Zero-PGM TWC with High Redox Reversibility

• US 20160361711A1
• Filed: 06/14/2016
• Published: 12/15/2016
• Est. Priority Date: 06/15/2015
• Status: Abandoned Application

• Current Assignee: Clean Diesel Technologies, Inc.
• Original Assignee: Clean Diesel Technologies, Inc.
• Inventors: Golden, Stephen J., Nazarpoor, Zahra
• Application Number:
  US15/182,330
• Publication Number:
  US 20160361711A1
• Time in Patent Office: Days
• US Class Current: 1/1
• CPC Class Codes: B01D 2255/2073 Manganese
• CPC Class Codes: B01D 2255/20761 Copper
• CPC Class Codes: B01D 2255/405 Spinels
• CPC Class Codes: B01D 2255/65 Catalysts not containing noble metals
• CPC Class Codes: B01D 2255/908 O2-storage component incorporated in the catalyst
• CPC Class Codes: B01D 53/945 characterised by a specific catalyst
• CPC Class Codes: B01J 23/005 Spinels
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: C01G 3/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/02 Oxides; Hydroxides
• CPC Class Codes: C01G 45/1221 Manganates or manganites with a manganese oxidation state of Mn(III), Mn(IV) or mixtures thereof
• CPC Class Codes: C01G 45/1235 of the type [Mn2O4]2-, e.g. Li2Mn2O4, Li2[MxMn2-x]O4
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/85 by XPS, EDX or EDAX data
• CPC Class Codes: C01P 2004/04 obtained by TEM, STEM, STM or AFM
• CPC Class Codes: Y02C 20/10 of nitrous oxide (N2O)
• CPC Class Codes: Y02T 10/12 Improving ICE efficiencies

Abstract

The present disclosure describes zero-platinum group metals (ZPGM) material compositions including binary Cu—Mn spinel oxide powders having stable reduction/oxidation (redox) reversibility useful for TWC and oxygen storage material applications. The behavior of Cu—Mn spinel oxide powder is analyzed under oxidation-reduction environments to determine redox reversibility, catalytic activity, and spinel structure stability. Characterization of spinel powder is performed employing X-ray diffraction analysis, hydrogen temperature-programmed reduction technique, transmission electron microscopy analysis, and X-ray photoelectron spectroscopy analysis. Test results confirm the phase and structural stability of the Cu—Mn spinel oxide during redox reaction, thereby indicating that the Cu—Mn spinel oxide can be employed in a plurality of TWC applications.

Claims

1. A catalytic composition of a binary Cu—

Mn spinel in which the catalytic composition comprises

a) a binary Cu—

Mn spinel of the formula Cu_XMn<sub>3−

X</sub>O₄, wherein X is a number from 0.01 to 2.99, and wherein the spinel comprises mixed phases of CuO, MnO and Cu_XMn<sub>3−

X</sub>O₄;

b) a mixture of Cu and MnO;

c) or a combination of a) and b).

2. The catalytic composition of claim 1, wherein the Cu—

Mn spinel is CuMn₂O₄.

3. The catalytic composition of claim 1, wherein the composition is in the form of a powder.

4. The catalytic composition according to claim 1, wherein the Cu—

Mn spinel is in a partially reduced state.

5. The catalytic composition according to claim 1, wherein the Cu—

Mn spinel is in a fully reduced state.

6. The catalytic composition according to claim 1, wherein the composition comprises a CuO phase surrounded by a MnO phase.

7. The catalytic composition of claim 6, wherein the MnO phase is surrounded by Cu—

Mn spinel particles.

8. The catalytic composition of claim 1, wherein the composition is free of platinum group metals.

9. The catalytic composition of claim 1, wherein a concentration of Cu²⁺ is higher than a concentration of Cu¹⁺ in the catalytic composition.

10. A catalytic converter comprising the composition of claim 1.

11. A method of removing one or more of nitrous oxide (NOx), carbon monoxide (CO) and hydrocarbons (HC) from an exhaust stream comprising the step of contacting the exhaust stream comprising one or more of NOx, CO, or HC with a catalytic composition, the catalytic composition comprising a) a binary Cu—

Mn spinel of the formula Cu_XMn<sub>3−

X</sub>O₄, wherein X is a number from 0.01 to 2.99, and wherein the spinel comprises mixed phases of CuO, MnO and Cu_XMn<sub>3−

X</sub>O₄;

b) a mixture of Cu and MnO;

c) or a combination of a) and b).

12. The method of claim 11, wherein the catalytic composition comprises said mixed phases of CuO, MnO and Cu_XMn₃₋

XO₄.

13. The method of claim 11, wherein the catalytic composition comprises a mixture of Cu and MnO, and wherein the step of contacting the exhaust stream is carried out at a temperature of 400°

C. to 600°

C.

14. The method of claim 11, wherein the Cu—

Mn spinel is CuMn₂O₄.

15. The method of claim 11, further comprising the step of oxidizing the catalyst composition to form a binary Cu—

Mn spinel of the formula Cu_XMn<sub>3−

X</sub>O₄, wherein X is a number from 0.01 to 2.99.

16. A method of removing pollutants from a gas stream comprising:

a) contacting an exhaust stream comprising one or more of NOx, CO, or HC with a catalytic composition comprising a binary Cu—

Mn spinel of the formula Cu_XMn<sub>3−

X</sub>O₄, wherein X is a number from 0.01 to 2.99, and wherein the step of contacting results in a reduction of one or more of NOx, CO, or HC in the exhaust stream, and in the Cu—

Mn spinel being reduced or partially reduced;

b) contacting the exhaust stream with the reduced or partially reduced Cu—

Mn spinel at a temperature that is between about 400°

C. to about 600°

C.; and

c) oxidizing the catalytic composition following step b) to form a binary Cu—

Mn spinel of the formula Cu_XMn<sub>3−

X</sub>O₄.

17. The method of claim 16, wherein the partially reduced Cu—

Mn spinel comprises mixed phases of CuO, MnO and Cu_XMn<sub>3−

X</sub>O₄.

18. The method of claim 16, wherein the reduced Cu—

Mn spinel comprises a mixture of Cu and MnO.

19. The method of claim 16, wherein the Cu—

Mn spinel is in a partially reduced state, and wherein the composition comprises a CuO phase surrounded by a MnO phase on which Cu—

Mn spinel particles are deposited.

20. The method of claim 16, wherein following step c), the concentration of Cu²⁺ is higher than the concentration of Cu¹⁺ in the catalytic composition.