PROCESS FOR THE REDUCTION OF NITROGEN OXIDES IN AN EFFLUENT

Abstract: A process is presented for the reduction of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. The process comprises introducing a treatment agent comprising a composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfurylacetate, tetrahydrofuran, 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose into an effluent under conditions effective to reduce the concentration of nitrogen oxides in the effluent.

Description: DESCRIPTION PROCESS FOR THE REDUCTION OF NITROGEN OXIDES IN AN EFFLUENT Related Applications This application is a continuation-in-part of copending and commonly assigned U.S. Patent Application entitled "Reduction of ' Nitrogen-Based Pollutants Through the Use of Urea Solutions Containing Oxygenated Hydrocarbon Solvents" having Serial Number 784,828, filed October 4, 1985 in the name of Bowers; copending and commonly assigned U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent" having Serial Number 014,431, filed February 13, 1987 in the names of Epperly and Sullivan; copending and commonly assigned U.S. Patent Application entitled "Process for Reducing Nitrogen Oxides in an Effluent Using a Hydrocarbon or Hydrogen Peroxide" having Serial Number 022,799, filed March 6, 1987 in the name of Sullivan; copending and commonly assigned U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent Using Sugar'2 having Serial Number 025,350, filed March 13, 1987 in the names of Epperly and Sullivan; copending and commonly assigned U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent Using a Heterocyclic Hydrocarbon" having Serial Number 025,493, filed March 13, 1987 in the names of Epperly and Sullivan; copending and commonly assigned U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent Using a Hydroxy Amino Hydrocarbon" having Serial Number 039,013, filed April 15, 1987 in the names of Sullivan and Epperly; and copending and commonly assigned U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent" having Serial Number 100,128, filed September 23, 1987 in the names of Epperly, Sullivan and Sprague. The disclosures of each of these patent applications is hereby incorporated by reference herein in their entireties. Technical Field The present invention relates to a process for the reduction of nitrogen oxides (NOx) in the effluent, especially the oxygen-rich effluent, from the combustion of a carbonaceous fuel by introduction of a treatment agent comprising a composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4, 5-tetra- carboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic an hydride, oxalic acid, mucic acid and d-galactose into the effluent. Carbonaceous - fuels can be made to burn more completely, and with reduced emissions of carbon monoxide and unburned hydrocarbons, when the oxygen concentrations and air/fuel ratios employed are those which permit high flame temperatures, When fossil fuels are used to fire large utility boilers, temperatures above about 20000F., and typically about 22000F. to about 30000F., are generated. Unfortunately, such high temperatures, as well as hot spots of higher temperatures, tend to cause the production of thermal NOX, the temperatures being so high that free radicals of oxygen and nitrogen are formed and chemically combine as nitrogen oxides. Nitrogen oxides can form even in circulating fluidized bed boilers which operate at temperatures which typically range from 13000F. to 17000F. Nitrogen oxides, especially NO2, are troublesome pollutants which are found in the combustion effluent streams of boilers when fired as described above, and comprise a major irritant in smog. It is further believed that nitrogen oxides can undergo a process known as photo-chemical smog formation, through a series of reactions in the presence of sunlight and hydrocarbons. Moreover, nitrogen oxides comprise a major portion of acid rain. Unfortunately, the temperatures within a utility or circulating fluidized bed boiler render most common methods of reducing NOx concentrations, such as effluent scrubbing or catalyst grids, either uneconomical, infeasible, or both. Background Art Various methods and compositions for reducing the NOx concentration in the effluent from the combustion of a carbonaceous fuel have been proposed. For instance, Arand et al, in U.S. Patent No. 4,208,386, disclose a method for reducing NO, in combustion effluents by injecting urea, either as a solid powder or in solution, at effluent temperature in excess of 1300 F. The preferred urea solutions are those having at least 10 weight percent urea. For operation at temperatures below 16000F., the use of reducing materials such as paraffinic, olefinic, aromatic and oxygenated hydrocarbons, as well as hydrogen, are required. Similarly, Lyon, in U.S. Patent No. 3,900,554, discloses the introduction of ammonia, as a pure substance or in the form of ammonium formate, ammonium oxalate or ammonium carbonate, into effluents at temperatures between 13000F. and 20000F. For operation at temperatures below 16000F., the use of reducing materials, as is the case with Arand at al., such as paraffinic, olefinic, aromatic and oxygenated hydrocarbons, as well as carbon monoxide and hydrogen, are required. Although the prior art processes for reducing nitrogen oxides concentrations are generally effective, there exists a present need for a process which elicits still further NOx reductions in an economical and convenient manner. Disclosure of Invention The present invention relates to a process for reducing nitrogen oxides in the effluent from the combustion of a carbonaceous fuel. More particularly, the present invention relates to a process which comprises injecting into the effluent from the combustion of a carbonaceous fuel a treatment agent comprising a composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3-dioxolane, 1,4 dioxane, tetrahydrofuran, furfuryl anne, furfuryl alcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3-butylene glycol, methylal, tetrahydrofurfuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3 4, 5-tetra- carboxylic acid, tetrahydrofurfurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose under conditions effective to reduce the nitrogen oxides concentration in the effluent. Best Mode for Carrying Out the Invention For the purposes of this description, all temperatures herein are measured using an unshielded K-type thermocouple. Unless otherwise indicated, all parts and percentages are based on the weight of the composition at the particular point of reference. The terms "NH4-lignosulfonate" and "calcium lignosulfonate" as used herein refer respectively to the ammonium and calcium salts of lignosulfonic acid, which are sulfonate salts kade from the lignin of sulfite pulp-mill liquors. The term "1,3 dioxolane" as used herein refers to a five-membered heterocyclic hydrocarbon having oxygen at the 1 and 3 positions (also ethylene methylene dioxide). The term "fish oil" as used herein refers to a drying oil obtained chiefly from menhaden, pilchard, sardine and herring, extracted from the entire body of the fish by cooking and compressing. It will be understood that the compositions disclosed as being useful in the treatment agent of this invention can be substituted or unsubstituted. When substituted, typical substituents include hydrogen, alkyl, alkenyl, carboxyl, acyl, carbocyclic, aryl, amino, carbonyl, hydroxyl, alkoxyalkyl, hydroxyalkyl, thiohydroxyalkyl, alkoxy, and combinations thereof. Additionally, any two adjacent substituent groups can be linked, directly or indirectly, to form another ring. Preferred substituents for each of the compositions of the present invention include hydrogen, straight and branched-chain, substituted and unsubstituted aliphatic groups, oxygenated hydrocarbon groups, hydroxyl groups and amino groups. Moreover, it is understood that the claimed compositions include polymerization and condensation products thereof. As used herein, the term alkyln refers to a straight or branched chain hydrocarbon containing no unsaturation, e.g., methyl, ethyl, isopropyl, 2-butyl, neopentyl, n-hexyl, etc.; the term "alkoxy" refers to a univalent radical composed of an alkyl group linked through an oxygen atom having its free valence bond therefrom, e.g., methoxy (-O-CH3), ethoxy (-O-CH2-CH3), etc.; the term "acyl" refers to a carboxyl group in which the hydroxyl group has been replaced with another radical, such as alkyl, aryl, etc., e.g., acetyl EMI7.1 etc.; the term "carbocyclic" refers to an organic radical whose 'skeleton1 is in the form of a closed ring of carbon atoms; the term "aryl" refers to an aromatic hydrocarbon group, e.g., phenyl, benzyl, naphthyl, etc.; the term "carboxyl" refers to a univalent radical composed of a carbonyl group and a hydroxyl group linked through a carbon atom having its free valence bond therefrom, e.g., EMI7.2 the term "carbonyl" refers to a bivalent radical having the formula EMI7.3 the term "hydroxyl" refers to the univalent group -OH which is characteristic of alcohols; the term "hydroxyalkyl" refers to an alkyl group having at least one hydrogen substituted with an hydroxyl group; the term "alkoxyalkyl" refers to an alkyl group having at least one hydrogen substituted with an alkoxy group; the term "thiohydroxyalkyl" refers to a hydroxyalkyl group wherein the oxygen of the hydroxyl group is replaced with sulfur; and the term "alkenyl" refers to an unsaturated radical of lower branched or unbranched alkyl groups it is derived from, having at least one double bond therein. Advantageously, the treatment agent of this invention is introduced into the effluent in solution or as a dispersion or mixture in a suitable solvent. Water is a preferred solvent due to the economy of aqueous solutions, dispersions and mixtures and the fact that they can be employed with suitable effectiveness in most situations. For ease of description, the term "mixture will be used to denote mixtures, dispersions and solutions. The effective mixture comprising the treatment agent of this invention will range from saturated to dilute. While water is an effective solvent for most applications, it will be recognized that there may be instances where other solvents may be advantageously used, either alone or in combination with water, as would be known to the skilled artisan. The level of the composition selected from the group consisting of N114-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose present in the mixture is preferably in the range of about 0.5% to about 50% by weight, most preferably about 5% to about 25% by weight. The treatment agent of this invention is preferably introduced into the effluent in an amount effective to elicit a reduction in the nitrogen oxides concentration in the effluent. Advantageously, the treatment agent of this invention is introduced into the effluent in an amount sufficient to provide a weight ratio of the treatment agent to the baseline nitrogen oxides level of about 1:10 to about 10:1. More preferably, the treatment agent is introduced into the effluent to provide a molar ratio of treatment agent to baseline nitrogen oxides level of about 1:6 to about 5:1, most preferably about 1:5 to about 3:1. Conditions under which nitrogen oxides can be reduced by use of a treatment agent which comprises a composition selected from the group consisting of Nii4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose include the effluent temperature at the point of introduction of the treatment agent, which is preferably less than about 14500F., most preferably less than about 13000F., although in many cases NOx reduction can be achieved at higher temperatures. It is surprising in view of the state of the art that these materials have independent nitrogen oxides reduction properties and that they may themselves be used as primary NOx reducing agents, especially at such low temperatures. It is an advantageous aspect of this invention that the concentration of nitrogen oxides in an effluent from the combustion of a carbonaceous fuel can be reduced significantly at such temperatures, which are below the effective operating temperatures of most prior art NO, reducing compositions and/or processes, such as those which utilize urea or ammonia. There is no known lower limit of temperatures at which the present invention is effective at nitrogen oxides reduction, and significant reductions have been observed at temperatures as low as 8000F. The compositions of this invention may, in addition to their use as a primary NO, reducing agent themselves, also be used to enhance the nitrogen oxides reduction achieved by known NOx reducing compositions, referred to herein as principal nitrogen oxides reducing compositions. Exemplary of such principal nitrogen oxides reducing compositions are urea or ammonia. The terms "urea" and "ammonia" as used in this description includes the compositions themselves, . as well as compositions equivalent in effect. Thus, unless otherwise specified, reference in this disclosure to urea or ammonia should not be taken as limiting to urea or ammonia themselves, but should extend to urea or ammonia and all of their equivalents. It is pointed out that the term equivalent is not limited to exact equivalents, and various equivalents will be optimally operable at some conditions which are different than those for other equivalents. Moreover, some equivalents may be more effective than others. The term "ammonia" is specifically intended for the purposes of this disclosure to include ammonia precursors, that is, compositions which produce ammonia upon vaporization, such as ammonium salts of organic acids like ammonium formate, ammonium oxalate, ammonium carbonate and ammonium binoxalate. Other principal nitrogen oxides reducing compositions include hydroxy amino hydrocarbons, disclosed by Sullivan and Epperly in U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent Using a Hydroxy Amino Hydrocarbon", Serial Number 039,013, filed April 15, 1987; ammonium salts of organic acids having a carbon to nitrogen ratio of greater than 1:1, disclosed by Epperly, Sullivan and Sprague in U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent", Serial Number 090,962, filed August 28, 1987; and five or six membered heterocyclic hydrocarbons having at least one cyclic nitrogen, disclosed by Epperly, Sullivan and Sprague in U.S. Patent Application entitled "Process for the Reduction of Nitrogen Oxides in an Effluent", Serial Number 100,128, filed September 23, 1987, the disclosures of each of which are incorporated herein by reference. When the principal NOx reducing composition included in the treatment agent of this invention is ammonia, the enhancer used is most preferably selected from the group consisting of N4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3-dioxolane, 1,4 dioxane, tetrahydrofuran, furfuryl amine, furfuryl alcohol, gluconic acid, citric acid, n-butyl acetate, 1,3-butylene glycol, methylal, tetrahydrofurfuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurfurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, mucic acid and d-galactose. When the principal NOx reducing composition included in the treatment agent of the present invention comprises urea or any of the other principal nitrogen oxides reducing compositions disclosed above, the enhancer used can be any selected from the group consisting of NH4-lignosulfonat'e, calcium lignosulfonate, 2-furoic acid, 1,3-dioxolane, 1,4 dioxane, tetrahydrofuran, furfuryl amine, furfuryl alcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3-butylene glycol, methylal, tetrahydrofurfuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurfurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose. where urea, ammonia or any of the other disclosed principal nitrogen oxides reducing compositions is employed in the treatment agent, it should preferably be present in the mixture in the range of about 2% to about 60%, most preferably about 5% to about 30% by weight. The weight ratio of the composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose to such principal nitrogen oxides reducing composition should advantageously be about 1:10 to about 4:1, more preferably about 1:5 to about 3:1. The most preferred weight ratio in the mixture is about 1:4 to about 2.5:1. The treatment agent, when further comprising urea, ammonia or other principal nitrogen oxides reducing composition, whether in a mixture or introduced in pure form, is advantageously introduced into the effluent gas stream at a point where the effluent is at a temperature above about l2000F. Preferably, the treatment agent is introduced at a point where the effluent temperature is above about l3000F., more preferably above about 14000and most preferably above about 14500F. The temperature of the effluent at the point of introduction will have an influence on the concentration of the mixture. At temperatures up to about 1700 F., the mixture will tend to operate effectively at high concentration, e.g., about 10% to about 65% by weight treatment agent. On the other hand, at temperatures in excess of about 17000F., the mixture will tend more towards dilute. At these higher temperatures, water (or the solvent in case of non-aqueous solutions) may comprise greater than 80%, 85% or even 95% by weight of the mixture. Large industrial and circulating fluidized bed boilers of the types employed for utility power plants and other large facilities will typically have access only at limited points. In the most typical situations, the boiler interior in the area above the flame operates at temperatures which at full load approach 19000F., even 21000F. and sometimes higher still. After subsequent heat exchange, the temperature will be lower, usually in the range between about 10000F. and about 19000F. At these temperatures, the treatment agent of this invention can be effectively introduced to accomplish substantial reduction of nitrogen oxides in the effluent. The treatment agent utilized according to this invention is preferably introduced by injecting it at a number of spaced positions from nozzles or other apparatus which are effective to uniformly distribute the treatment agent through the combustion effluent. The effluent into which the treatment agent of this invention is introduced is preferably oxygen-rich, meaning that there is an excess of oxygen in the effluent. Advantageously, the excess of oxygen is greater than about 1% by volume. More preferably, the excess of oxygen is in the range of about 1% to about 12% or greater by volume, most preferably about 16 to about 6% by volume. It will be understood that the NOx reducing treatment agents of this invention are useful not only where substantial nitrogen oxides reductions are accomplished by directly applying the disclosed method as the principal NOx reducing method, but can also be employed as a discrete step in combination with other chemical, catalytic or other procedures for reducing nitrogen oxides concentrations as well as other pollutants such as sulfur dioxide (SO2), while preferably controlling levels of residual pollutants such as ammonia and/or carbon monoxide. Such a suitable "multi-step" process is disclosed in copending and commonly assigned U.S. Patent Application entitled "Nultl-Stage Process for Reducing the Concentration of Pollutants in an Effluent" filed in the names of Epperly, Peter-Hoblyn, Shulof and Sullivan on March 6, 1987 and assigned Serial Number 022,716, the disclosure of which is incorporated herein by reference. A further advantageous aspect of the practice of this invention is in the reduced production of other pollutants, such as ammonia and carbon monoxide, during the nitrogen oxides reduction process. The presence of ammonia in the effluent should be avoided because, among other reasons, it can react with 803 to form ammonium bisulfate which can foul heat exchange surfaces in a boiler. Moreover, ammonia has detrimental effects on ambient air quality, as has carbon monoxide. Such lower levels of the production of other pollutants such as ammonia and carbon monoxide can most effectively be achieved by introducing the treatment agents of this invention on the right side of their nitrogen oxides reduction versus effluent temperature curve, especially on the right side of the curve plateau. This process is fully explained and taught in copending and commonly assigned U.S. Patent Application Serial Number 050,198, entitled "Process for Nitrogen Oxides Reduction and Minimization of the Production of Other Pollutants", filed May 14, 1987 in the names of Epperly, O'Leary and Sullivan, the disclosure of which is incorporated herein by reference. The following examples further illustrate and explain the invention by detailing the operation of a treatment agent comprising a five or six-membered heterocyclic hydrocarbon having at least one cyclic nitrogen in the reduction of nitrogen oxides emissions. Example I The burner used is a burner having an effluent flue conduit, known as a combustion tunnel, approximately 209 inches in length and having an internal diameter of 8 inches and walls 2 inches thick. The burner has a flame area adjacent the effluent entry port and flue gas monitors adjacent the effluent exit port to measure the concentration of compositions such as nitrogen oxides, sulfur oxides, ammonia, carbon monoxide, carbon dioxide, percent excess oxygen and other compounds of interest which may be present in the effluent. The effluent flue conduit additionally has thermocouple ports for temperature measurement at various locations. The temperature of the effluent into which the treatment agents are introduced is measured at the point of injection utilizing a K-type thermocouple. Atomizing injectors described in copending and commonly assigned U.S. Patent Application entitled "Process and Apparatus for Reducing the Concentration of Pollutants in an Effluent" having Serial Number 009,696, filed in the name of Burton on February 2, 1987, the disclosure of which is incorporated herein by reference, are positioned through ports in the effluent flue conduit in order to introduce and distribute the treatment agents into the effluent stream. The agents are introduced into the effluent at a rate of 300 ml/hr. The burner fuel is a Number 2 fuel oil, and the burner is fired at a rate of 8.4 lbs/hr to 10.2 lbs/hr. to achieve the desired temperature. A baseline nitrogen oxides concentration reading is taken prior to beginning each run to calculate the introduction ratio of treatment agent to baseline nitrogen oxides, and a final nitrogen oxides reading is taken during and downstream from introduction of the treatment agents to calculate the reduction in the nitrogen oxides concentration in the effluent elicited by each of the treatment agents introduced. Additionally, ammonia and carbon monoxide readings are taken during and downstream from introduction of the treatment agents to measure the production of other pollutants. The percent excess oxygen for each treatment agent introduction, the baseline NOX, final NOx, % reduction of NOx, ammonia level and carbon monoxide level for each run is set out in Table 1. The following runs are made: 1) the treatment agent introduced is an aqueous solution which comprises 15% by weight of NH4-lignosulfonate and 0.1% by weight of a commercially available surfactant and the introduction temperature is 13450F. (run la) and 11850F. (run lib); 2) the treatment agent introduced is an aqueous solution which, comprises 15% by weight of calcium lignosulfonate and 0.1% of a commercially available surfactant and the introduction temperature is 13450F. (run 2a) and l2000F. (run 2b); ; 3) the treatment agent introduced is an aqueous solution which comprises 10% by weight of 1,3-dioxolane and 0.1% of a commercially available surfactant and the introduction temperature is l2100F.; 4) the treatment agent introduced is an aqueous solution which comprises 10% by weight of 1,4 dioxane and 0.1% by weight of a commercially available surfactant and - the introduction temperature is 12300F. (run 4a) and 12150F. (run 4b); ; 5) the treatment agent introduced is an aqueous solution which comprises 10% by weight of tetrahydrofuran and 0.18 by weight of a commercially available surfactant and the introduction temperature is 12300F. (run 5a) and 12200F. (run 5b); 6) the treatment agent introduced is an aqueous solution which comprises 10% by weight of furfuryl amine and 0.1% by weight of-a commercially available surfactant and the introduction temperature is 15250F.; 7) the treatment agent introduced is an aqueous solution which comprises 10% by weight of furfuryl alcohol and 0.1% by weight of a commercially available surfactant and the introduction temperature is 13500F.; ; 8 the treatment agent introduced is an aqueous solution which comprises 10% by weight of gluconic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is l2300F.; 9) the treatment agent introduced is an aqueous solution which comprises 10% by weight of citric acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12300F.; 10) the treatment agent introduced is an aqueous solution which comprises 10% by weight of formic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12300F.; ; 11) the treatment agent introduced is an aqueous solution which comprises 10% by weight of n-butyl acetate and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12300fit 12) the treatment agent introduced is an aqueous solution which comprises 10% by weight of 1,3-butylene glycol and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12450F.; 13) the treatment agent introduced is an aqueous solution which comprises 10% by weight of methylal and 0.18 by weight of a commercially available surfactant and the introduction temperature is 12450F.; ; 14) the treatment agent introduced is an aqueous solution which comprises 10% by weight of tetrahydrofuryl alcohol and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12500F.; 15) the treatment agent introduced is an aqueous solution which comprises 10% by weight of fish oil and 0.1% by weight of a commercially available surfactant and the introduction temperature is l2050F.; 16) the treatment agent introduced is an aqueous solution which comprises 108 by weight of coumalic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12050F.; ; 17) the treatment agent introduced is an aqueous solution which comprises 10% by weight of furfuryl acetate and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12000F.; 18) the treatment agent introduced is an aqueous solution which comprises 108 by weight of tetrahydrofuran 1,2,3, 4-tetrahydrocarboxylic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12000F.; 19) the treatment agent introduced is an aqueous solution which comprises 10 by weight of tetrahydrofurfurylamine and 0.1% by weight of a commercially- available surfactant and the introduction temperature is 1200 F.; ; 20) the treatment agent introduced is an aqueous solution which comprises 10t by weight of tetrahydropyran and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12000F.; 21) the treatment agent introduced is an aqueous solution which comprises 10% by weight of 2,5-furandimethanol and 0.1% by weight of a commercially available surfactant and the introduction temperature is l2100F., 22) the treatment agent introduced is an aqueous solution which comprises 10% by weight of mannitol and 0.19 by weight of a commercially available surfactant and the introduction temperature is 12150F.; ; 23) the treatment agent introduced is an aqueous solution which comprises 10% by weight of hexamethylenediamine and 0.1% by weight of a commercially .available surfactant and the introduction temperature is 15 2 OOF . (run 23a) and 1190 F. (run 23b) ; 24) the treatment agent introduced is an aqueous solution which comprises 10% by weight of acetic anhydride and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12100F.; 25) the treatment agent introduced is an aqueous solution which comprises 10% by weight of oxalic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 1210 F.; ; 26) the treatment agent introduced is an aqueous solution which comprises 10% by weight of mucic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12150fit and 27) the treatment agent introduced is an aqueous solution which comprises 10% by weight of d-galactose and 0.1% by weight of a commercially available surfactant and the introduction temperature is 12200F. Table 1 Run O NOx (ppm) NOx red. NH3 CO (%) Base- Final (%) (ppm) (ppm) line la 3.0 195 184 5.6 -- 260 lb 3.0 197 182 7.6 -- 220 2a 3.0 195 186 4.6 -- 140 2b 3.0 197 175 11.2 -- 220 3 3.0 157 103 34.4 5 440 4a 3.2 160 115 28.1 20 600 4b 2.9 164 132 19.5 4 300 5a 3.2 160 132 17.5 12 720 5b 3.0 166 143 13.9 4 315 6 3.1 209 143 31.6 6 22 7 3.0 209 188 10.0 1.6 250 8 3.2 163 136 16.6 3 450 9 3.2 163 148 9.2 3 290 10 2.8 174 167 4.0 6 52 11 3.2 208 183 12.0 7 420 Table 1 (cont.) Run O2 NO, (ppm) NO, red. NH3 CO (%) Base- Final (%) (ppm) (ppm) line 12 3.2 208 179 13.9 7 355 13 3.2 208 169 18.8 11 370 14 3.0 208 185 11.1 6 350 15 3.0 145 105 27.6 10 454 16 3.0 147 130 11.6 3 205 17 3.0 148 138 6.8 2 57 18 3.0 148 126 14.9 2 165 19 3.0 149 107 28.2 10 290 20 3.1 164 130 20.7 8 380 21 3.2 164 132 19.5 4 395 22 3.0 164 135 17.7 4 288 23a 3.0 168 122 27.4 10 '22 23b 3.1 185 142 23.2 14 260 24 3.0 192 172 10.4 2 117 25 3.0 192 186 3.1 5 32 Table 1 (cont.) Run o NO, (ppm) NO, red. NH3 CO (i) 13ase- Final (t)- (ppm) (ppm) line 26 2.8 161 145 9.9 2 155 27 2.7 161 125 22.4 3 276 Example II The process of Example I is repeated except that the burner is fired at a rate of 9.6 lbs/hr. to 10.2 lbs/hr. to achieve the desired temperature. A baseline nitrogen oxides concentration reading is taken prior to beginning each run to calculate the introduction ratio of treatment agent to baseline nitrogen oxides, and a final nitrogen oxides reading is taken during and downstream from introduction of the treatment agents to calculate the reduction in the nitrogen oxides concentration in the effluent elicited by each of the treatment agents introduced. Additionally, ammonia and carbon monoxide readings are taken during and downstream from introduction of the treatment agents to measure the production of other pollutants. The percent excess oxygen for each treatment agent introduction, the baseline NOx, final NOx, % reduction of NOx, ammonia level and carbon monoxide level for each run is set out in Table 2. The following runs are made: 1) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 15% by weight of NU4-lignosulfonate and 0.1% by weight of a commercially available surfactant and the introduction temperature is l53'00F.; 2) the treatment agent introduced is an aqueous solution¯ which comprises 10% by weight of urea, 15% by weight of calcium lignosulfonate and 0.1% of a commercially available surfactant and the introduction temperature is 15250F.; ; 3) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of 1,3-dioxolane and 0.1% 'of a commercially available surfactant and the introduction temperature is 1550 0F.; 4) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of 1,4 dioxane and 0.1% by weight of a commercially available surfactant and the introduction temperature is l5550F., 5) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of tetrahydrofuran and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15500F.; ; 6) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of furfuryl alcohol and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15250F.) 7) the treatment agent introduced is an aqueous solution which comprises 10S by weight of urea, 15% by weight of gluconic acid and 0.1S by weight of a cÏmmercially available surfactant and the introduction temperature is l525O?.; 8) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 15% by weight of citric acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15500F.; ; 9) the treatment agent introduced is an aqueous solution which comprises 10 by weight of urea, 10% by weight of formic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15250F.; 10) the treatment agent introduced is an aqueous solution which comprises 10S by weight of urea, 10% by weight of n-butyl acetate and 0.1% by weight of a commercially available surfactant and the introduction temperature is 14950F.; 11) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of 1,3-butylene glycol and 0.1% by weight of a commercially available surfactant and the introduction temperature is l4950F.; ; 12) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of methylal and 0.1% by weight of a commercially available surfactant and the introduction temperature is 14900F.; 13) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of tetrahydrofuryl alcohol and 0.1% by weight of a commercially available surfactant and the introduction temperature is 14900F.; ; 14) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of fish oil and 0.1% by weight of a commercially available surfactant and the introduction temperature is l5000F., 15) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of coumalic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15050F.; 16) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 109 by weight of furfuryl acetate and 0.1% by weight of a commercially available surfactant and the introduction temperature is 1515 F.; ; 17) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of tetrahydrofuran 2,3,4,5-tetra-hydrocarboxylic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15150F.; 18) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of tetrahydrofurfurylamine and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15150F.; 19) the treatment agent introduced is an aqueous solution which comprises 109 by weight of urea, 10% by weight of furylacrylic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 151ooh.; ; 20) the treatment agent introduced is an aqueous solution which comprises 101 by weight of urea, 10% by weight of tetrahydropyran and 0.19s by weight of a commercially available surfactant and the introduction temperature is 15150F.; 21) the treatment agent introduced is an aqueous solution which comprises 10%- by weight of urea, 10% by weight of 2,5-furandimethanol and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15200F.; 22) the treatment agent introduced is an aqueous solution which comprises 102 by weight of urea, 10% by weight of mannitol and 0.1t by weight of a commercially available surfactant and the introduction temperature is 1520 F.; ; 23) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of hexamethylenediamine and 0.1% by weight of a commercially available surfactant and the introduction temperature is 1525 F.; 24) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of acetic anhydride and 0.1% by weight of a commercially available surfactant and the introduction temperature is 1520 F.; ; 25) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of oxalic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is 15100fit 26) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of mucic acid and 0.1% by weight of a commercially available surfactant and the introduction temperature is l5150F.; and 27) the treatment agent introduced is an aqueous solution which comprises 10% by weight of urea, 10% by weight of d-galactose and 0.1% by weight of a commercially available surfactant and the introduction temperature is l5150F. Table 2 Run o NO, (ppm) NO, red. NH3 CO (i) Base- Final (%) (ppm) (ppm) line 1 2.7 189 80 57.7 47 160 2 2.7 189 80 57.7 33 75 3 3.0 228 115 49.6 47 104 4 2.9 228 125 45.2 42 120 5 2.8 228 78 72.9 29 68 6 3.0 209 86 58.9 40 190 Table 2 (cont.) Run O NO, (ppm) NO red. NH3 CO Base Final (8) (ppm) (ppm) line 7 2.8 197 83 57.9 37 68 8 3.1 197 80 59.4 53 75 9 3.2 186 97 47.8 87 96 10 3.0 211 97 54.0 57 170 11 3.0 211 98 53.6 60 168 12 3.0 211 147 30.3 85 245 13 3.0 211 100 52.6 37 205 14 2.9 213 90 57.7 13 50 15 3.0 213 125 41.3 87 187 16 3.0 213 90 57.7 87 155 17 3.0 213 118 44.6 73 155 18 2.9 213 75 64.8 56 104 19 3.2 199 82 58.8 78 160 20 3.1 199 74 62.8 35 60 21 3.2 199 77 61.3 40 82 Table 2 font.) Run 0 NOx (ppm) NOX red. NH3 CO ( Base- Final (%) (ppm) (ppm) line 22 3.2 200 78 61.0 50 112 23 3.0 169 72 57.4 73 110 24 3.0 169 84 50.3 82 135 25 3.0 163 125 23.3 65 56 26 3.0 163 132 19.0 92 125 27 2.9 163 82 49.7 89 180 Example III The process of Example I is repeated except that the burner is fired at a rate of 10.2 lbs/hr'. to achieve the desired temperature. A baseline nitrogen oxides concentration reading is taken prior to beginning each run to calculate the introduction ratio of treatment agent to baseline nitrogen oxides, and a final nitrogen oxides reading is taken during and downstream from introduction of the treatment agents to calculate the reduction in the nitrogen oxides concentration in the effluent elicited by each of the treatment agents introduced. Additionally, ammonia and carbon monoxide readings are taken during and downstream from introduction of the treatment agents to measure the production of other pollutants. The percent excess oxygen for each treatment agent introduction, the baseline NOx, final NOx, 8 reduction of NOX, ammonia level and carbon monoxide level for each run is set out in Table 3. The following runs are made: 1) the treatment agent introduced is an aqueous solution which comprises 6% by weight of ammonia, 10% by weight of furfuryl alcohol and 0.1t by weight of a commercially available surfactant and the introduction temperature is l4450F., 2) the treatment agent introduced is an aqueous solution which comprises 6% by weight of ammonia, 10% by weight of n-butyl acetate and 0.1% of a commercially available surfactant and the introduction temperature is 1450 F.; 3) the treatment agent introduced is an aqueous solution which comprises 6% by weight of ammonia, 10% by weight of tetrahydrofurfuryl alcohol and 0.1% of a commercially available surfactant and the introduction temperature is 14500F.; ; 4) the treatment agent introduced is an aqueous solution which comprises 6% by weight of ammonia, 10% by weight of fish oil and 0.1% by weight of a commercially available surfactant and the introduction temperature is 14500F.; 5) the treatment agent introduced is an aqueous solution which comprises 6% by weight of ammonia, 10% by weight of tetrahydrofurfurylamine and 0.1% by weight of a commercially available surfactant and the introduction temperature is 14500F.; ; and 6) the treatment agent introduced is an aqueous solution which comprises 6% by weight of ammonia, 10sus by weight of tetrahydropyran and 0.19s by weight of a commercilly available surfactant and the introduction temperature is 14500F.- Table 3 Run O NO, (ppm) No, red. NH3 CO () Base- -Final (%) (ppm) (ppm) line 1 3.0 176 132 25.0 7 420 2 3.0 176 122 30.7 8 300 3 2.9 176 122 30.7 8 495 4 3.2 176 101 42.6 6 440 5 3.0 176 120 31.8 10 340 6 2.9 176 109 38.1 4 405 It is clear from the foregoing examples that the practice of this invention leads to substantial reductions in the nitrogen oxides concentration in the effluent from the combustion of a carbonaceous fuel. The compositions disclosed herein as being useful components of NO, reducing treatment agents have been shown to be effective alone, especially at lower temperatures, and as enhancers for urea or ammonia. The above description is for the purpose of teaching the person of ordinary skill in the art how to practice the present invention, and it is not intended to detail all of those obvious modifications and variations of it which will become apparent to the skilled worker upon reading the description. It is intended, however, that all such obvious modifications and variations be included within the scope of the present invention which is defined by the following claims.

Claims: Claims 1. A process for the reduction'of the concentration of nitrogen oxides in the effluent from the combustion of a carbonaceous fuel, the process comprising introducing a treatment agent which comprises a composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol; mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose. 2. The process of claim 1 wherein the temperature of the effluent is no greater than about 21000F. 3. The process of claim 2 wherein the temperature of the effluent is no greater than about 14500F. 4. The process of claim 3 wherein the temperature of the effluent is no greater than about 13000F. 5. The process of claim 1 wherein said treatment agent is introduced into the effluent at a weight ratio of said treatment agent to the baseline nitrogen oxides level of about 1:10 to about 10:1. 6. The process of claim 5 wherein the weight ratio of treatment agent to the baseline nitrogen oxides level is about 1:6 to about 5:1. 7. The process of claim 1 wherein said treatment agent is in solution, in a mixture or in a dispersion. 8. The process of claim 7 wherein the solvent used in said solution, mixture or dispersion comprises water. 9. The process of claim 1 wherein said treatment agent further comprises a principal nitrogen oxides reducing composition. 10. The process of claim 9 wherein said principal nitrogen oxides reducing composition comprises urea or ammonia. 11. The process of claim 9 wherein said principal nitrogen oxides reducing composition is present in said solution, mixture or dispersion in an amount of about 2% to about 60% by weight. 12. The process of claim 11 wherein said composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose is present in said solution, mixture or dispersion in an amount of about 0.5% to about 50% by weight. 13. The process of claim 1 wherein the effluent comprises an excess of oxygen. 14. The process of claim 13 wherein said effluent has an excess of oxygen of no greater than about 129 by volume. 15. The process of claim 14 wherein said excess of oxygen in the effluent is about 1% to about 6% by volume. 16. A process for the reduction of the concentration of nitrogen oxides in the oxygen-rich effluent from the combustion of a carbonaceous fuel, the process comprising introducing a treatment agent which comprises a principal nitrogen oxides reducing composition and further comprises a composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose into an effluent having a temperature up to about 2100 F. under conditions effective to reduce the concentration of nitrogen oxides in the effluent. 17. The process of claim 16 wherein said principal nitrogen oxides reducing composition comprises urea or ammonia. 18. The process of claim 16 wherein the effluent is at a temperature of greater than about 13000F. 19. The process of claim 18 wherein the effluent is at a temperature of greater than about l4500F. 20. The process of claim 16 wherein said treatment agent is in solution, in a mixture or in a dispersion. 21. The process of claim 20 wherein the solvent used in said solution, mixture or dispersion comprises water. 22. The process of claim 21 wherein urea or ammonia is present in said solution, mixture or dispersion in an amount of about 2% to about 605 by weight 23. The process of claim 22 wherein said composition selected from the group consisting of NH4-lignosulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid, furfuryl acetate, tetrahydrofuran 2,3,4,5-teracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-gaiactose is present in said solution, mixture or dispersion in an amount of about 0.5% to about 25% by weight. 24. The process of claim 16 wherein said treatment agent is introduced into the effluent at a molar ratio of said treatment agent to the baseline nitrogen oxides level of about 1:10 to about 10:1. 25. The process of claim 24 wherein the molar ratio of said treatment agent to baseline nitrogen oxides level is about 1:6 to about 5:1. 26. The process of claim 16 wherein said effluent has an excess of oxygen of no greater than about 12% by volume. 27. A process for the reduction of the concentration of nitrogen oxides in the oxygen-rich effluent from the combustion of a carbonaceous fuel, the process comprising introducing a treatment agent which comprises an aqueous solution, mixture or dispersion of about 2% to about 60% by weight of urea or ammonia and about 0.5% to about 25% by weight of a composition selected from the group consisting of NH4-ligno- sulfonate, calcium lignosulfonate, 2-furoic acid, 1,3 dioxolane, 1,4 dioxane, tetrahydrofuran, furfurylamine, furfurylalcohol, gluconic acid, citric acid, formic acid, n-butyl acetate, 1,3 butylene glycol, methylal, tetrahydrofuryl alcohol, furan, fish oil, coumalic acid; furfuryl acetate, tetrahydrofuran 2,3,4,5-tetracarboxylic acid, tetrahydrofurylamine, furylacrylic acid, tetrahydropyran, 2,5-furandimethanol, mannitol, hexamethylenediamine, barbituric acid, acetic anhydride, oxalic acid, mucic acid and d-galactose into an effluent having an excess of oxygen of about 1% to about 12% by volume and a temperature below about 20000F. in an amount sufficient to provide a molar ratio of said treatment agent to the baseline nitrogen oxides level of about 1:6 to about 5:1, under conditions effective to reduce the nitrogen oxides level in the effluent.

Inventors: EPPERLY WILLIAM ROBERT, SPRAGUE BARRY NORMAND, SULLIVAN JAMES CHRISTOPHER, EPPERLY, WILLIAM, ROBERT, SPRAGUE, BARRY, NORMAND, SULLIVAN, JAMES, CHRISTOPHER
Applicants: FUEL TECH INC, FUEL TECH, INC.
Application year: 1988
Main classification: B01D53
IPC codes: B01D53