# Patent

## Title
Methods and formulations for enhancing NH3 adsorption capacity of selective catalytic reduction catalysts

## Abstract

According to one embodiment of the present invention, an enhanced NH3 adsorbing automotive exhaust composition including a catalyst composition suitable for use in a selective catalytic reduction (SCR) system and an acidified support composition for enhancing NH3 adsorption capacity of the automotive exhaust composition is disclosed.

## Background
BACKGROUND OF THE INVENTION
1. Field of the Invention
One aspect of the present invention is related to methods and formulations for enhancing NH3 adsorption capacity of selective catalytic reduction catalysts.
2. Background Art
Environmental concerns and governmental regulations have been a continuing impetus for improvements in pollution control from automotive vehicles. The treatment or removal of noxious combustion by-products from the vehicle exhaust stream is a major focus of such efforts. Typically, these combustion by-products include incomplete combustion by-products such as carbon monoxide and hydrocarbons. Moreover, the exhaust of these vehicles may include various nitrogen oxides (NOx) and sulfur oxides. It is desirable and, in certain instances, mandated that certain of these compounds be reduced during vehicle operation.
Currently, the exhaust systems of automotive vehicles include one or more catalyst systems to affect the control of such by-products. One known system utilizes a selective catalytic reduction (SCR) process to control emissions of potentially harmful by-products, e.g. to reduce the amount of NOx exiting the vehicle exhaust. These systems have been implemented in lean burn engine vehicles, such as diesel engine vehicles. The system utilizing the SCR process, i.e. the SCR system, includes a substrate upon which a SCR catalyst composition is applied (via a wash coating process, for example). The SCR catalyst composition includes an SCR catalyst, which can be a vanadium-based catalyst or zeolite-containing catalyst. According to one SCR process, a gaseous or liquid reductant is added to a flue gas stream and is adsorbed onto a SCR catalyst. NH3 can be used as the reductant, and can be delivered in gaseous form or via urea injection with subsequent decomposition to NH3.
The reduction of NOx with NH3 over SCR catalysts can be significantly influenced by the amount of NH3 adsorbed on the catalysts. An increase in NH3 adsorption capacity can increase the catalytic rate of reduction. In many applications, the SCR reaction occurs at temperatures above 150° C., and therefore, it may be desirable in such applications to use have SCR catalysts that have a substantial adsorption capacity of NH3 at temperatures that exceed 150° C. In certain applications, it is desirable to have SCR catalysts possessing a relatively high capacity of NH3 adsorption and relatively strong bonding to NH3.
One common drawback of certain known SCR systems is NH3 slip, which occurs when exhaust gas temperatures are too cold for the SCR reaction to occur and/or too much reductant is fed into the exhaust gas stream for the amount of NOx in the stream. A variety of strategies have been developed to deal with NH3 slip, including the fitting of extra catalysts after the SCR catalyst.
In light of the foregoing, methods and formulations relating to SCR for addressing one or more of the disadvantages and/or providing one or more of the benefits identified above is needed.
SUMMARY OF THE INVENTION
One aspect of the present invention is a method and/or formulation relating to SCR for enhancing the NH3 adsorption capacity of SCR systems is provided. Another aspect of the present invention is a method and/or formulation relating to SCR for enhancing the NH3 bonding strength of SCR systems is provided. Yet another aspect of the present invention is a method and/or formulation relating to SCR for providing substantial NH3 adsorption capacity at relatively high temperatures, e.g. greater than 150° C. is provided. In yet another aspect of the present invention, a method and/or formulation relating to SCR for addressing NH3 slip is provided.
According to one embodiment of the present invention, an enhanced NH3 adsorbing automotive exhaust composition including a catalyst composition and an acidified support composition for enhancing NH3 adsorption capacity is disclosed.
The acidified support composition can include a support composition and a conjugate base oxide of an inorganic acid having a Ka in the range of 5.0×10−7 to 1.0. In certain embodiments, the Ka is in the range of 5.0×10−5 to 5.0×10−1. The conjugate base oxide can be the conjugate base of an acid selected from the group consisting of H3PO4, H2TiO3, H2WO4, H2MoO3, HTa2O6, HNb2O6, H2CrO4 and combinations thereof. The support composition can be selected from the group consisting of Al2O3, SiO2, TiO2, ZrO2, CeO2 and combinations thereof. The NH3 desorption per gram of acidified support composition is in the range of 3 to 25 ml upon substantially complete thermal release of the NH3. In certain embodiments, the acidified support composition desorbs a substantial amount of NH3 in the range of temperatures from 150 to 350° C. during substantially complete thermal release of NH3 after saturation of the acidified support composition with NH3.
According to another embodiment of the present invention, an SCR system including a substrate and a catalyst composition coated upon the substrate comprising an acidified support composition for enhancing NH3 adsorption capacity is disclosed.
The acidified support composition can include a support composition and a conjugate base oxide of an inorganic acid having a Ka in the range of 5.0×10−7 to 1.0. In certain embodiments, the Ka is in the range of 5.0×10−5 to 5.0×10−1. The conjugate base oxide can be the conjugate base of an acid selected from the group consisting of H3PO4, H2TiO3, H2WO4, H2MoO3, HTa2O6, HNb2O6, H2CrO4 and combinations thereof. The support composition can be selected from the group consisting of Al2O3, SiO2, TiO2, ZrO2, CeO2 and combinations thereof. The NH3 desorption per gram of acidified support composition is in the range of 3 to 25 ml upon substantially complete thermal release of the NH3. In certain embodiments, the acidified support composition desorbs a substantial amount of NH3 in the range of temperatures from 150 to 350° C. during substantially complete thermal release of NH3 after saturation of the acidified support composition with NH3.
According to yet another embodiment of the present invention, a method of enhancing NH3 adsorption capacity in an automobile exhaust catalyst composition is disclosed. The method includes acidifying a support composition for use in an automobile exhaust catalyst composition with a conjugate base oxide of an inorganic acid having a Ka to obtain an acidified support composition.



BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A depicts the NH3 desorption characteristics of an unmodified alumina catalyst support as a function of time and temperature according to one embodiment of the present invention; and
FIG. 1B depicts the NH3 desorption characteristics of a P-modified alumina catalyst support as a function of time and temperature according to one embodiment of the present invention.



DETAILED DESCRIPTION OF EMBODIMENTS OF THE PRESENT INVENTION
Except where expressly indicated, all numerical quantities in this description indicating amounts of material or conditions of reaction and/or use are to be understood as modified by the word “about” in describing the broadest scope of the present invention. Practice within the numerical limits stated is generally preferred.
The description of a single material, compound or constituent or a group or class of materials, compounds or constituents as suitable for a given purpose in connection with the present invention implies that mixtures of any two or more single materials, compounds or constituents and/or groups or classes of materials, compounds or constituents are also suitable. Also, unless expressly stated to the contrary, percent, “parts of,” and ratio values are by weight. Description of constituents in chemical terms refers to the constituents at the time of addition to any combination specified in the description, and does not necessarily preclude chemical interactions among constituents of the mixture once mixed. The first definition of an acronym or other abbreviation applies to all subsequent uses herein of the same abbreviation and applies mutatis mutandis to normal grammatical variations of the initially defined abbreviation. Unless expressly stated to the contrary, measurement of a property is determined by the same technique as previously or later referenced for the same property.
In at least one embodiment of the present invention, a selective catalytic reduction (SCR) system and method is disclosed. The SCR system includes a SCR catalyst composition, which includes SCR catalyst, for example, a vanadium-based catalyst or zeolite-containing catalyst. The SCR catalyst composition can also include a catalyst support composition. Such support compositions can provide a mechanism for holding and dispersing the active components of the SCR catalyst composition and for increasing the surface area for adsorption of the species being altered by the action of the catalyst. Suitable supports include, but are not limited to, Al2O3, SiO2, TiO2, ZrO2, CeO2 and combinations thereof. The support composition can be delivered to the SCR catalyst composition via a molecular sieve or sol-gel process known to one of ordinary skill in the art. Further, the supports composition can be provided as a powder and mixed in with the other components of the SCR catalyst composition in forming a slurry mixture to be applied by a washcoating process.
The SCR catalyst composition can also include a metal or metal-containing compound. Suitable non-limiting examples of metals include those from the group of metals known as the noble metal group (Ru, Rh, Pd, Os, Ir and Pt) and certain metals (Fe, Cu and Ag) from the group known as the late transition metal group. In certain embodiments, Pt, Pd and Rh can be utilized.
The SCR catalyst composition can also include a combination of a cerium-containing oxide compound and non-cerium-containing metal compound selected from the group consisting of alkali metal containing compounds, alkaline-earth metal containing compounds and combinations thereof. Suitable cerium-containing oxides include mixed oxides selected from the group consisting of Ce/Zr oxide, Ce/Pr oxide, Ce/Pr/Zr oxide, and combinations thereof.
The SCR catalyst composition can also include metal ions of a metal or metal-containing compound bonded to a conjugate base of an inorganic acid. The metal ions that are bonded to the conjugate base can be selected from the group consisting of alkali metal ions, alkaline-earth metal ions, and combinations thereof. Suitable metal ions include, for example, ions derived from Ba, Li, Na, K, Cs, Mg, Ca, Sr and combinations thereof. Typically, the metal or metal containing compound will alter the amount of a chemical component in the automobile exhaust (e.g., the NO, CO, SO2, hydrocarbons, etc). Moreover, the conjugate base of an inorganic acid can be a conjugate base oxide of an inorganic acid. As used herein in at least one embodiment of the present invention, “conjugate base” means the ion formed when an acid loses one or more hydrogen ions (i.e., H+). As used herein in at least one embodiment of the present invention, “conjugate base oxide” means a conjugate base that has one or more bonds between oxygen and another element.
In at least one embodiment, the inorganic acid for which the base oxide is conjugate has a Ka such that the SCR catalyst composition provides enhanced NH3 adsorption and/or increases the number of acid sites on the SCR system for adsorbing NH3. Typically, this inorganic acid has a Ka value from about 5.0×10−7 to about 1.0. In other variations, the inorganic acid for which the base oxide is conjugate has a Ka value from about 5.0×10−5 to about 1.0×10−1.
The conjugate base oxides are derived from acids selected, for example, from the group consisting of H3PO4, H2TiO3, H2WO4, H2MoO3, HTa2O6, HNb2O6, H2CrO4 and combinations thereof. In at least one embodiment of the present invention, the component having metal ions bonded to a conjugate base oxide of an inorganic acid is present in an amount from about 0.3 weight percent to about 50 weight percent of the total weight of the SCR catalyst composition. In at least one embodiment of the present invention, the component having metal ions bonded to a conjugate base oxide of an inorganic acid is present in an amount from about 1 weight percent to about 20 weight percent of the total weight of the SCR catalyst composition.
According to at least one embodiment of the present invention, an SCR catalyst system is made by first forming a slurry mixture of powders of each of the constituents included in the SCR catalyst composition and a suitable solvent, e.g. water. The slurry mixture is washcoated onto a substrate, such as the interior channels of a honeycombed-shaped brick. The coated brick is then dried and calcined at a relatively high temperature, e.g. greater than 500° C. Accordingly, the conjugate base oxides can be milled or ground into fine particles suitable for washcoating onto the substrate. Alternatively, the conjugate base oxide can be provided as nanoparticles to allow facile incorporation into SCR catalyst compositions.
The following examples illustrate the various embodiments of the present invention. Those skilled in the art will recognize many variations that are within the spirit of the present invention and scope of the claims.
EXAMPLE 1
The modification of alumina with phosphoric acid (P) was accomplished by dissolving a known amount of phosphate-salt into a predetermined volume of distilled water, adding a weighed sample of gamma-alumina into the solution under constant agitation, drying the solid mixture at 70° C., and calcining the solid sample at 600° C. for 6 hours.
According to this Example, a 3.2% of P doped on alumina (i.e. Al2-3.20P) was prepared by (1) dissolving 0.6818 grams of (NH4)2HPO4 in distilled water to form 9.150 ml solution, (2) adding 5.01 grams of high purity gamma-alumina into the solution with constant stirring, (3) drying the resulted mixture at 70° C. overnight, and (4) calcining the dried mixture at 600° C. for 6 hours. The high purity gamma-alumina used in this Example is available under the tradename MI307 from W.R. Grace & Co. of Columbia, Md. Table 1 lists several examples of phosphate-modified alumina that were made with various weight percentages of phosphorus.











TABLE 1





P-modified

Alumina
(NH4)2HPO4
Solution


alumina
P %
weight (g)
weight (g)
volume (ml)



















Al2-0.16P
0.16
5.01
0.03406
9.150


Al2-0.32P
0.32
5.01
0.06813
9.150


Al2-0.80P
0.80
5.01
0.1704
9.150


Al2-1.60P
1.60
5.01
0.3406
9.150


Al2-3.20P
3.20
5.02
0.6818
9.150









For comparison purposes, an unmodified alumina was prepared in the same way as described above for the phosphate-doped alumina sample, by providing a distilled water solution having a volume of 9.50 ml, (2) adding 5.00 grams of high purity gamma-alumina into the solution with constant stirring, (3) drying the resulted mixture at 70° C. overnight, and (4) calcining the dried mixture at 600° C. for 6 hours.
The P-modified (3.2 wt % P/Al2O3) and unmodified alumina catalyst supports were each saturated with 300 PPM NH3 and then exposed to thermal heating. 0.1939 grams of the P-modified alumina was saturated and thermally heated, while 0.2056 grams of the unmodified alumina was saturated and thermally heated.
FIG. 1A depicts the NH3 desorption characteristics of the unmodified alumina catalyst support as a function of time and temperature. According to FIG. 1A, a relatively large amount of desorption occurred in a relatively low temperature range, i.e. from 70° C. to 170° C. Moreover, the total amount of NH3 desorbed during thermal heating was 0.507 ml. Accordingly, 2.47 ml of NH3 was desorbed per gram of alumina.
FIG. 1B depicts the NH3 desorption characteristics of the P-modified alumina catalyst support as a function of time and temperature. According to FIG. 1B, a relatively large amount of desorption occurred in a relatively higher temperature range than that of the unmodified alumina. The higher temperature range was 140° C. to 420° C. This result confirms the relative high NH3 bonding strength of the P-modified alumina catalyst support at relatively high temperatures. This beneficial result may also provide decreased NH3 slip during operation. Moreover, the total amount of NH3 desorbed during thermal heating was 1.584 ml. Accordingly, 8.17 ml of NH3 was desorbed per gram of P-modified alumina. Table 2 shows a comparison of the results of the P-modified and unmodified alumina tests.










TABLE 2






Alumina
NH3 desorbed
ml NH3 desorbed


Alumina
weight (g)
(ml)
per g alumina







unmodified
0.2056
0.507
2.47


P-modified
0.1939
1.584
8.17









While not wanting to be bound to any particular theory or principle, the comparison demonstrates that the use of acidified catalyst materials can enhance the adsorption of NH3 in quantity and in strength.
In at least one embodiment, it has been found that the acidified catalyst materials can provide NH3 desorption per gram of P-modified alumina in the range of 2.5 to 20 ml. In at least one embodiment, it has been found that the acidified catalyst materials can provide beneficial NH3 desorption in the range of temperatures from 150 to 350° C. These beneficial operating ranges are not provided by the non-modified alumina catalyst materials, as supported by the results of this Example.
As required, detailed embodiments of the present invention are disclosed herein. However, it is to be understood that the disclosed embodiments are merely exemplary of an invention that may be embodied in various and alternative forms. While embodiments of the have been illustrated and described, it is not intended that these embodiments illustrate and describe all possible forms of the invention. Rather, the words used in the specification are words of description rather than limitation, and it is understood that various changes may be made without departing from the spirit and scope of the invention.
In accordance with the provisions of the patent statute, the principle and mode of operation of this invention have been explained and illustrated in its various embodiments. However, it must be understood that this invention may be practiced otherwise than as specifically explained and illustrated without departing from its spirit or scope.

## Claims

1. An enhanced NH3 adsorbing automotive exhaust composition comprising:
a catalyst composition suitable for use in a selective catalytic reduction (SCR) system wherein the catalyst composition comprises a combination of a cerium-containing oxide compound and non-cerium-containing metal compound selected from the group consisting of alkali metal containing compounds, alkaline-earth metal containing compounds and combinations thereof; and
an acidified support composition for enhancing NH3 adsorption capacity of the automotive exhaust composition.

2. The automotive exhaust composition of claim 1 wherein the acidified support composition comprises a support composition and a conjugate base oxide of an inorganic acid having a Ka in the range of 5.0×10−7 to 1.0.

3. The automotive exhaust composition of claim 2 wherein the Ka is in the range of 5.0×10−5 to 5.0×10−1.

4. The automotive exhaust catalyst composition of claim 2 wherein the conjugate base oxide is the conjugate base of an acid selected from the group consisting of H3PO4, H2TiO3, H2WO4, H2MoO3, HTa2O6, HNb2O6, H2CrO4 and combinations thereof.

5. The automotive exhaust catalyst composition of claim 2 wherein the support composition is selected from the group consisting of Al2O3, SiO2, TiO2, ZrO2, CeO2 and combinations thereof.

6. The automotive exhaust catalyst composition of claim 2 wherein the NH3 desorption per gram of acidified support composition is in the range of 3 to 25 ml upon substantially complete thermal release of NH3.

7. The automotive exhaust catalyst composition of claim 2 wherein the acidified support composition desorbs a substantial amount of NH3 in the range of temperatures from 150 to 350° C. during substantially complete thermal release of NH3 after saturation of the acidified support 5 composition with NH3.

8. A SCR system comprising:
a substrate; and
a catalyst composition coated upon the substrate comprising an acidified support composition for enhancing NH3 adsorption capacity of the SCR system, wherein the catalyst composition comprises a combination of a cerium-containing oxide compound and non-cerium-containing metal compound selected from the group consisting of alkali metal containing compounds, alkaline-earth metal containing compounds and combinations thereof.

9. The SCR system of claim 8 wherein the acidified support composition comprises a support composition and a conjugate base oxide of an inorganic acid having a Ka in the range of 5.0×10−7 to 1.0.

10. The SCR system of claim 9 wherein the Ka is in the range of 5.0×10−5 to 5.0×10−1.

11. The SCR system of claim 9 wherein the conjugate base oxide is the conjugate base of an acid selected from the group consisting of H3PO4, H2TiO3, H2WO4, H2MoO4, HTa2O6, HNb2O6, H2CrO4 and combinations thereof.

12. The SCR system of claim 9 wherein the support composition is selected from the group consisting of Al2O3, SiO2, TiO2, ZrO2, CeO2 and combinations thereof.

13. The SCR system of claim 9 wherein the NH3 desorption per gram of acidified support composition is in the range of 3 to 25 ml upon substantially complete thermal release of NH3 after saturation of the acidified support composition with NH3.

14. The SCR system of claim 9 wherein the acidified support composition desorbs a substantial amount of NH3 in the range of temperatures from 150 to 350° C. during substantially complete thermal release of NH3 after saturation of the acidified support composition with NH3.