent existing at a pressure of approximately 1 atmosphere and a reaction time of 5.0 seconds. When the temperature is in the range of approximately 400°C, however, no reduction reaction between the methanol and SO₃ takes place, and NH₄HSO₄ forms. The same is true when NH₃ is not present. Under these conditions H₂SO₄ forms. This is also true for excessively high temperatures. For example, methanol may be injected into a stream of combustion effluents having the following composition: Pressure is held at approximately 1 atmosphere and the reaction time is about 0.05 seconds. When the temperature is at about 1050°C, the concentration of SO₃ increases from 10 ppm to 12.1 ppm. This illustrates generally that temperatures in excess of about 950°C are not desirable for the selective reduction of SO₃ with methanol. Similarly, when the methanol is introduced into the effluent stream at a temperature in the range of from about 500°C to about 950°C, it is very important to control the reaction time used so that the CO produced by methanol oxidation is not again oxidized to CO₂. As mentioned above, it is well known that the oxidation of CO produces concentrations of oxygen atoms and OH radicals, and that oxygen and OH radicals can oxidize SO₂ back to SO₃. Consequently, in order to minimize the reoxidation of SO₂ to SO₃, one must limit the reaction time used so as to minimize the oxidation of CO. Since combustion effluents cool as they flow through the boiler, furnace, or other burner facility, it is convenient to consider reaction time in terms of the interval between the time at which the combustion effluents are contacted by methanol and the time at which they cool to a particular temperature. It is presently preferred that reaction times be held within the range of from about 0.01 to about 5.0 seconds; the preferred reaction time will vary with the temperature at which the reaction occurs, as discussed hereinafter. If methanol is contacted into the combustion effluents at a temperature of greater than 900°C, the interval between the time the combustion effluences are contacted with methanol and the time at which the combustion effluents cool to a temperature of about 900°C or below is preferably no greater than 0.05 seconds. If the methanol contacts the effluents at a temperature greater than 800°C but less than 900°C, the interval between that contacting and the time at which the combustion effluents cool to about 800°C is preferably no greater than 0.2 seconds. In a typical boiler or furnace, heat is removed from the combustion effluents by causing them to flow past rows of heating exchange tubes. These heat exchange tubes are typically arranged in banks with cavities between the banks. Thus, the combustion effluents flow through the cavities between the banks. The gases experience a time at nearly constant temperature but they cool at a high rate as they pass through each of the banks. It is within the scope of the present invention to introduce the methanol into the combustion effluents both while they are passing through a tube bank and in the cavity between tube banks. According to the present invention, the combustion effluents may be contacted with gaseous methanol, liquid methanol, and/or an aqueous solution of methanol. In addition to methanol, certain other species may be acceptable for use in the reactions of the present invention. Such species include, for example, formaldehyde. Methanol, however, is presently preferred in that methanol is very low in cost and is also extremely high in efficiency in driving the desirable reactions of the present invention. In one embodiment of the present invention, liquid methanol, or an aqueous solution of methanol, is atomized by a jet of gas and then injected into the combustion effluents. The vaporization of the liquid droplets is a process requiring a finite time. Hence, contacting the methanol with the combustion effluents occurs not immediately upon injection but only after some delay. In one embodiment, the gas used to atomize the methanol solution contains NH₃. Thus, with a single injection, it is possible to obtain immediate contacting of the combustion effluents with NH₃ and a subsequent contacting with methanol. This process achieves both the selective reduction of NO and a subsequent selective reduction of SO₃ to SO₂. It is well known that complex chemical reactions occur by a series of elementary reactions, and that if one knows the rate constants of such steps a theoretical kinetic mechanism can be developed and used to calculate the behavior of the reaction under any set of conditions. Mechanisms describing the oxidation of light oxygenated hydrocarbons, such as methanol, the interconversion of NO and other nitrogen compounds at high temperatures, and the interconvers of sulfur compounds have been developed. Seeker et al., "Gas Phase Chemistry Development and Verification of a Mechanism for NO Formation and Destruction in Hydrocarbon Flames," EPA-600/7-85-6. Final Report contract EPA 68-02-2631, 1985; Vandooren et al., "Experimental Investigation of Methanol Oxidation in Flames: Mechanisms and Rate Constants of Elementary Steps," Eighteenth Symposium (Intl.) on Combustion, The Combustion Institute 473-483 (1981); Smith et al., 30 Combustion Science and Technology, 241 (1983); and Martin et al., 90 Journal of Physical Chemistry, 4143 (1986). Assembling these mechanisms produces a kinetic mechanism. Such a mechanism is assumed in the examples set forth below. III. Examples of Preferred Embodiments of the Present Invention The following examples are given to illustrate the process of the present invention, but the examples are not intended to limit the scope of the present invention. Example 1 Methanol is injected into an effluent stream having the following composition: The reaction time is 3.0 seconds and the pressure is held at 1 atmosphere. The temperature is set at a constant 600°C. It is found under these conditions that at the end of 3.0 seconds, the SO₃ is reduced from 10 ppm to 0.04 ppm and no significant amounts of NH₄HSO₄ are formed. This example illustrates that in temperatures in excess of 500°C, selective reduction of SO₃ takes place with methanol, and thus formation of NH₄HSO₄ is prevented. Example 2 Methanol is injected into an effluent stream having the following composition: The reaction time is 0.05 seconds and the pressure is held at 1 atmosphere. The reaction temperature is set at 900°C. It is found under these conditions that SO₃ is reduced from 10 ppm to 1.74 ppm and no significant amounts of NH₄HSO₄ are formed. This example illustrates that temperatures below 950°C can be useful for the selective reduction of SO₃ with methanol and prevention of the formation of NH₄HSO₄. Example 3 In this example, methanol is injected into a combustion effluent stream. Pressure is held at approximately 1 atmosphere and constant temperature at 700°C is maintained. The composition of the effluent stream, including methanol, is as follows: In this example the reaction time is about 1.0 second. It is found that SO₃ is reduced from 10 ppm to 0.11 ppm and that no significant amounts of NH₄HSO₄ formed. However, the CO concentration at the conclusion of the reaction is 1256 ppm. This example illustrates that selective reduction of SO₃, and prevention of NH₄HSO₄ formation, occurs under these conditions. However, emissions of CO increase dramatically to a generally unacceptable level. Example 4 Methanol is injected into an effluent stream having the same composition as that illustrated in Example 3 except that initial methanol concentration is reduced from 1600 ppm to 800 ppm, which is within the generally accepted limits for CO emissions into the atmosphere. It is found under these conditions that SO₃ is reduced from 10 ppm to 0.044 ppm and that no significant amounts of NH₄HSO₄ are formed. Furthermore, the CO concentration is only 606 ppm. This example illustrates that initial concentration of methanol less than approximately 1,000 ppm are effective for selectively reducing SO₃ without resulting in excessive CO emissions. Example 5 In this example, methanol is injected into a combustion effluent stream. Pressure is held at 1 atmosphere and constant temperature at 900°C is maintained. The reaction time is about 0.10 seconds. The composition of the effluent stream, including methanol, is as follows: Component Concentration NH₃ 5 ppm SO₃ 10 ppm SO₂ 500 ppm NO 100 ppm CH₃OH 300 ppm O₂ 3% CO₂ 10% H₂O 14% N₂ balance It is found that SO₃ is reduced from 10 ppm to 0.009 ppm and that no significant amounts of NH₄HSO₄ are formed. The CO level increases to 96.5 ppm. It is noted that the ratio of moles of NO and SO₃ is 2.73. Example 6 Methanol is injected into an effluent stream having the same composition as that illustrated in Example 5, except that the initial concentration of methanol is reduced to 150 ppm. It is found under these conditions that SO₃ concentration is reduced to 0.016 ppm, and the CO concentration is only 53.7 ppm. In this example the ratio of the concentration of CH₃OH to the sum of the concentrations of SO₃ and NO is 1.36. This example, along with Example 5, illustrate that the use ratio of moles of CH₃OH to the sum of moles of NO plus SO₃ in the range 0.8 to 2.0 is sufficient to reduce SO₃ efficiently without causing larger than necessary emissions of CO to the atmosphere. Example 7 Methanol is injected into an effluent stream. Pressure is held at approximately 1 atmosphere and a constant temperature of 950°C is maintained. The reaction time is 0.3 seconds. The composition of the effluent stream, including methanol, is as follows: Following this reaction, the temperature is abruptly decreased until no further reaction occurs. In this example it is found that SO₃ concentration increases from 10 ppm to 12.3 ppm with corresponding NH₄HSO₄ formation. CO concentration is 3.6 ppm. This is due to reaction temperatures in excess of 900°C coupled with a reaction time in excess of 0.05 seconds. Example 8 Methanol is injected into an effluent stream having the same composition as that illustrated in Example 7. Reaction time is decreased to 0.05 seconds. The result is that SO₃ in the effluent stream decreases from 10 ppm to 0.12 ppm and CO was 53 ppm. This example, taken in conjunction with comparative Example 7, illustrates that if methanol is contacted into combustion effluents at a temperature greater than 900°C, the interval between the point of contact and the point at which the combustion effluents cool to 900°C should be no greater than about 0.05 seconds. Use of an interval which is not greater than 0.05 seconds in this example produces a satisfactory reduction of SO₃, whereas in Example 7 use of an interval which is greater than 0.05 proved counterproductive due to oxidation of CO to CO₂. Example 9 Methanol is injected into an effluent stream having the same composition as that illustrated in Example 7. The reaction time is 1.0 second at a constant temperature of 900°C and a pressure of 1 atmosphere. Following this reaction time, the mixture is abruptly cooled to a temperature such that no further reaction occurs. SO₃ increases from 10 ppm to 10.27 ppm and CO is 1.1 ppm. Example 10 Methanol is injected into an effluent stream having the same composition as that illustrated in Example 7. The reaction time is 0.1 seconds at a constant temperature of 900°C and a pressure of one atmosphere. Following this reaction time, the mixture is abruptly cooled to a temperature such that no further reaction occurs. The result is that SO₃ is reduced from 10 ppm to 0.018 ppm and CO is 56 ppm. The results of this example, taken in conjunction with Example 9 illustrates that if methanol is contacted into combustion effluents at a temperature greater than 800°C, the interval between contacting and the point at which the combustion effluents cool to 800°C should preferably be no greater than 0.2 seconds. Use in this example of an interval which was not greater than 0.2 seconds produces a satisfactory reduction of SO₃ to SO₂ whereas in Example 9 use of of an interval greater than 0.2 seconds proves counterproductive due to the oxidation of CO to CO₂. Example 11 In this example, the experiment described in Example 1 is repeated, however, NH₃ is eliminated from the effluent stream. It is found under these conditions that at the end of 3.0 seconds, the SO₃ is reduced from 10 ppm to 0.04 ppm and no significant amounts of H₂SO₄ are formed. Example 12 In this example, the experiment described in Example 2 is repeated, however, NH₃ is eliminated from the effluent stream. It is found under these conditions that SO₃ is reduced from 10 ppm to 1.74 ppm and that no significant amounts of H₂SO₄ are formed. Example 13 In this example, the experiment described in Example 3 is repeated, however, NH₃ is eliminated from the effluent stream. It is found in this example that SO₃ is reduced from 10 ppm to 0.11 ppm and no significant amounts of H₂SO₄ are formed. However, the CO concentration at the conclusion of the reaction is 1256 ppm. Example 14 In this example, the experiment described in Example 4 is repeated, however, NH₃ is eliminated from the effluent stream. It is found under these conditions that SO₃ is reduced from 10 ppm to 0.044 ppm and that no significant amounts of H₂SO₄ are formed. Furthermore, the CO concentration is only 606 ppm. Example 15 In this example, the experiment described in Example 5 is repeated, however, NH₃ is eliminated from the effluent stream. It is found that SO₃ is reduced from 10 ppm to 0.009 ppm and that no significant amounts of H₂SO₄ are formed. The CO level increases to 96.5 ppm. Example 16 In this example, the experiment described in Example 6 is repeated, however, NH₃ is eliminated from the effluent stream. It is found under these conditions that SO₃ concentration is reduced to 0.016 ppm, and the CO concentration is only 53.7 ppm. Example 17 In this example, the experiment described in Example 7 is repeated, however, NH₃ is eliminated from the effluent stream. In this example it is found that SO₃ increases from 10 ppm to 12.3 ppm with corresponding H₂SO₄ formation. CO concentration is 3.6 ppm. Example 18 In this example, the experiment described in Example 8 is repeated, however, NH₃ is eliminated from the effluent stream. Reaction time is 0.05 seconds. The result is that SO₃ in the effluent stream decreases from 10 ppm to 0.012 ppm and CO is 53 ppm. Example 19 In this example, the experiment described in Example 9 is repeated, however, NH₃ is eliminated from the effluent stream. It is found under these conditions that SO₃ increases from 10 ppm to 10.27 ppm and CO is 1.1 ppm. Example 20 In this example, the experiment described in Example 10 is repeated, however, NH₃ is eliminated from the effluent stream. The result is that SO₃ is reduced from 10 ppm to 0.01 ppm and CO is reduced to 56 ppm. IV. Summary In view of the foregoing discussion and examples of the preferred embodiments of the present invention, it will be appreciated that the present invention accomplishes each of the objects of the invention set forth above. In particular, the present invention provides a method for preventing the formation of NH₄HSO₄ during the reduction reaction of NO x when ammonia or ammonium precursors are present. In particular, SO₃ tends to react with the species present in the effluent stream to produce NH₄HSO₄. As a result, the present invention provides an effective method for reducing SO₃ to SO₂ so that NH₄HSO₄ does not form in the effluent stream. Similarly, the present invention provides methods for preventing H₂SO₄ formation when NH₃ is absent. As mentioned above, SO₃ reacts with H₂O to form H₂SO₄ under the conditions described above. In addition, it will be appreciated that the reaction parameters of the processes of the present invention are specific. Thus, only limited amounts of methanol are required in order to reduce the SO₃ to SO₂; otherwise, other undesirable species, such as carbon monoxide, are produced in significant amounts by the process.

Claims: A method for minimising the formation of H₂SO₄ or NH₄HSO₄ in a combustion effluent having NO, at least 1 ppm SO₃, water vapour, and in the case of NH₄HSO₄ formation, ammonia, the method being characterised by the step of contacting the combustion effluents with methanol, in an amount such that the mole ratio of the methanol to the sum of the NO and SO₃ is in the range of from about 0.8 to about 2.0, at a temperature in the range from about 500°C to about 950°C and for a reaction time in the range 0.01 to 5 seconds, such that the methanol reduces SO₃ in the combustion effluent to SO₂, thereby minimising the formation of H₂SO₄ and NH₄HSO₄. A method according to Claim 1 characterised in that the combustion effluent comprises at least 50 ppm SO x . A method according to Claim 1 or Claim 2 characterised in that the methanol injected comprises less than approximately 1,000 ppm of the total combustion effluents. A method according to Claim 1 or Claim 2 characterised in that the methanol injected comprises less than approximately 500 ppm of the total combustion effluents. A method according to claim 1 characterised in that the ratio of moles of methanol to the sum of moles of NO and SO₃ is in the range of from approximately 0.9 to approximately 1.5. A method according to claim 1 characterised in that the temperature of the combustion effluents at the point of contacting the methanol is at least 900°C and wherein the period between the time at which the methanol is introduced into the effluents and the time in which the effluents cool to below 900°C is no greater than approximately 0.05 seconds. A method according to claim 1 characterised in that the temperature of the combustion effluents at the point of contacting with methanol is between approximately 800°C and approximately 900°C and wherein the period between the time at which the methanol is introduced into the effluents and the time when the effluents cool to below 800°C is no greater than approximately 0.2 seconds. A method according to any of the preceding claims characterised in that the methanol is in liquid form. A method according to any of the preceding claims characterised in that the methanol is atomized and propelled into the stream of effluents by a jet of gas. A method according to claim 10 characterised in that the jet of gas comprises ammonia. A method according to claim 1 characterised in that the temperature of the combustion effluents at the point of contacting with methanol is between approximately 800°C and approximately 900°C and wherein the period between the time at which the methanol is introduced into the effluent and the time when the effluents cool to below 800°C is no greater than approximately 0.2 seconds.

Inventors: LYON, RICHARD K.
Applicants: ENERGY AND ENVIRONMENTAL RESEARCH CORPORATION
Application year: 1988
Main classification: B01D53
IPC codes: B01D53