Catalytic decomposition of N2O

Abstract: The invention describes a highly efficient catalytic pollution control process for removing N₂O from gaseous mixtures. The catalytic process, which is substantially unaffected by the presence of oxygen, comprises contacting an N₂O-containing gaseous mixture with a catalyst comprising a crystalline zeolite which, at least in part, is composed of five membered rings having a structure type selected from the group consisting of BETA, MOR, MFI, MEL and FER wherein the crystalline zeolite has been at least partially ion-exchanged with a metal selected from the group consisting of copper, cobalt, rhodium, iridium, ruthenium and palladium under conditions sufficient to convert the N₂O into gaseous nitrogen and gaseous oxygen.

Description: TECHNICAL FIELD OF THE INVENTION The present invention describes a highly efficient pollution control process for catalytically converting nitrous oxide (N₂O) into nitrogen gas and oxygen gas. The catalysts comprise particular crystalline zeolites which are at least partially exchanged with a metal selected from copper, cobalt, rhodium, iridium, ruthenium or palladium. BACKGROUND OF THE INVENTION In the past, nitrous oxide (N₂O) has received little attention as an atmospheric pollutant and has not been considered a constituent of the gaseous pollutants collectively referred to as nitrogen oxides (NO x ) which have received wide attention as pollutants harmful to the environment. However, recent studies indicate that N₂O in the Earth's atmosphere may be increasing by about 0.2% per year and that this increase appears to be caused by anthropogenic activity. N₂O is a major stratospheric source of NO, has been linked to the destruction of the ozone layer and is recognized to be a green-house gas. Because N₂O has an atmospheric lifetime of approximately 150 years, a strong effort is underway to identify sources of the pollutant and to limit further production of the harmful gas. Recent reports such as an article by Thiemens and Trogler, Science , 251 (1991)932 suggest that various industrial processes significantly contribute to the increased levels of N₂O found in the Earth's atmosphere. For example, nitrous oxide is a by-product in the manufacture of monomers for producing 6,6- and 6,12-nylon. Approximately 1.24 X 10⁹ kg of nylon were produced in the United State in 1898, alone. Nylon polymers are typically formed by condensation polymerization of a dicarboxylic acid and a diamine. The most widely used dicarboxylic acid, adipic acid, is prepared primarily by air oxidation of cyclohexane to form a cyclohexanol/cyclohexanone mixture followed by oxidation with HNO₃ to form adipic acid and N₂O. According to calculations by Thiemens and Trogler, the reaction stoichiometry for producing N₂O in the preparation of adipic acid is about 1 mol of N₂O per mole of adipic acid. Assuming a global yearly adipic acid production of 2.2 x 10⁹ kg yr⁻¹, about 1.5 x 10¹⁰ mol yr⁻¹ of N₂O by-product or 10% of the annual atmospheric N₂O increase can be attributed to this single process. According to the NOx information Book, March, 1983, DOE/NBB-0044, prepared for the U.S. Department of Energy, N₂O was not previously considered a major atmospheric pollutant. For example, Chapter 2, "Characteristics and Origins of Oxides of Nitrogen", states that the term 'NOx' is used in the air quality field to signify NO and NO₂. The reference also states that "N₂O is not considered an air pollutant, but it is a principal reactant in upper atmospheric reactions decomposing ozone". This preliminary data may explain why N₂O emissions are not currently regulated by the Environmental Protection Agency. Several catalysts have been studied for N₂O decomposition. However, the objective of most of the literature studies was to develop an understanding of catalytic mechanisms. Slinkin and coworkers, Kinetika i Kataliz, 19 (1978)992 and 20 (1979)515, studied the catalytic decomposition of N₂O over dealuminized H-mordenites and mordenites containing nickel cations. The investigators reported reaction rates of 1.5 x 10⁻⁵ mol g⁻¹h⁻¹ for H-mordenite and 9.5 x 10⁻⁶ mol g⁻¹h⁻¹ for Ni-mordenite at 450°C. Hall and coworkers, J. Catal., 86 (1984)392, studied the catalytic decomposition of N₂O over various iron-exchanged catalysts. Iron-exchanged Y zeolite provided a rate of 5.5 x 10⁻⁶ mol g⁻¹h⁻¹ at 498°C., and iron-exchanged mordenite provided a rate of 2.6 x 10⁻⁴ mol g⁻¹h⁻¹ at the same temperature. Neither Na-M nor Na-Y performed as catalysts in the subject reaction. Pomonis and coworkers, J. Chem. Soc., Farady Tran., 81 (1985)2043, studied Fe₂O₃/Al₂0₃ as a catalyst for N₂O decomposition. At 500°C and a space velocity of about 3,000 h⁻¹, a conversion of less than 1% N₂O was obtained which is equivalent to a reaction rate of 1.4 x 10⁻⁵ mol g⁻¹h⁻¹ at [N₂O] of 1000 ppm. Dumesic and coworkers, J. Catal., 110 (1988)330, studied N₂O decomposition over cation-exchanged Y zeolites (Fe-Y, FeEu-Y, Eu-Y, FeLa-Y, La-Y, Cu-Y, Co-Y, Cr-Y, Ni-Y and Mn-Y). Among these catalysts, FeEu-Y and Cu-Y were most active. At 450°C, the reaction rates were 1.8 x 10⁻⁴ and 1.4 x 10⁻⁴ mol g⁻¹h⁻¹, for FeEu-Y and Cu-Y, respectively. Panov and coworkers, J. Mol. Catal., 61 (1990)85, recently reported that FeZSM-5 was much more active than Fe₂O₃, Fe-Y and Fe-mordenite in the decomposition of N₂O to gaseous nitrogen and oxygen. Comparison of these rates with the steady-state reaction rates of others is difficult because the investigators utilized a static system for their reaction. Since N₂O is now considered an environmental pollutant due to its contribution to the greenhouse effect and to its catalytic effect on the destruction of the stratospheric ozone layer, an urgent need exists to develop catalytic processes for destroying N₂O emissions prior to venting commercial process effluent streams into the atmosphere. Although catalytic decomposition of N₂O has been studied extensively in academic institutions, no commercially viable process is known for decomposing N₂O into its respective components, namely gaseous nitrogen and gaseous oxygen. BRIEF SUMMARY OF THE INVENTION The present invention relates to a process for catalytically removing N₂O from exhaust streams which utilizes a unique and unobvious class of catalysts. The process comprises reacting the N₂O-containing stream in the presence of an effective amount of an enumerated catalyst under conditions sufficient to convert the N₂O to gaseous nitrogen and gaseous oxygen. Applicants have discovered that high conversion of N₂O to its corresponding decomposition products can be achieved by utilizing a catalytic system comprising a crystalline zeolite having a structure type which, at least in part, is composed of five-membered rings selected from the group consisting of BETA, MOR, MFI, MEL and FER wherein the crystalline zeolite has a metal component which has been at least partially ion-exchanged with a metal or an oxide of a metal selected from the group consisting of copper, cobalt, rhodium, iridium, ruthenium and palladium. The crystalline zeolites provide a favorable environment for the active metal catalysts such that unexpectedly improved catalytic activity is achieved over known processes employing active metal catalysts which are exchanged onto amorphous or crystalline supports other than those disclosed by the Applicants. Typical amounts of the active metals to be exchanged onto the subject crystalline zeolites range from 0.01 to about 15 wt% based upon the total weight of the catalyst. The process is typically run at temperatures ranging from about 200°C to 800°C and pressures between 0.1 and 300 atmospheres. The process according to this invention can be run under a wide variety modes including in a fixed bed reactor utilizing a gas hourly space velocity ranging from 1,000 hr⁻¹ to 300,000 hr⁻¹. Applicants' process and the results obtained therefrom are most unexpected in view of the collective teachings of the prior art. Prior to this invention, no long lived, catalytic process employing metal-exchanged crystalline zeolites as catalysts was known for effectively destroying N₂O in an oxygen-containing combustion product. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 compares reaction conversion of N₂O to gaseous nitrogen and oxygen over various catalysts as a function of temperature. FIG. 2 illustrates catalyst activities for N₂O decomposition over various metal-exchanged zeolite catalysts. FIG. 3 is illustrates catalyst activities for N₂O decomposition over various noble metal-exchanged zeolites. DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a highly efficient catalytic process for converting nitrous oxide (N₂O) into environmentally safe products, namely gaseous oxygen and gaseous nitrogen. The process utilizes a unique catalyst system formed from two components, an active metal component and a crystalline zeolite support having a specified morphology. While the zeolite is substantially noncatalytic toward the decomposition reaction in the absence of the metal component, the unique structure of the zeolites of the present invention provide unexpectedly superior conversion than other supports known in the art. More particularly, the crystalline zeolites provide a favorable environment for the active metal catalysts such that unexpectedly improved catalytic activity under moderate reaction conditions is achieved over known processes employing active metal catalysts which are exchanged onto amorphous or crystalline supports other than those disclosed by the Applicants. The process for destroying nitrous oxide comprises contacting a gaseous mixture containing the nitrous oxide with a catalyst under conditions sufficient to convert the nitrous oxide to gaseous nitrogen and gaseous oxygen wherein the catalyst comprises a crystalline zeolite having a structure type selected from the group consisting of BETA, MOR, MFI, MEL and FER wherein the crystalline zeolite has a metal component which has been modified, at least in part, by ion-exchange, with a metal selected from the group consisting of copper, cobalt, rhodium, iridium, ruthenium and palladium. The enumerated crystalline zeolites according to the present invention represent structures having a unique morphology. Each zeolite is composed, at least in part, of five-membered rings which form portions of the channels within the zeolite. The zeolites of the present invention contain five-membered rings as secondary building units. Secondary building units are the smallest groupings of linked tetrahedra which comprise the three dimensional zeolite framework structure. The concept of secondary building units is described in D. W. Breck, Zeolite Molecular Sieves, p. 46, (John Wiley & Sons, 1974). Such five membered rings may also exist in combination with smaller or larger rings. Specific crystalline zeolites which possess such five-membered rings and which are suitable for ion exchange with the metals according to the present invention include zeolites falling under the IUPAC designation (MOR). Representative zeolites of the (MOR) designation include, but are not limited to, mordenite, Na-D, Ptilolite and Zeolon. Zeolites under the IUPAC designation (MFI) include, but are not limited to ZSM-5, Silicalite-1, Silicalite, Zeta-1, Zeta-3, NU-3, NU-4 and AZ-1. Zeolites under the (MEL) designation include ZSM-11 and Silicalite-2 and zeolites under the (FER) designation include ferrierite. Additional zeolites suitable for practicing the present invention which possess the required channels formed from five-membered rings include naturally occurring zeolites such as dachiardite, epistilbite and bikitaite and synthetic zeolites such as theta-1, sigma-2, EU-1, mazzite, ECR-1, ZSM-39, ZSM-23 and ZSM-12. Boron- or gallium-substituted pentasil framework structures such as Boralite, AMS-1B and AMS-2B are also suitable for practicing the present invention. The crystalline zeolites of the present invention can be used either in the alkali metal form, e.g., the sodium or potassium form; the ammonium form; the hydrogen form or another univalent or multivalent cationic form to the extent that such zeolites are capable of being exchanged with the metals discussed herein. Suitable crystalline zeolites falling under the enumerated IUPAC designations include those materials which are stable under the described reaction conditions. Preferably, the crystalline zeolites to be exchanged reside in their sodium form. Typically, the pore size of the base zeolite will range from about 5 to 15 angstroms although such a range is not to be construed as limiting the scope of this invention. A preferred zeolite for practicing the present invention is ZSM-5 which can be prepared by the procedures disclosed in U.S. Patent 3,702,886, I & EC 24, 507 (1985) and Shiralkar, et. al., Zeolite, 9, 363, (1989), the disclosures which are specifically incorporated by reference herein. The term, mordenite, is meant to include those synthetic and naturally occurring zeolites having the mordenite topology as included under the general IUPAC structural code of mordenite (MOR). While naturally occurring mordenites vary widely in purity, the synthetic zeolites tend to have higher purity and controlled pore structure thereby rendering the synthetic mordenites preferable for catalytic applications. Mordenite can be synthesized from a wide variety of starting materials of both chemical and natural origins. Synthetic mordenites are typically produced with Si/Al ratios ranging from 5 to about 12.5. Mordenite is a porous crystalline catalyst having a rigid three-dimensional anionic network with intracrystalline channels whose narrowest cross-section has essentially a uniform diameter. Mordenite is distinguished over crystalline alumino-silicate clays such as bentonite which have a two-dimensional layered structure and over alumino-silicates which are amorphous. LZ-M-5, a synthetic mordenite residing in the non-acid, sodium cation form and an example of a MOR structure type zeolite, is commercially available from Union Carbide Corporation, Chickasaw, Alabama. LZM-5 has the following chemical composition (wt% anhydrous) SiO₂ 78.7 Al₂O₃ 12.5 Na₂O 7.33 SiO₂/Al₂O₃ (molar ratio) 10.7 Na₂O/Al₂O₃ (molar ratio) 0.96 ZSM-11, an example of a zeolite falling under the IUPAC designation (MEL) can be prepared according to the general procedure presented in U.S. Patent 3,709,979. ZSM-11 is a crystalline zeolite having the composition 0.9 +/- 0.3 M₂O:W₂O₃:20 to 90 YO₂:ZH₂O wherein M is a cation, n is the valence of the cation, W is aluminum or gallium, Y is silicon or germanium and Z is from 6 to 12, the zeolite being characterized by specified X-ray diffraction values. The zeolite is prepared by digesting a reaction mixture comprising (R₄X)₂O, sodium oxide, and oxide of aluminum or gallium, an oxide of silicon or germanium, and water, R₄X being a cation of a quaternary compound. Ferrierite, an example of a zeolite under the IUPAC designation (FER) can be prepared by standard methods disclosed in the literature. Ferrierite is commercially available from TOSOH Corporation, No. 4560 Tonda, Shin-Nanyo City, Yamaguch Pref., Japan. The original alkali metal cations of the crystalline zeolites according to this invention are replaced in accordance with techniques well known in the art such as ion-exchange, acid-base and solid state reactions. For example, the alkali metal cations of the crystalline zeolites can be replaced, at least in part, by ion-exchange with from about 0.01 wt% to about 15 wt% (based upon the total weight of the catalyst) of one or more cations selected from copper, cobalt, rhodium, iridium, ruthenium and palladium. A suitable metal-exchange technique comprises contacting the zeolite with a solution which contains the salt of the desired replacing cation or cations. Examples of suitable salts include the halides such as chlorides, nitrates, carboxylates and sulfates. Preferred exchange solutions include cobalt(II) acetate and copper(II) nitrate. The catalysts of this invention may be subjected to thermal treatment prior to use in the process. The thermal treatment may be conducted in the reactor prior to contacting the reactants with the catalyst or as a separate step. The thermal treatment comprises heating the catalysts of this invention to above ambient temperature, preferably between about 80° and 150°C while under an inert atmosphere of about 1 to 220 atmospheres for a period ranging from about 0.5 to 12 hours to remove residual moisture. The catalyst may be dried during one or more periods utilizing one or more discrete temperatures or temperature ramping techniques known in the art. The dehydration can be carried out by any method capable of removing water from the catalyst without causing structural collapse of the zeolite structure. The amount of catalyst to be utilized in the present process varies depending upon the reaction conditions (i.e., temperature, pressure and the like), and the amount of N₂O residing in the process stream to be treated. Desirably, an effective amount of catalyst is used, i.e., that amount which causes a reaction to occur when N₂O is placed in contact with the enumerated catalysts under the specified reaction conditions. The catalysts of the invention can be fabricated onto fire-proof supports known in the art including those customarily used in the automotive industry. A preferred support has a honey-comb design whereby surface area is maximized to enhance catalytic activity. The process according to this invention is typically run at temperatures ranging from about 200°C to 800°C and pressures between about 0.1 and 300 atmospheres. However, higher temperatures may be utilized because the maximum temperature for conducting the process is limited only by the temperature stability of the zeolite itself. More particularly, the process can be advantageously run under fixed bed conditions at temperatures ranging from about 250°C to 800°C and a gas hourly space velocity ranging from 1,000 to 300,000 hr⁻¹, preferably 7,500 hr⁻¹ to 30,000 hr⁻¹. The following examples are provided to further illustrate various embodiments of this invention and to provide a comparison between the enumerated catalysts of this invention and prior art catalysts for destroying N₂O in N₂O-containing atmospheres in the presence and absence of oxygen. These examples are provided to illustrate the nature of the process described herein and are not intended to limit the scope of the claimed invention. Unless otherwise stated, parts and percentages in the examples are given by volume. EXAMPLE 1 PREPARATION OF METAL-EXCHANGED (MOR) STRUCTURE TYPE ZEOLITES The metal-exchanged mordenite catalysts of the present invention are prepared according to the following general procedure. By way of example, Co-LZ-M-5 was prepared by submersing fifteen grams of LZ-M-5, obtained from Union Carbide Company, Chickasaw, Alabama, in a 2 liter Co(II)acetate solution (0.02 M) with stirring at 80°C for 24 hours. The resulting cobalt exchanged catalyst was washed with 2 liters of distilled water for 1 hour and filtered followed by drying at 110°C overnight. EXAMPLE 2 PREPARATION OF METAL-EXCHANGED (MFI) STRUCTURE TYPE ZEOLITES The metal-exchanged MFI structure type catalysts of the present invention were prepared according to the following general procedure. For example, ZSM-5 was prepared according to the general procedure described in I & EC 24 (1985) 507 wherein a gel was prepared containing 30% silica solution, sodium hydroxide and aluminum hydroxide in the molar ratio of 3.9 Na₂O/36 SiO₂/Al₂O₃/720 water. The resulting gel was stirred at 165°C in a PARR mini-reactor, filtered and washed with de-ionized water. The composition was verified by X-ray diffraction and elemental analysis. Fifteen grams of the resulting Na-ZSM-5, (Si/Al = 14) were submersed in a 3.5 liter Co(II)acetate solution (0.01 M) with stirring at room temperature for 18 hours followed at 40°C and 80°C for 20 and 24 hours, respectively. The resulting cobalt-exchanged catalyst was washed with 3.5 liters of distilled water for 1 hour and filtered followed by drying at 110°C for 5 hours. Elemental analysis demonstrated that the catalyst contained 4.0 wt% cobalt with a Co/Al ratio of 0.70 which corresponds to 140% of the theoretical exchange level. EXAMPLE 3 PREPARATION OF METAL-EXCHANGED (MEL) STRUCTURE TYPE ZEOLITES The metal-exchanged MEL structure type catalysts of the present invention such as ZSM-11 were prepared according to the general procedure described in U.S. Patent 3,709,979. EXAMPLE 4 PREPARATION OF METAL-EXCHANGED (FER) STRUCTURE TYPE ZEOLITES The metal-exchanged (FER) structure type catalysts of the present invention were prepared according to the following general procedure. The ferrierite catalyst was converted into the pure potassium form by twice contacting the material with 1.0M KCl (50g zeolite/liter) at 100°C for six hours. Three grams of potassium ferrierite were slurried in 100 ml of 0.05M cobalt acetate solution and stirred at 80°C for at least 18 hours. This exchange was repeated two more times then the catalyst was separated by filtration and dried overnight at 100°C. EXAMPLE 5 PREPARATION OF PRECIOUS METAL EXCHANGED (MFI) STRUCTURE TYPE ZEOLITES The zeolites were prepared as described in Example 2. The precious metal was added as follows. Sodium ZSM-5 (Si/Al = 14) was slurried in about 0.01M solutions of the precious metal compounds of platinum, palladium and ruthenium proportioned to achieve 1% loadings. The compounds utilized for these exchanges were tetraamineplatinium nitrate, palladium(II) acetate and ruthenium(III) chloride. The rhodium loaded ZSM-5 was prepared by slurrying in an approximately 0.033M solution proportioned to give a 4% weight loading of rhodium(III) nitrate. Each was stirred at least 18 hours then filtered and calcined at 450°C for 3 hours. EXAMPLE 6 CATALYTIC DESTRUCTION OF N ₂ O OVER METAL-EXCHANGED CRYSTALLINE ZEOLITES The following general procedure was utilized for effecting the catalytic conversion of N₂O to gaseous nitrogen and gaseous oxygen over the catalysts of the present invention. A reactor was constructed having a 4 mm i.d. glass tube with an expanded section (8 - 13 mm i.d.) as a catalyst bed. A separate inlet for admixing oxygen with the N₂O was provided at a position to enable thorough mixing just prior to contacting the reactants with the desired catalyst. The weight of catalyst used in these tests varied from a few tenths of a gram to one gram. The GHSV can be varied between 1000 and 300,000 to achieve desired conversion levels. The reactor was surrounded by a temperature-controlled furnace. The temperature was monitored by a chromel-alumel thermocouple which was in contact with the catalyst bed. The activity measurements were made with a microcatalytic reactor in a steady-state flow mode. Product analysis was obtained using an on-line gas chromatograph with a thermal conductivity detector. The separation column was packed with 5A molecular sieve (80/100 mesh) and was 4 feet long having a 1/8" outer diameter. Chromatograph temperature was 25°C and the flow rate of the carrier gas was 30 cm³/min. The N₂O decomposition was carried out at ambient pressure. 0.1g of catalyst in a plug-flow reactor was used for each run. The flow rate of the feed was 100 cm³/min and remained constant resulting in a gas hourly space velocity (GHSV) of 30,000 h⁻¹. The reaction temperatures studied ranged from 200° to about 800°C. The catalysts studied were dried for one hour at 400° to 500°C over a helium stream prior to use. PRESENTATION OF DATA The catalysts according to Examples 1 through 4 and various prior art catalysts were tested according to the procedure of Example 5 for catalytic reduction of N₂O in the absence of oxygen and in the presence of oxygen. Reaction conditions were maintained constant using a feedstream of 0.1% N₂O and 99.9% helium. A N₂O feedstream containing 2.5% oxygen was used in experiments on the effect of oxygen on catalyst activity. The results presented in Table 1 and graphically depicted in Figure 1 compare reaction conversion of N₂O to gaseous nitrogen and oxygen for various catalysts as a function of temperature. The results demonstrate that Cu-ZSM-5 (Run 1) provides unexpectedly high conversion (94%) of N₂O to gaseous nitrogen and oxygen at 400°C compared to Cu-Y (Run 2) and Cu/Al₂O₃ (Run 3) which demonstrated conversions of 10% and 5%, respectively. Likewise, Co-ZSM-5 COMPARISON OF N₂O CONVERSION OVER VARIOUS METAL CATALYST AS A FUNCTION OF TEMPERATURE Run Catalyst Temp (°C) Ea (Kcal/nol) Metal Loading (wt%) 400 450 500 1 Cu-ZSM-5 94 N/A N/A 32 4.0 2 Cu-Y 10 16 29 11 9.6 3 Cu/Al₂O₃ 5 19 69 29 4.0 4 Cu-L N/A 7 N/A N/A N/A 5 Co-ZSM-5 51 N/A N/A 32 4.0 6 Co-Y 4 7 14 16 11.8 7 Co-L 16 37 N/A N/A 3.5 8* Co/Al₂O₃ 7 12 31 15 10.0 9 Fe-ZSM-5 7 20 66 27 1.0 10 Ni-ZSM-5 - 5 12 19 4.3 11 Mn-ZSM-5 - - 5 24 3.0 12 Na-ZSM-5 - - - - 2.5 N/A: Data not available - : No activity detected Ea : Activation energy (a parameter reflecting the degree of temperature dependency on reaction rate) (Run 5) provided unexpectedly superior conversion at 400°C compared to Co-Y (Run 6), Co-L (Run 7) and Co/Al₂O₃. Runs 8 through 10 demonstrate that reaction conversion is highly dependent upon the particular metal exchanged onto the crystalline zeolite. Run 11 confirms that the sodium exchanged ZSM-5 catalyst, in the absence of metal exchange possess essentially no catalytic activity for the subject reaction. Table 2 provides a comparison of conversions achieved by reacting N₂O over cobalt- and copper-exchanged ZSM-5 in the presence of 2.5% oxygen in the N₂O feedstream and in the absence of oxygen in the N₂O feedstream. The data presented in Table 2 demonstrate that the process for converting N₂O to gaseous nitrogen and oxygen is substantially unaffected by the presence of oxygen in the feedstream. Runs 13 through 17 demonstrate that average conversion of N₂O over cobalt-exchanged ZSM-5 at 410°C using a feedstream containing 2.5% oxygen was 62.2% versus 59.6% in the absence of oxygen in the feedstream. Runs 18 through 25 demonstrate that average conversion of N₂O over copper-exchanged ZSM-5 at 400°C using a feedstream containing 2.5% oxygen was 83.4% versus 91.0% in the absence of oxygen in the feedstream. EFFECT OF OXYGEN ADDITION ON ACTIVITY OF METAL-EXCHANGED ZSM-5 CATALYSTS Run Catalyst Temp(°C) Activity Without O₂ With O₂ 13 Co-ZSM-5 410 57 63 14 Co-ZSM-5 410 58 63 15 Co-ZSM-5 410 62 61 16 Co-ZSM-5 410 62 62 17 Co-ZSM-5 410 59 62 18 Cu-ZSM-5 400 94 83 19 Cu-ZSM-5 400 94 87 20 Cu-ZSM-5 400 94 82 21 Cu-ZSM-5 400 95 82 22 Cu-ZSM-5 400 82 85 23 Cu-ZSM-5 400 89 83 24 Cu-ZSM-5 400 88 85 25 Cu-ZSM-5 400 92 80 Table 3 illustrates catalyst activities for N₂O decomposition over metal-exchanged zeolite catalysts. The data is graphically depicted in Figure 2. Each Run demonstrates that higher conversions were achieved overall when reaction temperature was elevated from 350°C to 400°C. Comparative examples 30 and 31 demonstrate that zeolites which do not possess a structure including five-membered rings provide poor conversion. While each of the catalysts of the present invention provided a substantial degree of conversion, copper-exchanged ZSM-5 (Run 34) provided 94% conversion at 400°C. CATALYST ACTIVITIES FOR N₂O DECOMPOSITION OVER METAL-EXCHANGED MORDENITE AND ZEOLITE BETA Run Catalyst Metal Loading (wt%) Conversion 350°C 400°C 26 Co-M 5.6 16 49 27 Co-BETA 2.3 23 67 28 Co-ZSM-5 3.6 11 51 29 Co-Y 11.8 - 4 30 Co-Erionite 4.5 - 15 31 Co-L 3.5 - 16 32 Cu-M 6.5 8 37 33 Cu-BETA 3.6 24 58 34 Cu-ZSM-5 3.7 17 94 35 Co-Ferrierite 7.6 11 35 36 Co-ZSM-11 3.7 14 35 - No activity detected Table 4 demonstrates catalyst activities for N₂O decomposition over various noble metal-exchanged zeolites. The data are graphically depicted in Figure 3. Runs 37, 39 and 41 demonstrate that exceptionally high conversion was achieved using rhodium-, palladium-, and ruthenium-exchanged ZSM-5 when the process was run at 350°C. In contrast, platinum-exchanged ZSM-5 (Run 41) demonstrated no catalytic activity under the cited conditions. Comparative Runs 38, 40 and 42 demonstrate that the subject metals provide very poor conversion when deposited onto amorphous alumina. The expected results obtained by the present invention are evident when a direct comparison is made between the conversions obtained by using Applicants' zeolite based catalysts which contain the enumerated five-membered rings versus catalysts based upon alumina. CATALYST ACTIVITIES FOR N₂O DECOMPOSITION OVER NOBLE-METAL-EXCHANGED ZSM-5 Run Catalyst Metal Loading (wt%) Conversion 300°C 350°C 37 Rh-ZSM-5 0.6 72 98 38 Rh-Al₂O₃ 1.2 39 N/A 39 Pd-ZSM-5 3.4 24 68 40 Pd-Al₂O₃ 4.2 - <5 41 Ru-ZSM-5 0.6 64 97 42 Ru-Al₂O₃ 1.0 N/A 29 43 Pt-ZSM-5 2.6 - - 44 Cu-ZSM-5 3.7 N/A 17 N/A: Data not available. - No activity detected Table 5 provides a comparison of conversions achieved by reacting N₂O over noble-metal exchanged ZSM-5 in the presence of 2.5% oxygen in the N₂O feedstream and in the absence of oxygen in the N₂O feedstream. The data presented in Table 5 demonstrate that the process for converting N₂O to gaseous nitrogen and gaseous oxygen is substantially unaffected by the presence of 2.5% oxygen in the N₂O feedstream. The data also illustrate that conversion of N₂O over rhodium-exchanged ZSM-5 (Run 43) and palladium-exchanged ZSM-5 (Run 44) at 400°C was not affected by the presence of 2.5% oxygen in the process feedstream. EFFECT OF OXYGEN ADDITION ON ACTIVITY OF NOBLE-METAL EXCHANGED ZSM-5 Run Catalyst Temp(°C) Activity Without O₂ With O₂ 45 Rh-ZSM-5 350 98 90 46 Pd-ZSM-5 374 91 91 47 Ru-ZSM-5 350 97 37 The enumerated catalysts of the present invention provide several improvements over prior art processes for removing N₂O from combustion processes. First, the claimed catalysts are unexpectedly more active than prior art catalysts in converting N₂O to nitrogen gas and oxygen gas. Second, the catalysts are not significantly deactivated in the presence of oxygen in the process feedstream.

Claims: A process for removing nitrous oxide (N₂O) from a gaseous mixture comprising: contacting the gaseous mixture containing the nitrous oxide with a catalyst comprising a crystalline zeolite having a structure type selected from the group consisting of BETA, MOR, MFI, MEL and FER which has been at least partially ion exchanged with a metal selected from the group consisting of copper, cobalt, rhodium, iridium, ruthenium and palladium. The process according to claim 1 wherein the crystalline zeolite has been exchanged with from 0.01 to about 15 wt% of the metal based upon the total weight of the catalyst. The process according to claim 1 or 2 wherein the reacting is conducted at temperatures ranging from 200° to 800°C and pressures ranging from 0.01 to 300 bar. The process according to any one of claims 1 to 3 wherein the reacting is conducted in a fixed bed reactor with a gas hourly space velocity ranging from 1,000 hr⁻¹ to 300,000 hr⁻¹. The process according to any one of claims 1 to 4 wherein the MOR structure type crystalline zeolite is selected from the group consisting of a synthetic mordenite, a natural mordenite, Na-D and ptilolite. The process according to any one of claims 1 to 4 wherein the MFI structure type crystalline zeolite is selected from the group consisting of ZSM-5, silicalite-1, silicalite, Zeta-1, Zeta-3, NU-4, NU-5 and AZ-1. The process according to any one of claims 1 to 4 wherein the MEL structure type crystalline zeolite is selected from the group consisting of ZSM-11 and silicalite-2. The process according to any one of claims 1 to 4 wherein the FER structure type crystalline zeolite is ferrierite.

Inventors: ARMOR JOHN NELSON, LI YUEJIN, ARMOR, JOHN NELSON, LI, YUEJIN
Applicants: ENGELHARD CORP, ENGELHARD CORPORATION
Application year: 1992
Main classification: B01D53
IPC codes: B01D53, B01J29