Patent Application
20090004083
The invention concerns a new device and process for reducing NOx emissions, particularly for mobile diesel and other lean-burn engines.
Internal combustion engines, particularly non-spark ignited (diesel) engines, are desirable because of their energy efficiency. Diesel and lean-burn gasoline engines provide particular advantages in fuel economy and are favored for this reason. However, they tend to produce high concentrations of nitrogen oxides (NOx) in the combustion gas because of the high temperature involved in the combustion process. Efforts to reduce the combustion temperature, by water injection, exhaust gas recycle or the like, can be successful, but tend to increase the emission of other undesirable components, particularly carbon monoxide and products of incomplete combustion.
Emissions of NOx can also be reduced by post-combustion techniques. A particularly good example of such techniques is selective catalytic reduction (SCR). In the SCR process, NOx is reacted with NH3, or similar nitrogen containing compounds such as urea and like materials, over a catalyst to yield nitrogen gas (N2) and water (H2O). There are many catalysts that have been described in the literature but each catalyst tends to have a relative narrow temperature range over the catalyst is effective. Such behavior has been described in detail by R. M. Heck, I. M. Chen and B. K. Speronello of the Engelhard Corporation. In “Operating Characteristics and Conunercial Operating Experience with High Temperature SCR NOx Catalyst”, Environmental Progress, Vol. 13, No. 4, pp. 221-225.
The exhaust gas from a typical diesel engine can have a gas temperature that ranges from about 150° C. all the way up to 600° C. and perhaps even higher. This range arises from variations in the engine load with increasing load resulting in higher gas temperatures. No single catalyst has been found to be effective over this entire temperature range. Thus, NOx reduction has been limited for engines that operate under transient conditions wherein exhaust gas temperature can very over the entire range.
Despite the availability of devices and systems of the type described there remains a current need for an economical and effective answer to the problems associated with reducing NOx, particularly for mobile diesel and other lean-burn engines.
The invention provides a new device and a new process addressing the above needs.
A multi-stage NOx reduction system employs catalysts effective at different temperature ranges and has reagent injectors associated with each or a means for directing reagent to each. A controller moves reagent introduction from one catalyst to the other as temperature and other conditions dictate. Valving could redirect exhaust to particular catalyst zones, if necessary.
Many of the preferred aspects of the invention are described below. Equivalent structures, procedures and compositions are contemplated.
The invention will be better understood and its advantages will be more apparent when the following detailed description is read in light of the accompanying drawings, wherein:
As noted above, the invention relates to a new device and a new process addressing the above needs and is intended for use with diesel engines, but has applicability to any combustors having similar wide variations in exhaust gas temperatures, such as turbines, boilers, furnaces, process heaters, heat recovery units, and the like, utilizing carbonaceous, e.g., fossil or bio-derived, fuels such as distillates, residual and gaseous fuels.
It has now been found that the overall performance of the SCR process for diesel engines can be improved by utilizing two, or more, catalysts in series or in parallel where the reagent for NOx reduction (NH3, urea or the like) is selectively injected to take advantage of the appropriate operating range for each catalyst. NOx-reducing reagent can, for example, be selected from the group consisting of ammelide, ammeline, ammonia, ammonium carbonate, ammonium bicarbonate, ammonium carbamate, ammonium cyanate, ammonium salts of inorganic acids, ammonium salts of organic acids, biuret, cyanuric acid, hexamethylenetetramine, isocyanic acid, lower alkyl amines, melamine, tricyanourea and urea.
Referring to
There is a further benefit to the proposed system. Most of the emissions of NOx from diesel engines is in the form of nitrogen monoxide (NO). However, it has been found that nitrogen dioxide (NO2) tends to react more rapidly over a typical SCR catalyst. Catalyst 1 typically will promote oxidation reactions when the temperature exceeds the normal operating window for SCR. Thus, for catalysts of the LT-1 or LT-2 types, oxidation of the NOx reducing reagent (e.g., NH3) becomes a problem when the temperature exceeds 250-300° C., thus necessitating the switch in injection points from zone I to zone 2. Catalyst 1 retains its property to promote oxidation at the higher temperature and this can yield several benefits. Carbon monoxide (CO) will be oxidized to CO2. Unreacted hydrocarbons will be converted to CO2. Finally, NO will tend to be converted to NO2. In this mode of operation, the exhaust gas containing NOx, mostly as NO2, will be passed through the zone 2 catalyst to achieve higher than normal NOx reduction.
In yet another variation of the basic series set up of
The NO2 formed in catalyst zone 1 will tend to react more rapidly with the NOx reducing reagent (NH3) in catalyst zone 2. Thus, the efficiency of catalyst 2 will be improved because of the more reactive species involved in the reaction:
4NH3+4NO+O2=4N2+6H2O (fast)
6NH3+4NO2+1/2O2=5N2+9H2O (faster)
It should be noted that the same advantages can be achieved by putting three or more catalysts in series and changing the point of reagent injection to follow the optimum performance curve for each individual catalyst. The number of catalysts to be employed will be constrained only by costs and the physical limitations imposed by space within the exhaust system. An ARIS™ injector and injection system, e.g., as described in U.S. Pat. No. 5,976,475 and U.S. Pat. No. 6,279,603, is particularly well suited to be employed in the multiple catalyst system because of their small in size, an ability to operate without any secondary medium for atomization, such as air and it can be close-coupled to the catalyst zone. The control unit can also receive other control inputs as described in the above patents, which are incorporated herein by reference, and can control the fuel and air supply to the engine, and can control exhaust gas recirculation, EGR, as useful for NOx control and fuel economy as described in U.S. Pat. No. 5,924,280.
Valves such as those used with exhaust gas recirculation are known to be able to operate in this environment. Temperature signals are fed to an engine control unit (ECU) or other suitable controller, which controls the valve to regulate the flow of exhaust gas between catalyst 1 or catalyst 2 based on exhaust gas temp or an engine signal, such as load, speed or rpm, as a predictor of exhaust gas temperature. Urea or other NOx reducing reagent is injected upstream of the valve for single injector systems or downstream of the valve but upstream of each separate catalyst zone for dual injector systems. In single or dual injector systems the valve can regulate exhaust gas flow, and reagent injection rate is controlled to maximize NOx reduction across either catalyst No, or catalyst No. 2 or both in combination by regulating exhaust gas flow and injector feed rate of reagent.
The above description is intended to enable the person skilled in the art to practice the invention. All of the references cited above are hereby incorporated by reference in their entireties to show and describe the points illustrated herein, and should be taken as if fully and bodily incorporated. It is not intended to detail all of the possible modifications and variations which will become apparent to the skilled worker upon reading the description. It is intended, however, that all such modifications and variations be included within the scope of the invention which is seen in the above description and otherwise defined by the following claims. The claims are meant to cover the indicated elements and steps in any arrangement or sequence which is effective to meet the objectives intended for the invention, unless the context specifically indicates the contrary.
| Number | Date | Country | |
|---|---|---|---|
| Parent | PCT/US2003/040263 | Dec 2003 | US |
| Child | 10536170 | US |
