Catalyst for direct NOx decomposition and a method for making and using the catalyst

Abstract

Catalyst material comprising a ternary spinel mixed oxide for treatment of an exhaust gas stream via direct decomposition removal of NOx to N.sub.2 and O.sub.2. The low temperature (from about 400 C. to about 650 C.), direct decomposition is accomplished without the need of a reductant molecule. In one example, Mn may be incorporated into metal oxide, such as Cu.sub.yCo.sub.3-yO.sub.4 spinel oxide, synthesized using co-precipitation techniques.

Claims

1. A catalyst having activity for direct decomposition removal of NO.sub.x from an exhaust gas stream to N.sub.2 and O.sub.2, the catalyst comprising a material which comprises Mn-doped CuCo, wherein the Mn-doped CuCo comprises Mn.sub.xCu.sub.yCo.sub.3.0-x-yO.sub.4, wherein 0.1<x0.3 and 0.1<y0.9, said catalyst having activity for direct decomposition removal of NOx at a temperature of about 500 C.

2. The catalyst of claim 1, wherein the Mn-doped CuCo is selected from the group consisting of: Mn.sub.0.1Cu.sub.0.4Co.sub.2.5O.sub.4, Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4, Mn.sub.0.1Cu.sub.0.1Co.sub.2.8O.sub.4, Mn.sub.0.1Cu.sub.0.2Co.sub.2.7O.sub.4, and Mn.sub.0.1Cu.sub.0.3Co.sub.2.6O.sub.4.

3. The catalyst of claim 1, wherein 0.1<x0.3 and 0.1<y0.5.

4. The catalyst of claim 1, wherein the Mn-doped CuCo is Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4.

5. A method for direct decomposition removal of NO.sub.x from combustion engine exhaust, said method comprising: exposing an exhaust gas having NO.sub.x to a catalyst material which comprises Mn-doped CuCo having activity for direct decomposition to convert NO.sub.x to N.sub.2 and O.sub.2, wherein the Mn-doped CuCo comprises Mn.sub.xCu.sub.yCo.sub.3.0-x-yO.sub.4, wherein 0.1<x0.3 and 0.1<y0.9, and wherein the direct decomposition removal of NOx is at a temperature of about 500 C.

6. The method of claim 5, wherein the Mn-doped CuCo is selected from the group consisting of: Mn.sub.0.1Cu.sub.0.4Co.sub.2.5O.sub.4, Mn.sub.0.1Cu.sub.0.4Co.sub.2.4O.sub.4, Mn.sub.0.1Cu.sub.0.1Co.sub.2.8O.sub.4, Mn.sub.0.1Cu.sub.0.2Co.sub.2.7O.sub.4, and Mn.sub.0.1Cu.sub.0.3Co.sub.2.6O.sub.4.

7. The method of claim 5, wherein 0.1<x0.3 and 0.1<y0.5.

8. The method of claim 5, wherein the Mn-doped CuCo is Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4.

9. A method of making a catalyst for removal of NO.sub.x from a combustion engine, the catalyst comprising a material which comprises Mn-doped CuCo, wherein the Mn-doped CuCo comprises Mn.sub.xCu.sub.yCo.sub.3.0-x-yO.sub.4, wherein 0.1<x0.3 and 0.1<y0.9, said catalyst having activity for direct decomposition removal of NOx at a temperature of about 500 C., the method comprising: Co-precipitation using a precipitating agent selected from the group consisting of NaOH, Na.sub.2CO.sub.3, and (NH.sub.4).sub.2CO.sub.3; drying the obtained precipitate; and calcining at 500 C. for a time period of from 1 hr to 5 hrs at a ramp rate of from 0.1 C./min. to 20 C./min.

10. The method according to claim 9, wherein the precipitating agent is NaOH.

11. The method according to claim 9, wherein the time period is 1 hr.

12. The method according to claim 9, wherein the ramp rate is 2 C./min.

13. A catalytic converter, comprising: a body defining a chamber, the body having an inlet to receive an exhaust gas stream into the chamber, and an outlet to allow the exhaust gas stream to exit the body; and a catalyst arranged in the chamber for direct decomposition removal of NO.sub.x from exhaust gas stream, the catalyst comprising a material which comprises Mn-doped CuCo having activity for direct decomposition to convert NO.sub.x to N.sub.2 and O.sub.2, wherein the Mn-doped CuCo comprises Mn.sub.xCu.sub.yCo.sub.3.0-x-yO.sub.4, wherein 0.1<x0.3 and 0.1<y0.9.

14. The catalytic converter of claim 13, wherein the Mn-doped CuCo is selected from the group consisting of: Mn.sub.0.1Cu.sub.0.4Co.sub.2.5O.sub.4, Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4, Mn.sub.0.1Cu.sub.0.1Co.sub.2.8O.sub.4, Mn.sub.0.1Cu.sub.0.2Co.sub.2.7O.sub.4, and Mn.sub.0.1Cu.sub.0.3Co.sub.2.6O.sub.4.

Description

DRAWINGS

(1) The present teachings will become more fully understood from the detailed description and the accompanying drawings wherein:

(2) FIG. 1 is a plot of X-ray diffraction profiles of the CO.sub.3O.sub.4, CuCo.sub.2O.sub.4 and Mn.sub.0.1 Co.sub.1.9CuO.sub.4 catalysts.

(3) FIG. 2 illustrates Scheme 1 for direct NOx decomposition measurements.

(4) FIG. 3 illustrates NO conversion profiles (activity) over Mn at 0.1, 0.2 and 0.3 moles doped into Cu.sub.yCo.sub.3-yO.sub.4 with respect to Cu doping amount (moles).

(5) FIG. 4 illustrates X-ray diffraction profiles of the Cu.sub.yCo.sub.3-yO.sub.4 catalysts.

(6) FIG. 5 illustrates X-ray diffraction profiles of the Mn.sub.0.1Cu.sub.yCo.sub.3-yO.sub.4 catalysts.

(7) FIG. 6 illustrates CuO crystallinity formation (%) vs Cu doping amounts (moles) for the Cu.sub.yCo.sub.3-yO.sub.4 and Mn.sub.0.1Cu.sub.yCo.sub.3-yO.sub.4.

(8) It should be noted that the figures set forth herein are intended to exemplify the general characteristics of the methods, algorithms, and devices among those of the present technology, for the purpose of the description of certain aspects. These figures may not precisely reflect the characteristics of any given aspect and are not necessarily intended to define or limit specific embodiments within the scope of this technology. Further, certain aspects may incorporate features from a combination of figures.

DESCRIPTION

(9) The present teachings provide ternary spinel mixed oxide catalyst materials for direct NO decomposition applications to remove NOx from exhaust gas systems. The ternary spinels refer to spinels consisting of 3 transition metals. The materials include Mn as a dopant for CuCo, which improves the activity, and stability of CuCo catalysts for direct NO decomposition. Direct decomposition, as discussed herein, refers to catalytic transformation of nitrogen oxides to elemental nitrogen and oxygen. This differs, for example, from catalytic reduction of nitrogen oxides to ammonia and water. The low temperature (i.e., from about 400 C. to about 650 C.), direct decomposition is accomplished without the need of a reductant or secondary reducing reagents (i.e., H.sub.2, CO, C.sub.3H.sub.6 or other hydrocarbons, and/or soot), thereby improving fuel efficiency. This is greatly beneficial to improve the energy utilization of a vehicle engine because the reducing agents of carbon monoxide and unburnt hydrocarbons are produced as a result of inefficient combustion.

(10) In one aspect, the ternary spinel mixed oxide catalyst materials have a general formula of Mn.sub.xCu.sub.yCo.sub.3.0-x-yO.sub.4, wherein 0.01<x1.5 and 0.01<y1.5. In an embodiment, 0.1<x1.5. In another embodiment 0.01<x0.3. In another embodiment, 0.1<y1.0. In yet another embodiment, x=0.1 and y=0.5.

(11) In another aspect, the ternary spinel mixed oxide catalyst materials are active in a temperature region preferably from about 400 C. to about 800 C., and more preferably in a temperature region of about 400 C. to about 650 C., covering the typical exhaust temperatures of emission gas from gasoline or diesel engines. In another embodiment, the catalysts are active at a temperature of about 500 C.

(12) The catalyst material of the present disclosure can be used in a chamber or enclosure, such as a catalytic converter having and inlet and an outlet. As is commonly known to those of ordinary skill in the art, such a chamber or enclosure can be configured to receive an exhaust gas stream through the inlet and to exit the exhaust gas stream through the outlet such that the exhaust gas stream has a particular defined flow chamber direction.

(13) In yet another aspect, a catalyst material of the present disclosure is synthesized by a co-precipitation method using a precipitating agent selected from NaOH, Na.sub.2CO.sub.3, (NH.sub.4).sub.2CO.sub.3; drying the obtained precipitate; and calcining at 500 C. for a time period of from 1 hr to 5 hrs at a ramp rate of from 0.1 C./min. to 20 C./min. In one embodiment, the time period is 1 hr. In another embodiment the ramp rate is 2 C./min. In yet another embodiment the precipitating agent is NaOH.

(14) Examples

(15) Various aspects of the present disclosure are further illustrated with respect to the following examples. It is to be understood that these examples are provided to illustrate specific embodiments of the present disclosure and should not be construed as limiting the scope of the present disclosure in or to any particular aspect.

(16) Synthesis and Material Characterization

(17) The Mn doped CuCo ternary spinel oxide catalyst materials were synthesized by a co-precipitation method using NaOH as a precipitating agent. The required amounts of Co(NO.sub.3).sub.3, Cu(NO.sub.3).sub.3 and Mn(NO.sub.3).sub.2 were dissolved separately in deionized water and mixed. A 2M (200 ml) solution of sodium hydroxide (NaOH) was prepared and slowly added to the salt solution dropwise. The pH of the solution was constantly monitored as the NaOH solution was added. The reactants were constantly stirred using a magnetic stirrer until a pH level of 9-10 was reached. To get free particles from sodium compounds, the precipitate was then washed several times with distilled water. The supernatant liquid was then decanted and filtered to obtain the precipitate. The precipitate was then dried overnight at 120 C. The acquired substance was then grinded into a fine powder. The catalyst materials were calcined at 500 C. for 1 hour at 2 C./min.

(18) Mn doped CuCo ternary spinel mixed oxide catalyst materials having the general formula Mn.sub.xCu.sub.yCo.sub.3-x-yO.sub.4 where 0.01<x1.5 and 0.01<y1.5 were synthesized as described above by varying the ratios between Co, Cu and Mn, accordingly. Examples include, but are not limited to, the following: Mn.sub.0.1Cu.sub.1Co.sub.1.9O.sub.4, Mn.sub.0.1Cu.sub.1.5Co.sub.1.4O.sub.4, Mn.sub.0.1Cu.sub.1.1Co.sub.1.8O.sub.4, Mn.sub.0.1 Cu.sub.0.4Co.sub.2.5O.sub.4, Mn.sub.0.1Cu.sub.0.5 Co.sub.2.4O.sub.4, Mn.sub.0.1Cu.sub.0.1Co.sub.2.8O.sub.4, Mn.sub.0.1Cu.sub.0.2Co.sub.2.7O.sub.4, and Mn.sub.0.1Cu.sub.0.3Co.sub.2.6O.sub.4.
Performance Evaluation

(19) The phase composition was determined by X-ray powder diffraction (XRD) using a Rigaku SmartLab X-ray diffractometer using Cu Ka radiation (1 1.5405 A). A glass holder was used to support the sample. The scanning range was from 10 to 80 (2) with a step size of 0.02 and a step time of 1 s. The XRD phases present in the samples were identified with the help of ICDD-JCPDS data files.

(20) The direct NOx decomposition measurements were performed in a fixed bed flow reactor following Scheme 1 as shown in FIG. 2. The direct NOx decomposition measurements were performed using 1% NOx balance helium with a gas hourly space velocity of 2,100 h-1 and at temperature region of 500 C. Before the reaction, catalysts were pretreated at 500 C. in the presence of 20% O.sub.2/He. After the pretreatment, the bed temperature was kept at 500 C. and direct NOx decomposition measurements were collected for 3 hours until it reached steady state. The direct NO decomposition activity values of Mn doped CuCo catalysts are presented in Table 1 along with the pure CuCo catalysts. As shown in Table 1 all the Mn doped CuCo catalysts exhibit better activity compared to the CuCo catalysts. At the same Cu concentration, Mn doped samples exhibits higher activity compared to pure CuCo samples. Among the various catalysts, Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4 catalyst exhibits best activity.

(21) TABLE-US-00001 TABLE 1 Direct NO decomposition activity values of CuCo and MnCuCo catalysts Catalysts Activity (mol/g/s) CuCo.sub.2O.sub.4 0.013 Cu.sub.1.5Co.sub.1.5O.sub.4 0.017 Mn.sub.0.1Co.sub.1.9Cu.sub.1O.sub.4 0.024 Mn.sub.0.1Co.sub.1.4Cu.sub.1.5O.sub.4 0.023 Mn.sub.0.1Co.sub.1.8Cu.sub.1.1O.sub.4 0.032 Cu.sub.0.4Co.sub.2.6O.sub.4 0.034 Mn.sub.0.1Cu.sub.0.4Co.sub.2.5O.sub.4 0.0461 Cu.sub.0.5Co.sub.2.5O.sub.4 0.031 Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4 0.0493

(22) Further, 0.1, 0.2, and 0.3 moles of Mn were doped into Cu.sub.yCo.sub.3-yO.sub.4 and the catalyst were evaluated for direct NO decomposition. As shown in FIG. 3, doping with 0.1 moles of Mn, i.e., Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4, exhibits superior activity.

(23) X-ray diffraction profiles of Cu.sub.yCo.sub.3-yO.sub.4 and Mn.sub.0.1Cu.sub.yCo.sub.3-yO.sub.4 were taken to determine the influence of Cu on the CO.sub.3O.sub.4 structure in the presence or absence of manganese (see FIG. 4 and FIG. 5). FIG. 6 shows that Mn delays the formation of crystalline CuO compared to pure Cu.sub.yCo.sub.3-yO.sub.4 and that Mn is responsible for the higher activity. Table 3 also shows that Mn increases the lattice constant of the CO.sub.3O.sub.4 and incorporates more Cu into the CO.sub.3O.sub.4 lattice and is still responsible for the higher activity.

(24) TABLE-US-00002 TABLE 3 Co.sub.3O.sub.4 lattice constant values of the Cu.sub.yCo.sub.3yO.sub.4 and Mn.sub.0.1Cu.sub.yCo.sub.3yO.sub.4 catalysts Catalyst Lattice constant Cu.sub.0.1Co.sub.2.9O.sub.4 8.0854 Cu.sub.0.3Co.sub.2.7O.sub.4 8.095 Cu.sub.0.4Co.sub.2.6O.sub.4 8.10675 Mn.sub.0.1Cu.sub.0.1Co.sub.2.8O.sub.4 8.112 Mn.sub.0.1Cu.sub.0.3Co.sub.2.6O.sub.4 8.11438 Mn.sub.0.1Cu.sub.0.4Co.sub.2.5O.sub.4 8.1206 Mn.sub.0.1Cu.sub.0.5Co.sub.2.4O.sub.4 8.129

(25) The preceding description is merely illustrative in nature and is in no way intended to limit the disclosure, its application, or uses. As used herein, the phrase at least one of A, B, and C should be construed to mean a logical (A or B or C), using a non-exclusive logical or. It should be understood that the various steps within a method may be executed in different order without altering the principles of the present disclosure. Disclosure of ranges includes disclosure of all ranges and subdivided ranges within the entire range.

(26) The headings (such as Background and Summary) and sub-headings used herein are intended only for general organization of topics within the present disclosure and are not intended to limit the disclosure of the technology or any aspect thereof. The recitation of multiple embodiments having stated features is not intended to exclude other embodiments having additional features, or other embodiments incorporating different combinations of the stated features.

(27) As used herein, the terms comprise and include and their variants are intended to be non-limiting, such that recitation of items in succession or a list is not to the exclusion of other like items that may also be useful in the devices and methods of this technology. Similarly, the terms can and may and their variants are intended to be non-limiting, such that recitation that an embodiment can or may comprise certain elements or features does not exclude other embodiments of the present technology that do not contain those elements or features.

(28) The broad teachings of the present disclosure can be implemented in a variety of forms. Therefore, while this disclosure includes particular examples, the true scope of the disclosure should not be so limited since other modifications will become apparent to the skilled practitioner upon a study of the specification and the following claims. Reference herein to one aspect, or various aspects means that a particular feature, structure, or characteristic described in connection with an embodiment or particular system is included in at least one embodiment or aspect. The appearances of the phrase in one aspect (or variations thereof) are not necessarily referring to the same aspect or embodiment. It should be also understood that the various method steps discussed herein do not have to be carried out in the same order as depicted, and not each method step is required in each aspect or embodiment.

(29) The foregoing description of the embodiments has been provided for purposes of illustration and description. It is not intended to be exhaustive or to limit the disclosure. Individual elements or features of a particular embodiment are generally not limited to that particular embodiment, but, where applicable, are interchangeable and can be used in a selected embodiment, even if not specifically shown or described. The same may also be varied in many ways. Such variations should not be regarded as a departure from the disclosure, and all such modifications are intended to be included within the scope of the disclosure.