Abstract:
A method is provided for operating a diesel engine with reduced emissions. The method comprises combusting a first biodiesel blend fuel in a diesel engine resulting in the production of diesel exhaust gases containing NOx. The diesel exhaust gases are admixed with a second biodiesel blend fuel, and the second biodiesel blend fuel is hydrolyzed to form reducing agents. The diesel exhaust gases containing NOx are passed through an NOx-reducing catalyst to reduce the NOx through a selective catalytic reduction reaction with the reducing agents. The invention further provides a method for operating a diesel engine with reduced emissions, comprising combusting a first biodiesel blend fuel in a diesel engine resulting in the production of diesel exhaust gases containing NOx. A second biodiesel blend fuel is converted in a fuel processor thereby forming reducing agents, and the diesel exhaust gases are admixed with the reducing agents. The diesel exhaust gases containing NOx are passed through an NOx-reducing catalyst to reduce the NOx through a selective catalytic reduction reaction with the reducing agents.

Description:
FIELD OF THE INVENTION 
     This invention relates to the use of biodiesel fuels in a diesel engine in combination with a selective catalytic reduction system to reduce NOx, particulates, and CO 2  emissions from the combustion process. 
     BACKGROUND OF THE INVENTION 
     Current emission control regulations necessitate reduction of pollutant species in diesel engine exhaust. These pollutants include carbon monoxide, unburned hydrocarbons, particulates or particulate matter, and nitrogen oxides (NOx). Additionally, reduction of CO 2  emissions is also being increasingly mandated. The decrease in the amounts of the pollutant chemical species produced during the engine operation is achieved by an optimized operation of the internal combustion engine, pre-treatments of the fuel and fuel additives, and post-treatment processing and filtration for conversion of exhaust into harmless gasses. Both oxidation and reduction processes, as well as catalytic oxidation and reduction processes are used for improving exhaust gas chemistry. The particulates are typically reduced by equipping diesel engines with particulate traps mounted in the exhaust stream, which trap or otherwise collect particulates from the exhaust to prevent their emission to the atmosphere. Catalytic oxidizers have been proposed to reduce the emission of particulates, gaseous hydrocarbons, and carbon monoxide from diesel engines. These devices do not trap the particulates, but are primarily intended to oxidize particulates while also oxidizing unburned hydrocarbons and carbon monoxide to reduce emissions of these substances. 
     NOx, principally NO and NO 2 , contributes to smog, ground level ozone formation and acid rain. NO is produced in large quantities at the high combustion temperatures associated with diesel engines. The NO 2  is formed principally by the post oxidation of NO in the diesel exhaust stream. Approaches to reduce NOx include, for instance, retarding engine timing, exhaust gas recirculation, or injection of a reducing agent; however, there is typically a tradeoff between NOx and particulates. For example, exhaust gas recirculation and engine timing changes can reduce the temperature of combustion to thereby decrease NOx formation, but combustion is also affected. When NO 2  is reduced due to lower temperature, particulate emissions tend to increase and conditions favoring low emissions of NOx often favor production of increased levels of CO and HC. Exhaust aftertreatment devices achieve NOx reduction by using a reductant agent, which is added to the exhaust gas entering the aftertreatment device and reacts with NOx over a catalyst in a process of selective catalytic reduction (SCR). In the selective catalytic reduction process NOx is reduced to N 2  by reacting with NH 3  (or urea as a source of NH 3 ) over a selective catalyst. SCR is efficient for NOx reduction as long as the exhaust temperature is within the active temperature range of the catalyst, which is typically above 300° C. 
     As noted above, a trade-off exists between particulates and nitrogen oxides, that is, when combustion conditions are modified to favor low nitrogen oxides emissions, particulates are increased. For example, when NOx reduction is attempted by modifying engine timing and/or recirculating exhaust gas, particulates typically are increased. Particulate traps do not directly increase NOx, but have been associated with increased production of carbon monoxide. In addition, even with a trap, unburned hydrocarbons remain a problem. By modifying combustion to achieve more complete oxidation, decreases can be achieved for pollutants resulting from incomplete combustion, but NOx is typically increased under these conditions. 
     Various combustion methods, fuel treatments and additives, post-combustion exhaust treatments, traps, and exhaust filtration systems have been proposed to reduce one or more of the noted pollutants or to solve a problem related to diesel exhaust. However, the achievement of lower emissions of NOx and overall CO 2  emissions reduction, while controlling particulates over reasonable periods of time, continues to present a technical challenge. 
     SUMMARY OF THE INVENTION 
     Embodiments of the invention provide methods and devices for improving the emission control in internal combustion engines fueled by diesel fuel, including lean-burn engines. Embodiments of the invention provide for the usage of biodiesel or biodiesel blend fuel for fueling diesel engines and generating exhaust streams with reduced particulates and lifecycle CO 2  emissions. Embodiments of the invention further provide for the production of reducing agents from biodiesel or biodiesel blend diesel fuel, and the use of these reducing agents for the catalytic reduction of NOx to N 2 . 
     Briefly stated, in accordance with one embodiment of the invention, there is provided a method for operating a diesel engine with reduced emissions, including combusting a first biodiesel blend fuel in a diesel engine resulting in the production of diesel exhaust gases containing NOx; admixing the diesel exhaust gases with a second biodiesel blend fuel; hydrolyzing the second biodiesel blend fuel to form reducing agents; and passing the diesel exhaust gases containing NOx through an NOx-reducing catalyst to reduce the NOx through a selective catalytic reduction reaction with the reducing agents. 
     In accordance with another embodiment of the invention, there is provided a method for operating a diesel engine with reduced emissions, including combusting a first biodiesel blend fuel in a diesel engine resulting in the production of diesel exhaust gases containing NOx; converting a second biodiesel blend fuel in a fuel processor thereby forming reducing agents; admixing the diesel exhaust gases with the reducing agents; passing the diesel exhaust gases containing NOx through an NOx-reducing catalyst to reduce the NOx through a selective catalytic reduction reaction with the reducing agents. 
    
    
     
       BRIEF DESCRIPTION OF THE DRAWINGS 
       The file of this patent contains at least one drawing executed in color. Copies of this patent with color drawings will be provided by the Patent and Trademark Office upon request and payment of the necessary fee. 
         FIG. 1  is a schematic representation of chemical processes carried out during the on-board thermal hydrolysis of biodiesel fuel and the SCR reduction of NOx in the exhaust stream in accordance with an embodiment of the invention. 
         FIG. 2  is a schematic block-diagram of a method for operating a diesel engine with reduced emissions in accordance with an embodiment of the invention. 
         FIG. 3  is a schematic diagram of an embodiment of the invention. 
         FIG. 4  is a schematic diagram of an alternative embodiment of the invention. 
         FIG. 5  is a schematic diagram of an alternative embodiment of the invention. 
         FIGS. 6(   a )- 6 ( d ) illustrate alternative embodiments of an exhaust treatment system for the reduction of NOx in accordance with an embodiment of the invention. 
         FIG. 7  is a graph of experimental results for the performance of a GaAg monolith with ULSD (Ultra Low Sulfur Diesel) and biodiesel. 
         FIG. 8  is a graph illustrating the yields of different reductant fractions obtained from ULSD as a function of fuel: air ratio. 
         FIG. 9  is a graph illustrating the yields of different reductant fractions obtained from a biodiesel blend (B20) as a function of fuel:air ratio. 
         FIG. 10  is a graph illustrating the performance of a GaAg monolith with a converted biodiesel (B100) as a reductant as a function of temperature. 
     
    
    
     DETAILED DESCRIPTION 
     Neat biodiesel and biodiesel blends reduce particulate matter, hydrocarbons, and carbon monoxide (CO) emissions, but increase NOx emissions compared with petrodiesel fuel. In addition, due to the renewable nature of biodiesel, overall emissions of CO 2  and impact on greenhouse gas emissions are considerably lower when using biodiesel and biodiesel blends. Biodiesel fuels are mainly methyl or ethyl esters of fatty acids, often containing unsaturated bonds and including palmitic, stearic, oleic, linoleic, and linolenic acids, among others. According to one embodiment of the present invention, ester functionality and its unsaturated character make biodiesel a suitable reductant of NOx contained in exhaust gas streams. 
     As shown in  FIG. 1 , on-board thermal hydrolysis of biodiesel esters results in the production of fatty acids and alcohols. This reaction is exemplified for a generic methyl ester having a formula 
                                
as follows:
 
                                
where the R group is a variable hydrocarbon chain.
 
     According to one embodiment of the present invention, the ester hydrolysis reaction is carried out in the diesel engine exhaust stream. Water for hydrolysis is present in the exhaust as the product of the diesel fuel combustion, along with CO 2  and other combustion products. The products of the ester hydrolysis reaction act as the reducing agents reacting with NOx present in the exhaust stream on the SCR catalyst, thus catalytically reducing NOx to N 2 . 
     The SCR reaction is carried out on the SCR catalysts, which are typically in the form of pellets or beads in a container, or coated on the walls of a monolithic structure, such as a monolithic structure in a honeycomb configuration. Monolithic structures are well known in the art and are typically composed of ceramic or metal material forming open channels from the inlet to the outlet, with channels in some cases having turns and bends. The catalyst material is typically formed into a sol or colloidal dispersion in a liquid carrier and then applied to internal surfaces of the monolithic metal or ceramic substrate to form a layer of catalyst coating on these internal surfaces. The cell size and shape of the monolithic structure are selected to obtain the desired surface area, pressure drop, and heat and mass transfer coefficients required for a particular application. Such parameters are readily ascertainable to one of skill in the art. In accordance with the present invention, the channels can be of any shape suitable for ease of production and coating, and appropriate flow of the gas stream. For example, for metal substrates, channels may be corrugated into straight, sinusoidal, or triangular shapes, and/or may include a herringbone or zig-zag pattern. For a ceramic substrate, the channels may be, for example, square, triangular, or hexagonal, or any shape that can be formed by extrusion or other methods of manufacture known in the art. Channel diameters are typically in the range of about 0.01 inches to about 0.2 inches, and are preferably from about 0.04 inches to about 0.1 inches. 
     The SCR catalyst herein refers to any catalyst known in the art that is useful for the catalytic reduction of NOx via reaction with a mixture of alcohols, fatty acids, and hydrocarbons. Typical active catalytic components of the NOx SCR catalyst include Pt, Pd, Rh, and Ir. High surface area refractory oxide supports or zeolites may be included. Typical refractory oxide supports are alumina, alumina with additives such as Si, Ca, Ba, Ti, La or other components to provide increased thermal stability. In addition, modifying components such as, for example, Na, Co, Mo, K, Cs, Ba, Ce, and La may be used to improve the selectivity of the reaction, by reducing the oxidation activity of the catalyst. Additional NOx selective reduction catalyst compositions may contain Cu, Co, Ni, Fe, Ga, La, Ce, Zn, Ti, Ca, Ba, Ag or mixtures thereof, or Pt, Ir, Rh or mixtures thereof. 
     The monolithic metal substrate can be formed of parallel plates, multiple tubular elements, corrugated metal foil, a honeycomb, or multi-cellular monolith and is made of a corrosion resistant metallic alloy suitable for high temperature service in aggressive environments characteristic of automotive exhaust. Such alloys include, but are not limited to, oxidation-resistant high temperature ferritic Cr—Al alloys. These iron-chromium-aluminum alloys typically contain up to seven percent of Al and some other additives. When exposed to high temperature oxidizing environments the alloy forms a corrosion-resistant layer of aluminum and chromium oxides, which prevents further oxidation. 
     Referring now to  FIG. 2 , a schematic block-diagram of operation of an embodiment of the invention is shown. A biodiesel or biodiesel blend is used to fuel a diesel engine, resulting in decreased emissions of particulate matter (PM) and also decreased lifecycle CO 2  emissions due to the renewable nature of biodiesel. Decreases in CO and hydrocarbon (HC) emissions are also possible. The biodiesel or biodiesel blend is also injected into the NOx-containing exhaust of the diesel engine and undergoes hydrolysis to produce the reducing agents as products. The SCR exhaust treatment process is then carried out. In this process, the reducing agents convert NOx into N 2 . Overall, operation of the embodiments of the invention produce exhaust streams with decreased NOx, particulate matter, and lifecycle CO 2  emissions into the atmosphere. Decreases in CO and hydrocarbon emissions are also possible. 
     Another embodiment of the present invention includes a fuel processor that converts a slip stream of biodiesel such as B100 (available from InterWest LC) or biodiesel blend such as B20 into NOx reductants (e.g. hydrocarbons and oxygenates) that are subsequently introduced in the exhaust upstream of the SCR catalyst for NOx reduction. 
     Referring now to  FIG. 3 , a schematic diagram of an embodiment of the present invention is shown. A fuel tank  10  containing a blend of biodiesel and petrodiesel is used to supply diesel fuel to a diesel engine  20  via a fuel supply line  15 . The biodiesel and petrodiesel blend can comprise from about 1 weight percent to about 100 weight percent biodiesel. Preferably, the biodiesel and petrodiesel blend comprises from about 10 weight percent to about 40 weight percent biodiesel. The biodiesel and petrodiesel blend from fuel tank  10  is also injected into an exhaust stream  30  from diesel engine  20  via exhaust treatment line  60 . The biodiesel injected into exhaust stream  30  then undergoes hydrolysis, reacting with water contained in exhaust stream  30  thereby forming the reducing agents. The resulting mixture of the reducing agents and diesel engine exhaust is then fed into an SCR unit  40  where selective catalytic reduction of NOx is carried out via reaction of NOx with the reducing agents. The treated exhaust stream  50  containing decreased NOx, particulate matter, and lifecycle CO 2  emissions is exhausted into the atmosphere. 
     Another embodiment of the present invention includes a fuel processor (not shown) that converts a slip stream of the biodiesel and petrodiesel blend from fuel tank  10  into NOx reductants (hydrocarbons, oxygenates) that are subsequently injected into exhaust stream  30 . In this embodiment, conversion of the biodiesel and petrodiesel blend is performed in the fuel processor instead of or in addition to hydrolysis in the exhaust stream  30 . Conversion of the biodiesel and petrodiesel blend may be performed in the fuel processor via a reaction using a diesel conversion catalyst. Suitable examples of a diesel conversion catalyst for use in the invention include Rh, Pt, Pd, Sn, Ir, La, Ce, Co, or a combination thereof, deposited on alumina, zeolite, or YSZ supports. 
     As illustrated in  FIG. 4 , a biodiesel fuel tank  12  and a petrodiesel fuel tank  14  supply blended fuel to diesel engine  20  via a fuel supply and mixing line  16 . According to this embodiment of the invention, biodiesel and petrodiesel are mixed in proportions which are defined by the type of diesel engine  20 , operating conditions, optimized emissions control, and other parameters. The blend of biodiesel and petrodiesel supplied through the fuel supply and mixing line  16  comprises about 1 weight percent to about 100 weight percent biodiesel. Preferably, the biodiesel and petrodiesel blend supplied through the fuel supply and mixing line  16  comprises from about 10 weight percent to about 40 weight percent biodiesel. Biodiesel fuel tank  12  and petrodiesel fuel tank  14  also supply fuel for injection into exhaust stream  30  via exhaust treatment and mixing line  62 . The biodiesel and petrodiesel blend supplied through the exhaust treatment and mixing line  62  comprises about 1 weight percent to about 100 weight percent biodiesel. Preferably, the biodiesel and petrodiesel blend supplied through the exhaust treatment and mixing line  62  comprises from about 75 weight percent to about 100 weight percent biodiesel. The biodiesel injected into exhaust stream  30  then undergoes hydrolysis, reacting with water contained in exhaust stream  30 , thereby forming reducing agents. The resulting mixture of the reducing agents and diesel engine exhaust is then fed into SCR unit  40  where the selective catalytic reduction of NOx is carried out via the reaction of NOx with the reducing agents. The resulting treated exhaust stream  50  containing decreased NOx, particulate matter, and lifecycle CO 2  emissions is exhausted into the atmosphere. 
     Referring to  FIG. 5 , a schematic diagram of an embodiment of the invention similar to the embodiment shown in  FIG. 4  is presented. In this embodiment, only biodiesel, and no petrodiesel, is supplied for injection into exhaust stream  30  via exhaust treatment and mixing line  62 . Thus, the composition of fuel supplied through exhaust treatment and mixing line  62  is 100% biodiesel. 
     In  FIG. 6 , several embodiments of an exhaust treatment system for the reduction of NOx via a SCR process are shown. Exhaust stream  30  enters an exhaust line  70  which is connected to SCR unit  40 . SCR unit  40  contains an SCR catalyst preferably coated on a multi-channel, high surface area monolithic structure  80 , such as a honeycomb-like structure with low resistance to exhaust gas flow. After SCR reduction of NOx, the resulting treated exhaust stream  50  containing decreased NOx, particulate matter, and lifecycle CO 2  emissions is exhausted into the atmosphere. 
     As illustrated in  FIG. 6A , a biodiesel fuel, or biodiesel and petrodiesel blend fuel is injected via exhaust treatment and mixing line  62  or exhaust treatment line  60  into exhaust line  70 . The biodiesel is then hydrolyzed via reaction with water contained in exhaust stream  30 . The resulting mixture of the reducing agents and diesel engine exhaust is then fed into an SCR unit  40  where the selective catalytic reduction of NOx is carried out via reaction of NOx with reducing agents. 
     Referring to  FIG. 6B , a biodiesel fuel, or biodiesel and petrodiesel blend fuel is injected via exhaust treatment and mixing line  62  or exhaust treatment line  60  into a hydrolysis and mixing zone  90  established along exhaust line  70 . The biodiesel is then hydrolyzed in hydrolysis and mixing zone  90  via reaction with water contained in exhaust stream  30 . The resulting mixture of the reducing agents and diesel engine exhaust is then fed into SCR unit  40  where the selective catalytic reduction of NOx is carried out via reaction of NOx with the reducing agents. 
     As shown in  FIG. 6C , the biodiesel, or biodiesel and petrodiesel blend fuel is injected via exhaust treatment and mixing line  62  or exhaust treatment line  60  into a hydrolysis and mixing zone  90 ′ established within SCR unit  40 . The biodiesel is then hydrolyzed in hydrolysis and mixing zone  90 ′ via reaction with water contained in exhaust stream  30 . The resulting mixture of the reducing agents and diesel engine exhaust is then processed on an SCR unit  40  catalyst where the selective catalytic reduction of NOx is carried out via reaction of NOx with the reducing agents. 
     Referring to  FIG. 6D , a portion of exhaust stream  30  is redirected into a hydrolysis zone  92  as shown by arrow  32 . Exhaust stream  30  is fed directly into SCR unit  40  via exhaust line  70 . The biodiesel fuel, or biodiesel and petrodiesel blend fuel is injected via exhaust treatment and mixing line  62  or exhaust treatment line  60  into a hydrolysis zone  92 . The biodiesel is then hydrolyzed in hydrolysis zone  92 . The resulting mixture of the reducing agents and diesel engine exhaust is then fed into SCR unit  40  as shown by arrow  34  where the selective catalytic reduction of NOx is carried out via reaction of NOx with the reducing agents. 
     EXAMPLE 1 
     Use of Biodiesel Blends B100/B20 as SCR Reductants 
     Catalyst Preparation 
     DISPAL® boehmite gel (available from Sasol North America, Inc.) was slurried in de-ionized water in the presence of ammonium hydroxide until the pH of the slurry was 9. Separately, Ga(NO 3 ) 3 6 H 2 O (Alpha Aesar, 99.999% purity), and AgNO 3  (Alpha Aesar, 99.995% purity) were dissolved in water, and added to the alumina slurry. Finally, the content was mixed for fifteen minutes, dried in an IR oven to remove any liquid, sieved through a 60 mesh sieve followed by calcination at 650° C. in air for six hours. The temperature profile for the calcination was as follows: (a) 1.1° C./min ramp from 25° C. to 110° C., (b) soak at 110° C. for 1.5 hours, (c) 5° C./min ramp from 110° C. to 650° C., and (d) soak at 650° C. for 6 hours. The calcined powder was then re-slurried in water (at 40 wt. %) and then dip-coated on cordierite cores (230 CPSI, 2″ in diameter). The final composition of the catalyst was 15 wt. % Ga, 2 wt. % Ag at 110 g Al 2 O 3 /L monolith. 
     SCR Performance 
     The performance of the SCR monolith at a space velocity (SV) of 40,000 hr −1  was tested with the exhaust of a 5.9 L diesel engine (manufactured by Cummins, Inc.) using ULSD (15 ppm Sulfur, available from Sprague Energy Corporation) and biodiesel as reductants at a molar ratio of C 1 :NO=6, and a temperature of 375° C. The catalyst performance with diesel, B20, and biodiesel is shown in  FIG. 7 . 
     EXAMPLE 2  
     Converting B20 to Produce NOx Reductants 
     Diesel Conversion Catalyst Preparation 
     A disk of alumina foam (65 ppi, 20 mm diameter, 99.5% Al 2 O 3 ) was dipped in a slurry of alumina powder that contained the metal salt precursors (Pt, Ir, Rh) in water. The foam was dried in a vacuum oven until all water was removed, and then calcined in air at 600° C. 
     Diesel Conversion Performance 
     A mixture of diesel fuel (ULSD or B20) and air (fuel:air ratio=1 to 3) was finely dispersed via an atomizing nozzle and converted over a Pt—Ir—Rh catalyst into a mixture of smaller hydrocarbons at a temperature of 650° C., and space velocity of 100,000 hr−1. The reaction mixture was then separated into gaseous and liquid fractions by a series of condensers, and then analyzed by gas chromatography. Yields of different reductant fractions obtained from ULSD are presented in  FIG. 8  as C 3 -C 12  yield (C 1  basis) as a function of fuel:air ratio resulting from ULSD at a space velocity of 50,000 hr−1 and 150,000 hr−1. Yields of different reductant fractions obtained from B20 are presented in  FIG. 9  as C 3 -C 12  yield (C 1  basis) as a function of fuel:air ratio resulting from B20 at a space velocity of 50,000 hr −1 . 
     EXAMPLE 3  
     Performance of GaAg Monolith with Converted Biodiesel (B100) as Reductant 
     Performance of a GaAg monolith with converted biodiesel (B100) as a reductant as a function of temperature is illustrated in  FIG. 10 . SCR conditions of the experiment included a space velocity of 40,000 hr −1 , treatment of the exhaust from a 5.9 L diesel engine using ULSD; Diesel Conversion Catalyst (RhIrPt): space velocity of 150,000 hr −1 , temperature of 600° C., and fuel:air ratio=3. 
     All cited patents, patent applications, and other references are incorporated herein by reference in their entirety. 
     All ranges disclosed herein are inclusive of the endpoints, and the endpoints are combinable with each other. 
     It is to be noted that the terms “first,” “second,” and the like as used herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The modifiers “about” and “approximately” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., includes the degree of error associated with measurement of the particular quantity). The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. 
     While the invention has been described in detail in connection with only a limited number of embodiments, it should be readily understood that the invention is not limited to such disclosed embodiments. Rather, the invention can be modified to incorporate any number of variations, alterations, substitutions or equivalent arrangements not heretofore described, but which are commensurate with the spirit and scope of the invention. Additionally, while various embodiments of the invention have been described, it is to be understood that aspects of the invention may include only some of the described embodiments. Accordingly, the invention is not to be seen as limited by the foregoing description, but is only limited by the scope of the appended claims.