Abstract:
A method for managing the temperature of an E-diesel catalyst by distilling out a portion of the ethanol, injecting the distilled ethanol into exhaust gasses upstream of the catalyst, reacting the distilled ethanol with excess oxygen in the exhaust gasses to produce heat, and controlling the ethanol injection using various engine parameters.

Description:
CROSS-REFERENCE TO RELATED APPLICATIONS  
       [0001]     This application is a divisional of U.S. application Ser. No. 10/361,432 filed Feb. 10, 2003. 
     
    
     STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH  
       [0002]     This invention was made with United States Government support under Contract No. DE-AC05-00OR 22725 between the United States Department of Energy and UT-Battelle, LLC, and the United States Government has certain rights in this invention. 
     
    
     FIELD OF THE INVENTION  
       [0003]     This invention relates to control of pollution from diesel engines and particularly to methods for enhancing the catalytic reduction of oxides of nitrogen by extracting ethanol from E-diesel for injection into the engine exhaust.  
       BACKGROUND AND PRIOR ART  
       [0004]     Diesel-cycle engines have displaced Otto-cycle internal combustion engines in medium and heavy truck use and are becoming increasingly popular for passenger vehicles. The diesel is inherently more efficient but its lack of responsiveness, its noise and its distinctive odor historically limited its appeal to commercial trucks and business traveling salesmen and taxicab fleets. The advent of laws and regulations addressing emissions from “mobile sources” also limited the appeal of diesel cars and light tracks because they were perceived as dirty and regional regulations relating to emissions, especially soot, limited their availability. The Otto-cycle engines were easier to modify to comply with more stringent emissions requirements in part because there are more adjustable parameters and soot is not an issue. Recent advances in fuel injection management in combination with electronic systems have closed the gap but the strategies applied to Otto-cycle engines do not always work with diesels.  
         [0005]     Oxygenates such as MTBE and ethanol are frequently blended into gasoline to meet air pollution regulations. Ethanol is preferred because it is a renewable resource, is less toxic and politically popular since it is home-grown and its use is a subsidy for farmers. Ethanol is readily blended into gasoline, but is difficultly blended into diesel fuel which has a blend of thousands of paraffinic, naphthalenic and aromatic hydrocarbons ranging in carbon numbers between 10 and 22.  
         [0006]     Control of emissions from heavy duty diesel trucks and urban buses has become more stringent in recent years and will become more stringent in 2004, when emissions of oxides of nitrogen (NO x ) must be reduced to 2.0 g/bhp-hr and in 2007 when NO x  will be reduced to 0.2 g/bhp-hr. To achieve the latter levels and to allow for improved particulate matter (soot) traps and NO x  catalysts, ultra low sulphur fuel (15 ppm) will be phased-in in 2006. Alternative fuel blends and efficient catalysts will be required.  
         [0007]     WO 93/24593 discloses a stabilized, auto-igniting alcohol-containing fuel for use as a diesel fuel having 20 to 70% by volume lower order alcohol (ethanol), 30 to 80% by volume diesel fuel, 4.5 to 5.5% by volume higher order alcohol surfactant, 1 to 15% of a tertiary alkyl peroxide, 3% alkyl peroxide and 0.05 to 0.1% by volume of an anti-clogging additive.  
         [0008]     U.S. Pat. No. 6,068,670 discloses an emulsified fuel including water which is more stable than that disclosed in French patent application serial number 2 470 153 which included water and ethanol and was deemed to be unstable on storage.  
         [0009]     U.S. Pat. Nos. 6,190,427 and 6,306,184 disclose an E-diesel fuel which is believed to be a product commercially available at this time. The fuel contains 3 to 18% ethanol, 6.5 to 10% of a stabilizer (ethoxylated fatty alcohols), and the remainder commercial No. 2 diesel oil. Optionally, an alkyl ester of a fatty acid and a cosolvent may be added.  
         [0010]     U.S. published patent application 20020104256 is directed to the addition of oxygenates to ultra low sulphur automotive diesel oil (ULSADO), the form which will be required by 2006. Accepting the presumption that oxygenates reduce the production of particulates (soot), the reference discloses the use of oxygenates which are saturated, monohydric alcohols having 4 to 20 carbon atoms.  
         [0011]     WO 02/059236 discloses compositions to stabilize hydrocarbon fuel over a range of alcohol and water concentrations as an emulsion and includes three different non-ionic surfactants. Optionally, a cetane improver may be employed.  
         [0012]     A persistent problem for diesel engines has been production of oxides of nitrogen, typically a mixture of NO and NO 2  most frequently referred to as NO x . While oxides of sulphur can be reduced by using ULSADO, the primary source of NO x  is nitrogen in the air and the higher temperatures of lean burn engines exacerbates an already known problem. Catalysts will be required.  
         [0013]     Methods are known to reduce NO x  to N 2  and H 2 O. The most established methods use ammonia, isocyanic acid or precursors such as urea. Representative examples are U.S. Pat. Nos. 6,203,770; 6,066,303; and 4,403,473 and published patent application 20020152745.  
         [0014]     Ammonia is a viable and affordable method for controlling NO x  at fixed sources but is impractical for mobile sources, especially mid-sized and compact cars. The proven methods require introduction of the reductant downstream of the reducing catalyst, require separate storage of fuel and reductant, thereby requiring inter alia, separate fueling streams.  
         [0015]     An alternative reducing system uses hydrocarbons as the reductant. The hydrocarbon may be separate from the diesel fuel as disclosed in U.S. Pat. No. 6,006,515 and in SAE Paper No. 2000-01-2823, or a slip stream from the fuel. The disadvantage of such a system is that fuel economy is impacted and the fuel must be carefully metered to avoid hydrocarbon emissions.  
         [0016]     A second alternative is the use of ethanol as a reductant. According to U.S. Pat. Nos. 6,030,590; 6,045,765; 6,057,257; 6,129,713 and 6,284,211 as well as SAE paper 2001-01-1935. The ethanol is introduced between the exhaust valve and the catalyst, which is taught to be a silver compound. The Caterpillar DeNO x  catalyst system, available since 1996, uses such a protocol. The use of ethanol, a liquid, is less difficult than ammonia systems, less sensitive to control metering than hydrocarbons, but still requires a separate tank and a duel fueling capacity at fueling stations.  
         [0017]     There remains a need to develop an efficient system for NO x  control in a single ULSADO fuel.  
       BRIEF DESCRIPTION OF THE INVENTION  
       [0018]     It is an object of this invention to provide a means for reducing NO x  in a diesel exhaust. It is a further object of this invention to use a single fuel for both the power source and for the control of NO x  using selective catalytic reduction (SCR). It is a further objective of this invention to separate components of a commercially available diesel fuel to maximize fuel economy, emissions control, and catalyst temperature control.  
         [0019]     These and other objectives are obtained by providing a method for stripping a portion of the ethanol in E-diesel and injecting the extracted ethanol into the exhaust stream downstream of the exhaust valve but upstream of the SCR. Advantageously, the stripping of ethanol may be accomplished using heat from the diesel engine and manifold vacuum to lower the distillation temperature of the ethanol (non-turbocharged engines)  
         [0020]     Additionally, the temperature of an E-diesel catalyst is managed by distilling out a portion of the ethanol in the E-diesel under reduced pressure, injecting the distilled ethanol into exhaust gasses from the engine upstream of the catalyst, reacting the distilled ethanol with excess oxygen in the exhaust gasses to produce heat, and controlling the ethanol injection using at least one engine parameter selected from the group consisting of intake air flow, fuel mixture richness, engine operating temperature, catalyst temperature and NO x  sensor output. 
     
    
     BRIEF DESCRIPTION OF THE DRAWINGS  
       [0021]      FIG. 1  is a schematic of the basic components of the invention.  
         [0022]      FIG. 2  is a more detailed diagram showing the components.  
     
    
     DETAILED DESCRIPTION OF THE INVENTION  
       [0023]     Commercial E-diesel such as that available fro Pure Energy Corporation contains approximately 15% ethanol, 1.5% a “proprietary additive” designed to stabilized the fuel and 80-84% low sulphur No. 2 diesel. ASTM standard D975 specifies minimum standards for “diesel fuel,” including boiling point ranges. Accordingly to the standard for low sulphur No. 2, 90% of the fuel must distill between 282 and 338° C. Typically, the majority boils between 250 and 300° C. Ethanol boils at 78.5° C. at 760 mmHg. It has been found by experiment that 90% of the included ethanol can be stripped at a temperature of 80° C. This final product contains 95% by volume ethanol and 5% by volume hydrocarbon components. Since both ethanol and light hydrocarbons are effective reductants using available SCR catalysts, the stripped mixture need not be chemically pure to reduce NO x .  
         [0024]     Suitable selective catalyst reducing (SCR) materials suitable for use with ethanol include alumina-supported tin or tin oxides as disclosed in U.S. Pat. No. 6,030,590 and silver based catalysts as described in U.S. Pat. Nos. 6,045,765; 6,057,259; and 6,284,211 and in SAE papers 2000-01-2813 and 2001-01-1935, all incorporated herein by reference. However, because catalyst materials need to be developed in association with the reductant type, different fuel-borne reductants (i.e. propane, butane, etc.) would likely require other catalyst formulations for optimal NO x  conversion.  
         [0025]     The chemical process whereby NO and NO 2  are reduced on catalysts have been studied but a series of actual steps has been postulated only. Multiple steps are known to be involved and they have been shown to vary by type of catalyst, type of support, chemical nature of the reductant and temperature of the catalyst. An excellent review is R. Burch et al.,  Applied CatalVsis B: Environmental  39, 283 (2002). Each control system of SCR and reductant must be optimized to maximize N 2  yield while minimizing N 2 0 (a potential greenhouse gas) and NH 3 . Optimization includes matching the amount of reductant to the concentration of NO, in the exhaust at a given time and maintaining the temperature of the SCR catalyst to maximize conversion to N 2 . The inherent difficulty in reducing the NO, lies in the fact that modern compression ignition internal combustion engines operate using the lean-burn principle to maximize fuel economy and the exhaust gas contains an excess of oxygen (5-8%) so that the reduction must take place in a nominally oxidative (not reducing) atmosphere. Hence, multiple processes occur on or near the catalyst and oxides are inevitably included in the process which must be carefully controlled to limit or eliminate conversion to gaseous NO, NO 2 , or N 2 0.  
         [0026]      FIG. 1  is a schematic showing the basic components of the system. E-diesel fuel in tank  3  is normally delivered by fuel line  5  to engine  7 . Exhaust  9  is directed by a header to an SCR catalyst bed  11  and discharged through tailpipe  13 .  
         [0027]     A distillation chamber  15  is connected to tank  3  by line  17 . The distillation chamber is connected to a stripped ethanol receiver  19  from which it is metered through line  21  to injector  23  in the exhaust header. The residue from distillation is returned to fuel tank  3  through return line  25 .  
         [0028]     The still  15  may be a single metallic chamber heated by engine coolant or by a mantle containing a resistance wire heater or by a tubular resistance heater immersed in the fuel. A short packed column and a condenser would connect to receiver  19 . In this mode the batch distillation could be repeated periodically based on engine hours or the level of stripped ethanol in the receiver.  
         [0029]     Advantage may be taken of the design for fuel systems in modern diesel engines.  FIG. 2  illustrates the components in greater detail. Fuel from tank  103  is pumped through a filter/heater  104  which warms the fuel using re-circulated engine coolant and removes particulates is delivered through fuel line  105  to pressurized fuel rail  106  from which it is injected into the engine  107 . The exhaust  109  may or may not pass through a turbocharger (not shown) to SCR catalyst bed  111  before passing through tailpipe  113 . Fuel exiting the rail  106  is split into a return line  118  and a sample line  117 . The return line  118  circulates fuel through line  125  back to tank  103 . The sample line  117  carries fuel to distillation chamber  115 . A heater  131  which may be electric or use circulated coolant (or both) fractionates the fuel into a primarily ethanol fraction and a diesel fraction. The ethanol-rich fraction is condensed using condenser  133  and directed to receiver  119 . The residue is returned to the tank  103  through return line  125 .  
         [0030]     When manifold vacuum is not regularly available, an electric vacuum pump  135  may be used to reduce the heat requirement for distillation.  
         [0031]     A float or other sensor in receiver  119  may be used to start and stop the stripping process such as by turning off heat to heater  131 , adjusting the split between lines  117  and  118  or by returning stripped ethanol to the main tank  103 . A small electric pump  137  pressurizes lines  138  to ethanol injection  123 . A recirculating line  139  may circulate ethanol back to receiver  119 .  
         [0032]     The stripped ethanol may be injected into the exhaust near the exhaust port or downstream, near the SCR catalyst bed. For motors with exhaust gas recirculation, the downstream location is preferred, for greater control of the NO x :EtOH ratio. In the preferred embodiment, means such as a water jacket may be used to protect the injector from heat damage.  
         [0033]     There are currently 17 different test cycles in use to test emissions from diesel-powered vehicles. All involve engine or chassis dynamometers and are designed to duplicate operational cycles such as the Orange County Bus Cycle for transit buses. Europe currently has five test cycles; Japan four. ISO 8178 is used for some off-road certifications. The AVL 8-mode heavy-duty cycle is a steady-state engine test procedure designed to correlate closely with the emission results obtained using the U.S. FTP transient cycles for heavy duty trucks using an engine dynamometer. The AVL 8 is a weighted average of eight different combinations of engine speed and load and provides results more conveniently than the FTP transient protocol.  
         [0034]     The amount of ethanol required to sufficiently reduce NO x  emissions over a catalyst depends on the NO x  flux which, in turn, is dependent on the engine operating regime. Engine experiments showed that 3 parts ethanol is required to reduce 1 part NO x  (mole:mole basis). Using AVL 8-mode as a guideline, then approximately 38.6 ml of ethanol is required for 1000 ml of fuel. This means that approximately 3.86% of the ethanol in a 15% E-diesel fuel is required for proper mass balance. This results in 11.4% of the original ethanol being unused by the SCR system and therefore consumed by the engine from a 15% blend.  
         [0035]     In actual use, it is envisioned that a dynamic ethanol injection system would be employed based upon various engine parameters such as intake air flow, fuel mixture richness, operating temperature and probably an NO x  sensor in the exhaust.  
         [0036]     The data would be processed utilizing available computer processors and adjustable parameters changed accordingly to optimize efficiency. Since it is necessary to control the temperature of the catalyst under various load conditions but especially at idle and start-up, the reductant may be used to provide heat through combustion in the exhaust under lean conditions. An ignition source such as a spark plug or glow plug may be used for this purpose to initiate burning of some of the reductant to provide such heat. Optionally, an oxidizing catalyst may be used between injector and SCR catalyst to increase the heat and to control the amount of oxygen in the area of the SCR catalyst.  
         [0037]     A microemulsion was formed using No. 2 diesel fuel, ethanol (15% by vol.) and a proprietary additive (10%) available from G.E. Betz, Trevose Pa. prepared according to WO 02/059236. The mixture was splash blended to form the emulsion, and transferred to a still. A vacuum of 200 mm Hg was applied and the still heated to 80° C. (liquid temperature). The distillate was collected as a single phase and the percentage of ethanol determined by infrared spectrometer to be greater than 98% pure when approximately 3% of the total volume was stripped when continued, 90% of the available ethanol can be obtained at 95% purity.  
         [0038]     The invention has been described with reference to preferred and alternative embodiments of the invention. Modifications and alternatives to the invention will occur to those skilled in the art and it is intended that all such modifications and alterations fall within the scope of the invention and claims.