Fuel additive containing lattice engineered cerium dioxide nanoparticles

• US 10,435,639 B2
• Filed: 12/17/2008
• Issued: 10/08/2019
• Est. Priority Date: 09/05/2006
• Status: Active Grant

• Current Assignee: Cerion, LLC (Revstone Industries LLC)
• Original Assignee: Cerion, LLC (Revstone Industries LLC)
• Inventors: Difrancesco, Albert Gary, Allston, Thomas D., Hailstone, Richard K., Langner, Andreas, Reed, Kenneth J.
• Primary Examiner(s): McAvoy, Ellen M
• Assistant Examiner(s): Po, Ming Cheung
• Application Number:
  US13/140,648
• Publication Number:
  US 20120124899A1
• Time in Patent Office: 3,947 Days
• Field of Search: 44457
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/10 of rare earths
• CPC Class Codes: B01J 23/83 with rare earths or actinides
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/3712 Cerium
• CPC Class Codes: B01J 2523/48 Zirconium
• CPC Class Codes: B01J 2523/842 Iron
• CPC Class Codes: B01J 35/00 Catalysts, in general, characterised by their form or physical properties
• CPC Class Codes: B01J 35/23 in a colloidal state
• CPC Class Codes: B01J 35/393 Metal or metal oxide crystallite size
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C10L 1/1241 metal carbonyls
• CPC Class Codes: C10L 2200/0245 Lanthanide group metals: La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu
• CPC Class Codes: C10M 103/06 Metal compounds
• CPC Class Codes: C10M 177/00 Special methods of preparation of lubricating compositions; Chemical modification by after-treatment of components or of the whole of a lubricating composition, not covered by other classes
• CPC Class Codes: C10N 2010/06 Groups 3 or 13

Abstract

A process for making cerium dioxide nanoparticles containing at least one transition metal (M) utilizes a suspension of cerium hydroxide nanoparticles prepared by mechanical shearing of an aqueous mixture containing an oxidant in an amount effective to enable oxidation of cerous ion to ceric ion, thereby forming a product stream that contains transition metal-containing cerium dioxide nanoparticles, Ce_1-xM_xO₂, wherein “x” has a value from about 0.3 to about 0.8. The nanoparticles thus obtained have a cubic fluorite structure, a mean hydrodynamic diameter in the range of about 1 nm to about 10 nm, and a geometric diameter of less than about 4 nm. The transition metal-containing crystalline cerium dioxide nanoparticles can be used to prepare a dispersion of the particles in a nonpolar medium.

Claims

1. A process for making lattice engineered crystalline cerium dioxide nanoparticles containing at least one metal (M), said process comprising:

(a) providing an aqueous reaction mixture comprising a source of cerous ion, a source of one or more metal ions (M), a source of hydroxide ion, at least one water-soluble nanoparticle stabilizer, and an oxidant, wherein the metal ions (M) are ions of elements selected from the group consisting of rare earth metals and transition metals, and wherein said at least one water-soluble nanoparticle stabilizer comprises a compound selected from the group consisting of alkoxy substituted carboxylic acids, α

-hydroxyl carboxylic acids, α

-keto carboxylic acids, and polyacids, wherein said alkoxy substituted carboxylic acid comprises a compound of formula (Ia);

R—

O—

(CH₂CH₂O)_nCHR¹CO₂Y 

 

(Ia)

wherein;

R represents a methyl or an ethyl group;

R¹ represents a hydrogen or an alkyl group;

Y represents a hydrogen or a counter ion; and

n is an integer from 0 to 5;

(b) shearing said mixture, thereby forming a homogeneously distributed suspension of cerium hydroxide nanoparticles; and

(c) providing temperature conditions in the homogeneously distributed suspension of cerium hydroxide nanoparticles effective to enable oxidation of cerous ion to ceric ion, thereby forming a dispersion comprising metal-containing cerium dioxide nanoparticles, Ce_1-xM_xO₂, wherein “

x”

has a value from about 0.02 to about 0.8, said nanoparticles having a crystalline cubic fluorite structure, a mean hydrodynamic diameter in the range of about 1 nm to about 10 nm, and wherein a size distribution of said nanoparticles has a coefficient of variation of less than 32%.

2. The process according to claim 1 wherein said mechanical shearing is effected in a colloid mill.

3. The process according to claim 1 wherein said temperature conditions effective to enable oxidation of cerous ion to ceric ion comprise a temperature of about 50°

C. to about 100°

C.

4. The process according to claim 3 wherein said temperature conditions effective to enable oxidation of cerous ion to ceric ion comprise a temperature of about 60°

C. to about 90°

C.

5. The process according to claim 1 wherein said sources of ions are introduced into said reaction mixture either concurrently or sequentially during said mechanical shearing.

6. The process according to claim 1 wherein said metal-containing cerium dioxide nanoparticles have a mean hydrodynamic diameter of about 8 nm or less.

7. The process according to claim 1, wherein the at least one water-soluble nanoparticle stabilizer comprises a compound selected from the group consisting of lactic acid, gluconic acid enantiomers, ethylenediaminetetraacetic acid, tartaric acid, citric acid, pyruvic acid, methoxy acetic acid, 2-(methoxy)ethoxy acetic acid, 2-[2-(2-methoxyethoxy)ethoxy] acetic acid, 2-hydroxybutanoic acid, and combinations thereof.

8. A process for making lattice engineered crystalline cerium dioxide nanoparticles containing at least one metal (M), said process comprising:

(a) providing an aqueous reaction mixture comprising a source of cerous ion, a source of one or more metal ions (M), a source of hydroxide ion, at least one water-soluble nanoparticle stabilizer, and an oxidant, wherein the metal ions (M) are ions of elements selected from the group consisting of rare earth metals and transition metals, and wherein said at least one water-soluble nanoparticle stabilizer comprises a compound selected from the group consisting of alkoxy substituted carboxylic acids, α

-hydroxyl carboxylic acids, α

-keto carboxylic acids, and polyacids, wherein said alkoxy substituted carboxylic acid comprises a compound of formula (Ia);

R—

O—

(CH₂CH₂O)_nCHR¹CO₂Y 

 

(Ia)

wherein;

R represents a methyl or an ethyl group;

R¹ represents a hydrogen or an alkyl group;

Y represents a hydrogen or a counter ion; and

n is an integer from 0 to 5;

(b) shearing said mixture, thereby forming a homogeneously distributed suspension of cerium hydroxide nanoparticles; and

(c) providing temperature conditions in the homogeneously distributed suspension of cerium hydroxide nanoparticles effective to enable oxidation of cerous ion to ceric ion, thereby forming a dispersion comprising metal-containing cerium dioxide nanoparticles, Ce_1-xM_xO₂, wherein “

x”

has a value from about 0.02 to about 0.8, said nanoparticles having a crystalline cubic fluorite structure, a mean hydrodynamic diameter in the range of about 1 nm to about 10 nm, and a geometric diameter of less than 4 nm.