Alkaline earth/transition metal lean NOx catalyst

[0002] The present invention relates to a catalyst for purifying exhaust gases from an internal combustion engine. In particular, it relates to a lean NO_xcatalyst.

[0003] It is well known in the art to use catalyst compositions, including those commonly referred to as three-way conversion (“TWC”) catalysts to treat the exhaust gases of internal combustion engines. Such catalysts, containing precious metals like platinum, palladium, and rhodium, have been found both to successfully promote the oxidation of unburned hydrocarbons (HC) and carbon monoxide (CO) and to promote the reduction of nitrogen oxides (NO_x) in exhaust gas, provided that the engine is operated around balanced stoichiometry for combustion (“combustion stoichiometry”; i.e., between about 14.7 and 14.4 air/fuel (A/F) ratio).

[0004] However, fuel economy and global carbon dioxide (CO₂) emissions have made it desirable to operate engines under lean-burn conditions, where the air-to-fuel ratio is somewhat greater than combustion stoichiometry to realize a benefit in fuel economy. Diesel and lean-burn gasoline engines generally operate under highly oxidizing conditions (i.e., using much more air than is necessary to burn the fuel), typically at air/fuel ratios greater than 14.7 and generally between 19 and 35. Under these highly lean conditions, typical three-way catalysts exhibit little activity toward NOxreduction, as their reduction activity is suppressed by the presence of excess oxygen.

[0005] The control of NO_xemissions from vehicles is a worldwide environmental problem. Lean-burn, high air-to-fuel ratio, and diesel engines are certain to become more important in meeting the mandated fuel economy requirements of next-generation vehicles. Development of an effective and durable catalyst for controlling No_xemissions under net oxidizing conditions accordingly is critical.

[0006] Recently, copper-ion exchanged zeolite catalysts have been shown to be active for selective reduction of No_xby hydrocarbons in the presence of excess oxygen. Platinum-ion exchanged zeolite catalyst is also known to be active for No_xreduction by hydrocarbons under lean conditions. However, this catalytic activity is significant only in a narrow temperature range around the lightoff temperature of hydrocarbon oxidation. All the known lean-NO_xcatalysts reported in the literature tend to lose their catalytic activity for NO_xreduction when the catalyst temperature reaches well above the lightoff temperature of hydrocarbon oxidation. This narrow temperature window of the lean-No_xcatalysts is considered to be one of the major technical obstacles, because it makes practical application of these catalysts difficult for lean-burn gasoline or diesel engines.). As an example, the Cu-zeolite catalysts deactivate irreversibly if a certain temperature is exceeded. Catalyst deactivation is accelerated by the presence of water vapor in the stream and water vapor suppresses the NO reduction activity even at lower temperatures. Also, sulfate formation at active catalyst sites and on catalyst support materials causes deactivation. Practical lean-No_xcatalysts must overcome all three problems simultaneously before they can be considered for commercial use. In the case of sulfur poisoning, some gasoline can contain up to 1200 ppm of organo-sulfur compounds. Lean-NO_xcatalysts promote the conversion of such compounds to SO₂and SO₃during combustion. Such SO₂will adsorb onto the precious metal sites at temperatures below 300° C. and thereby inhibits the catalytic conversions of CO, C_xH_y(hydrocarbons) and No_x. At higher temperatures with an Al₂O₃catalyst carrier, SO₂is converted to SO₃to form a large-volume, low-density material, Al₂(SO₄)₃, that alters the catalyst surface area and leads to deactivation. In the prior art, the primary solution to this problem has been to use fuels with low sulfur contents.

[0007] Another alternative is to use catalysts that selectively reduce NO_xin the presence of a co-reductant, e.g., selective catalytic reduction (SCR) using ammonia or urea as a co-reductant. Selective catalytic reduction is based on the reaction of NO with hydrocarbon species activated on the catalyst surface and the subsequent reduction of NO_xto N₂. More than fifty such SCR catalysts are conventionally known to exist. These include a wide assortment of catalysts, some containing base metals or precious metals that provide high activity. Unfortunately, just solving the problem of catalyst activity in an oxygen-rich environment is not enough for practical applications. Like most heterogeneous catalytic processes, the SCR process is susceptible to chemical and/or thermal deactivation. Many lean-NO_xcatalysts are too susceptible to high temperatures, water vapor and sulfur poisoning (from SO_{x l ).}

[0008] Yet another viable alternative involves using co-existing hydrocarbons in the exhaust of mobile lean-burn gasoline engines as a co-reductant and is a more practical, cost-effective, and environmentally sound approach. The search for effective and durable non-selective catalytic reduction “NSCR” catalysts that work with hydrocarbon co-reductant in oxygen-rich environments is a high-priority issue in emissions control and the subject of intense investigations by automobile and catalyst companies, and universities, throughout the world.

[0009] A leading catalytic technology for removal of NO_xfrom lean-burn engine exhausts involves No_xstorage reduction catalysis, commonly called the “lean-No_xtrap”. The lean-No_xtrap technology can involve the catalytic oxidation of NO to NO₂by catalytic metal components effective for such oxidation, such as precious metals. However, in the lean NO_xtrap, the formation of NO₂is followed by the formation of a nitrate when the NO₂is adsorbed onto the catalyst surface. The NO₂is thus “trapped”, i.e., stored, on the catalyst surface in the nitrate form and subsequently decomposed by periodically operating the system under stoichiometrically fuel-rich combustion conditions that effect a reduction of the released NO_x(nitrate) to N₂.

[0010] The lean-NO_x-trap technology has been limited to use for low sulfur fuels because catalysts that are active for converting NO to NO₂are also active in converting SO₂to SO₃. Lean NO_xtrap catalysts have shown serious deactivation in the presence of SO_xbecause, under oxygen-rich conditions, SO_xadsorbs more strongly on NO₂adsorption sites than NO₂, and the adsorbed SO_xdoes not desorb altogether even under fuel-rich conditions. Such presence of SO₃leads to the formation of sulfuric acid and sulfates that increase the particulates in the exhaust and poison the active sites on the catalyst. Attempts with limited success to solve such a problem have encompassed the use of selective SO_xadsorbents upstream of lean No_xtrap adsorbents. Furthermore, catalytic oxidation of NO to NO₂is limited in its temperature range. Oxidation of NO to NO₂by a conventional Pt-based catalyst maximizes at about 250° C. and loses its efficiency below about 100 degrees and above about 400 degrees. Thus, the search continues in the development of systems that improve lean No_xtrap technology with respect to temperature and sulfur considerations.

[0011] Another NO_xremoval technique comprises a non-thermal plasma gas treatment of NO to produce NO₂which is then combined with catalytic storage reduction treatment, e.g., a lean NO_xtrap, to enhance No_xreduction in oxygen-rich vehicle engine exhausts. In the lean NO_xtrap, the NO₂from the plasma treatment is adsorbed on a nitrate-forming material, such as an alkali material, and stored as a nitrate. An engine controller periodically runs a brief fuel-rich condition to provide hydrocarbons for a reaction that decomposes the stored nitrate into benign products such as N₂. By using a plasma, the lean NO_xtrap catalyst can be implemented with known No_xabsorbers, and the catalyst may contain less or essentially no precious metals, such as Pt, Pd and Rh, for reduction of the nitrate to N₂. Accordingly, an advantage is that a method for NO_xemission reduction is provided that is inexpensive and reliable. The plasma-assisted lean NO_xtrap can allow the life of precious metal lean NO_xtrap catalysts to be extended for relatively inexpensive compliance to NO_xemission reduction laws. Furthermore, not only does the plasma-assisted lean No_xtrap process improve the activity, durability, and temperature window of lean No_xtrap catalysts, but it allows the combustion of fuels containing relatively high sulfur contents with a concomitant reduction of NO_x, particularly in an oxygen-rich vehicular environment.

[0012] What is needed in the art is an exhaust gas catalyst system having improved durability, as well as effective NO_xmanagement, over extended operating time. The present invention overcomes many of the shortcomings of the prior art.

[0013] Diesel exhaust emissions have high levels of CO, No_xand particulates. In addition, hydrocarbon is introduced into the exhaust stream as a reducing agent. All of these exhaust gas stream components must be reduced to meet emissions standards. The particulates in the exhaust gas stream initially are trapped as large particulates and converted to CO by the plasma reactor. The No_xcomponent of the exhaust gas stream is reduced on the first catalyst bed, containing an occluding material such as barium and a support such as a zeolite. However, the CO and hydrocarbon levels also must be reduced. Now, according to the present invention, an exhaust gas catalyst is provided to serve as a clean-up type catalyst bed that will oxidize CO to CO₂and HC to H₂O and CO₂, without re-oxidation of N₂to NO and NO₂, without re-oxidation of SO₂to SO₃.

[0014] Pursuant to the present invention, a catalyst is provided comprising an alkaline earth/transition metal oxide component and an alkaline earth/support component.

[0015] The invented catalyst is designed not to be poisoned by sulfur and not to convert gaseous SO₂to particulates formed from SO₃and H₂O. The catalyst exhibits good activity at relatively low temperatures. By inclusion of both a reducing catalyst component and an oxidizing catalyst component the bifunctional catalyst serves not increase the NO_xor particulate sulfate levels. Further, the catalyst is not significantly affected by the high levels of H₂O in a diesel exhaust stream.

[0016] The above-described and other features and advantages of the present invention will be appreciated and understood by those skilled in the art from the following detailed description, and appended claims.

[0017] The catalyst generally comprises a calcined coating of an alkaline earth/transition metal oxide, and an alkaline earth/support oxide coated onto a chemically stable and thermally insulating substrate, typically such as cordierite, mullite, and the like. The support oxide generally may be a zeolite or an aluminum oxide or a mixture of zeolite and aluminum oxide. Preferably, the catalyst coating also includes a ceramic oxide binder and/or stabilizer.

[0018] The alkaline earth/transition metal oxide catalyst component preferably comprises an alkaline earth content of about 1 wt % to about 50 wt %; about 18 wt % to about 36 wt % is particularly preferred.

[0019] The alkaline earth/support catalyst component preferably is not more than about 81 wt % of the total catalyst, and more preferred at not more than about 76 wt %. Particularly preferred is alkaline earth/support component at about 69 wt %. Preferably, the transition metal/alkaline earth oxide catalyst component is at least about 14 wt % and more preferred at least about21 wt %. Particularly preferred is transition metal/alkaline earth oxide at about 28 wt %. The ceramic binder preferably is greater than about 1 wt % and not more than about 7 wt %; about 3 wt % is particularly preferred.

[0020] A preferred calcined catalyst coating comprises less than about 46 wt % alkaline earth/zeolite, less than about 35 wt % alkaline earth/aluminum oxide, more than about 14 wt % transition metal/alkaline earth oxides and not more than about 7 wt % ceramic oxide binder. A more preferred calcined coating comprises less than about 42 wt % alkaline earth/zeolite, less than about 34 wt % alkaline earth/aluminum oxide, more than about 21 wt % transition metal/alkaline earth oxide, and not more than about 5 wt % ceramic oxide binder. A particularly preferred calcined coating comprises about 38 wt % alkaline earth/zeolite, about 31 wt % alkaline earth/aluminum oxide, about 28 wt % transition metal/alkaline earth oxide and about 3 wt % ceramic oxide binder.

[0021] Any alkaline earth may be utilized in the alkaline earth/transition metal component of the catalyst. Barium, strontium, and/or calcium are the preferred alkaline earths; strontium and calcium are more preferred; and, calcium is particularly preferred.

[0022] Suitable calcium compounds for introducing the alkaline earth include calcium succinate, calcium tartrate, calcium citrate, calcium acetate, calcium carbonate, calcium hydroxide, calcium oxylate, calcium oleate, calcium palmitate and calcium oxide. Calcium acetate, calcium oxylate, and calcium citrate are preferred. Calcium citrate is particularly preferred.

[0023] Suitable strontium compounds for introducing the alkaline earth include strontium citrate, strontium acetate, strontium carbonate, strontium hydroxide, strontium oxylate and strontium oxide. Strontium acetate, strontium oxylate, and strontium citrate are preferred. Strontium citrate is particularly preferred.

[0024] Suitable barium compounds for introducing the alkaline earth include barium butyrate, barium formate, barium citrate, barium acetate, barium oxylate, barium carbonate, barium hydroxide and barium oxide. Barium acetate, barium oxylate, and barium citrate are preferred. Barium citrate is particularly preferred.

[0025] Any transition metal may be utilized. Nickel, manganese, and/or cobalt are the preferred transition metals; manganese and cobalt are more preferred; and, cobalt is particularly preferred.

[0026] Suitable nickel compounds for introducing the transition metal include nickel formate, nickel acetate, nickel citrate, nickel nitrate, nickel carbonate, nickel hydroxide, nickel isopropoxide, nickel oxylate, nickel tartrate and nickel amine nitrate. Nickel acetate, nickel citrate, and nickel formate are more preferred. Nickel formate is particularly preferred.

[0027] Suitable manganese compounds for introducing the transition metal include manganese formate, manganese acetate, manganese citrate, manganese nitrate, manganese carbonate, manganese hydroxide, manganese isopropoxide, manganese oxylate, manganese tartrate and manganese amine nitrate. Manganese acetate, manganese citrate, and manganese formate are preferred. Manganese formate is particularly preferred.

[0028] Suitable cobalt compounds for introducing the transition metal include cobalt formate, cobalt acetate, cobalt citrate, cobalt nitrate, cobalt carbonate, cobalt hydroxide, cobalt isopropoxide, cobalt oxylate, cobalt tartrate and cobalt amine nitrate. Cobalt acetate, cobalt citrate, and cobalt formate are preferred. Cobalt formate is particularly preferred.

[0029] The surface area of the alkaline earth and transition metal oxides may be stabilized with other binder oxides, such as oxides of silicon, titanium, and/or zirconium. Titanium and zirconium are preferred; zirconium is particularly preferred. The binder/stabilizer preferably comprises not more than about 7 wt %; more preferred at not more than about 5 wt %; and, particularly preferred not more than about 3 wt %.

[0030] Suitable zirconium compounds for introduction of the surface area stabilizer include zirconium acetylacetonate, zirconium n-butoxide, zirconium nitrate, zirconium tetraamine nitrate, zirconium tetraamine citrate, zirconium 2-ethylhexanoate, and zirconium isopropoxide. Zirconium tetraamine citrate, zirconium butoxide, and zirconium isopropoxide are preferred; zirconium butoxide and zirconium isopropoxide are more preferred; and, zirconium isopropoxide is particularly preferred.

[0031] Suitable titanium compounds for introduction of the surface area stabilizer include titanium oxylate, titanium ethoxide, titanium methoxide, titanium isopropoxide, zirconium n-butoxide. Titanium butoxide, titanium ethoxide, and titanium isopropoxide are preferred; titanium ethoxide and titanium isopropoxide are more preferred; and, titanium isopropoxide is particularly preferred.

[0032] Suitable silicon compounds for introduction of the surface area stabilizer include silicon acetate, tetraethoxysilane, tetramethoxysilane, vinyltrimethoxysilane, ureidopropyltriethoxysilane and aminopropylsilanetriol. Tetraethoxysilane, silicon acetate, and tetramethoxysilane are preferred; silicon acetate and tetramethoxysilane are more preferred; and, tetramethoxysilane is particularly preferred.

[0033] The catalyst of the present invention comprises an alkaline earth/support component, wherein the support may be a zeolite and/or alumina. The alumina fraction of the support may be present in a proportion ranging from about 0 wt % to about 100 wt % of the alkaline earth/support fraction. A particularly preferred admixture comprises an alkaline earth/aluminum oxide fraction in a proportion ranging from about 35 wt % to about 45 wt %, and an alkaline earth/zeolite fraction in a proportion ranging from about 55 wt % to about 65 wt %.

[0034] Any type zeolite may be used; preferred zeolites include X type zeolite, Y type zeolite, and/or ZSM-5 type zeolite. A ZSM-5 zeolite with pores 4-5 A (angstroms) is preferred and an X zeolite is more preferred and a Y-type zeolite with pores 7-8 A is greatly preferred. A zeolite surface area of at least about 300 m²/gram is preferred, at least about 400 m²/g is more preferred, and a surface area of at least about 500 m²/g is particularly preferred. The preferred zeolite average particle size is less than about 0.9 microns; more preferred are zeolite particles of an average size less than about 0.6 microns; and particularly preferred are zeolites having an average particle size less than about 0.3 microns. The zeolite particles preferably feature average pore sizes ranging from about 4 to about 10 angstroms (“A”), with average pore sizes ranging from about 7 to 8 A particularly preferred. Preferably, the zeolite has a Na₂O content of at least about 3 wt %; a content of at least about 8 wt % is more preferred; and a content of at least about 13 wt % is particularly preferred.

[0035] The aluminum oxide particles providing the matrix comprise agglomerations of small psuedocrystalline alumina particles typically of about 0.3 microns or less. The agglomerations preferably are larger than about 10 microns and less than about 30 microns. The alumina matrix is mixed with a Ba-zeolite catalyst component, typically featuring a particulate size of about 0.3 microns. In general, the smaller the zeolite particle, the more hydrothermally stable the zeolite becomes, thereby improving its long-term activity. Pursuant to the invention, the zeolite active catalysts preferably are dispersed throughout the alumina matrix.

[0036] Preferably, the alumina has a surface area of at least about 150 m²/gram; a surface area of at least about 200 m²/g is more preferred; and, a surface area of at least about 250 m²/g is particularly preferred. An average alumina pore size of at least about 40 A is preferred; a pore size of at least about 60 A is more preferred; and, a pore size of at least about 80 A is particularly preferred. Specific acidity ranging from about 50 moles (millimoles) n-butylamine/m²×10⁻⁴to about 500 mmoles n-butylamine/m²×10⁻⁴is preferred; a specific acidity of about 350 mmoles n-butlyamine/m²×10⁻⁴is particularly preferred.

[0037] The zeolite catalyst component preferably comprises an alkaline earth content of about 18 wt % to about 36 wt %; about 24 wt % to about 30 wt % is particularly preferred. The aluminum oxide catalyst component preferably comprises an alkaline earth content of about 18 wt % to about 36 wt %; about 24 wt % to about 30 wt % is particularly preferred.

[0038] Any alkaline earth element may be used as the active catalyst. For example, the active catalyst element may comprise calcium, strontium, and/or barium. The use of barium is particularly preferred. Tests have indicated that calcium-doped catalysts generally convert about 30% NO_xto N₂; strontium-doped catalysts generally convert about 50% NO_xto N₂; barium-doped catalysts generally convert about 70% NO_xto N₂. Based on a desire in the industry to optimize conversion of NO_xto N₂at about 90% or better, barium is the particularly preferred occluding catalyst material.

[0039] Accordingly, Ba is the preferred occluding catalyst for both the zeolite and the alumina components of the present catalyst. The alumina matrix features enhanced trapping efficiency if it is doped with a material such as barium. In specific, nitrogen species can neutralize catalytically active sites. Barium is the most robust alkaline earth element for resistance to nitrogen poisoning. The alumina matrix provides sacrificial sites for nitrogen poisoning, thus precluding large polycyclic nitrogen compounds from entering and poisoning the small pores of the zeolite catalyst component. The zeolite catalyst component preferably comprises a barium content of about 18 wt % to about 36 wt %; about 24 wt % to about 30 wt % is particularly preferred. The alumina matrix catalyst component preferably has a barium content of at least about 14 wt %; at least about 21 wt % is more preferred; and, at least about 28 wt % is particularly preferred. Exhaust deposits of oil derived “glassy” compounds such as calcium phosphate and zinc phosphate can greatly reduce diffusion. High levels of alkaline earths, such as barium, prevent formation of these diffusion limiting barriers.

[0040] Suitable barium sources for preparation of a barium-alumina component include barium nitrate, barium acetate, barium hydroxide, barium ethoxide, barium isopropoxide, and/or barium 2-ethylhexanoate. Barium acetate, barium isopropoxide, and barium 2-ethylhexanoate are preferred. Barium 2-ethylhexanoate is particularly preferred.

[0041] The following examples are provided to further describe the invention. The examples are intended to be illustrative in nature and are not to be construed as limiting the scope of the invention.

[0042] Preparation of Ba-Cobalt Component

[0043] About 550 grams barium formate and 2090 grams cobalt formate are ball milled for 4 hours. The ball milled material is then calcined at 500° C. for 4 hours.

[0044] Preparation of a Ba-Zeolite Component.

[0045] About 1000 grams Y-Zeolite with a Na₂O content of 13 wt % is mixed with a saturated barium-nitrate solution and heated to 80° C. for 4 hours. The solids are filtered then washed then calcined at 740° C. for 2 hours.

[0046] Preparation of Catalyst Monolith

[0047] About 280 grams barium-cobalt oxide, 700 grams Ba-Zeolite, 88 grams zirconium acetate and 1150 grams 0.1 N ammonium hydroxide are well mixed. Ceramic monoliths containing 600 cells/in³are washcoated with the mixture then calcined at 500° C. for 4 hours.

[0048] Preparation of Ba-Cobalt Component

[0049] About 550 grams barium fornate and 2090 grams cobalt formate are ball milled for 4 hours. The ball milled material is then calcined at 500° C. for 4 hours.

[0050] Preparation of a Ba-Alumina Component

[0051] About 1000 grams gamma alumina with a surface area of at least 150 m²/gram with is mixed with a saturated barium-formate solution and heated to 80° C. for 4 hours. The solids are filtered then washed then calcined at 500° C. for 2 hours.

[0052] Preparation of Catalyst Monolith

[0053] About 280 grams barium-cobalt oxide, 700 grams Ba-aluminum oxide, 88 grams zirconium acetate and 1150 grams 0.1 N ammonium hydroxide are well mixed. Ceramic monoliths containing 600 cells/in³are washcoated with the mixture then calcined at 500° C. for 4 hours.

[0054] Preparation of Ba-Cobalt Component

[0055] About 550 grams barium formate and 2090 grams cobalt formate are ball milled for 4 hours. The ball milled material is then calcined at 500° C. for 4 hours.

[0056] Preparation of a Ba-Zeolite Component

[0057] About 1000 grams Y-Zeolite with a Na₂O content of 13 wt % is mixed with a saturated barium-nitrate solution and heated to 80° C. for 4 hours. The solids are filtered then washed then calcined at 740° C. for 2 hours.

[0058] Preparation of a Ba-Alumina Component

[0059] About 1000 grams gamma alumina with a surface area of at least 150 m²/gram with is mixed with a saturated barium-fornate solution and heated to 80° C. for 4 hours. The solids are filtered then washed then calcined at 500° C. for 2 hours.

[0060] Preparation of Catalyst Monolith

[0061] About 280 grams barium-cobalt oxide, 420 grams Ba-Zeolite, 280 grams Ba-aluminum oxide, 88 grams zirconium acetate and 1150 grams 0.1 N ammonium hydroxide are well mixed. Ceramic monoliths containing 600 cells/in³are washcoated with the mixture then calcined at 500° C. for 4 hours.

[0062] While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustration only, and such illustrations and embodiments as have been disclosed herein are not to be construed as limiting to the claims.