Cerium (IV) catalyst compounds and promoting combustion of hydrocarbon fuels therewith

• US 5,449,387 A
• Filed: 01/18/1994
• Issued: 09/12/1995
• Est. Priority Date: 06/17/1992
• Status: Expired due to Fees

• Current Assignee: Rhone-Poulenc Chemicals Limited (Solvac SA)
• Original Assignee: Rhone-Poulenc Chemicals Limited (Solvac SA)
• Inventors: Hawkins, Ian M., Mauermann, Heiko H. K.
• Primary Examiner(s): Willis, Jr., Prince
• Assistant Examiner(s): Diamond, Alan D.
• Application Number:
  US08/184,197
• Time in Patent Office: 602 Days
• Field of Search: 44/364, 44/355, 44/356, 44/354, 44/357, 44/358, 534/15, 534/16, 554/72, 556/1, 562/600, 252/313.1, 106/1.05, 106/14.36, 106/27 B:28 A, 106/30 C
• US Class Current: 44/364
• CPC Class Codes: B01J 23/10 of rare earths
• CPC Class Codes: C07C 305/06 Hydrogenosulfates
• CPC Class Codes: C07C 53/10 Salts thereof
• CPC Class Codes: C07C 53/122 Propionic acid
• CPC Class Codes: C07C 53/124 Acids containing four carbon atoms
• CPC Class Codes: C07C 53/128 the carboxylic group being bound to a carbon atom bound to at least two other carbon atoms, e.g. neo-acids
• CPC Class Codes: C07C 63/08 Salts thereof
• CPC Class Codes: C07F 9/11 with hydroxyalkyl compounds without further substituents on alkyl
• CPC Class Codes: C10L 1/301 derived from metals
• CPC Class Codes: C10L 10/00 Use of additives to fuels or fires for particular purposes additives for liquid carbonaceous fuels characterised by their chemical nature C10L1/10; using binders for briquetting solid fuels C10L5/10; using additives to improve the combustion of solid fuels C10L9/10

Abstract

Novel cerium (IV) oxidic compounds, well suited as catalysts, e.g., for the clean combustion of hydrocarbon fuels and for the "drying" of paint compositions, each Ce(IV) atom of which being coordinated with two anions of an organic oxyacid advantageously having a pKa greater than 1, preferably greater than 2, or a mixture of such oxyacids, and the oxidic oxygen atom or atoms of which being other than those comprising the organic oxyacids; representative such novel cerium (IV) oxidic compounds, whether yellow crystalline solids or yellow liquids, have the formula:

(H.sub.2 O).sub.p [CeO(A).sub.2 ·(AH).sub.n ·].sub.m

in which the radicals A, which may be the same or different, are each the residue of an organic oxyacid of formula AH, p is an integer ranging from 0 to 5, n ranges from 0 to 2 and m is an integer ranging from 1 to 12.

Claims

1. A cerium (IV) oxidic compound having the formula:

space="preserve" listing-type="equation">(H.sub.2 O).sub.p [CeO(A).sub.2 ·

(AH).sub.n ·

].sub.m

in which the radicals A, which are identical or different, are each an anion of an organic oxyacid of formula AH having a pKa greater than 1, p is an integer ranging from 0 to 5, n is a number ranging from 0 to 2, and m is an integer ranging from 1 to 12.

2. A cerium (IV) oxidic compound as defined by claim 1, having the formula:

space="preserve" listing-type="equation">(H.sub.2 O).sub.4 [CeO(A).sub.2 ·

(AH).sub.n ·

].sub.6

in which n is 0 or 2.

3. A cerium (IV) oxidic compound as defined by claim 1, said organic oxyacids having a pKa greater than 2.

4. A cerium (IV) oxidic compound as defined by claim 1, each of said organic oxyacids comprising a carboxylic, organosulfuric, organosulfonic, organophosphoric or organophosphonic acid.

5. A cerium (IV) oxidic compound as defined by claim 4, each of said organic oxyacids comprising a carboxylic acid.

6. A cerium (IV) oxidic compound as defined by claim 5, each of said carboxylic acids comprising a C₂ -C₂₀ monocarboxylic acid, or a C₄ -C₁₂ dicarboxylic acid.

7. A cerium (IV) oxidic compound as defined by claim 6, each of said organic oxyacids comprising a C₄ -C₁₂ alkanoic acid, benzoic acid, or an alkyl-substituted benzoic acid, the alkyl substituent of which having up to 12 carbon atoms.

8. A cerium-(IV) oxidic compound as defined by claim 4, each of said organic oxyacids comprising acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, 2-methylbutyric acid, 2,2-dimethylbutyric acid, 2-ethylbutyric acid, 2-methylpentanoic acid, 2-ethylhexanoic acid, ethylacetoacetic acid, 3,5-dimethylhexanoic acid, cyclohexane carboxylic acid, neohexanoic acid, neoheptanoic acid, neooctanoic acid, isononanic acid, neodecanoic acid, undecylenic acid, perfluorobutyric acid, benzoic acid, p-tert-butylbenzoic acid, naphthenic acid, anthranilic acid, behenic acid, maleic acid, sebacic acid, bis(2-ethylhexyl)phosphoric acid, dodecylbenzene sulfonic acid, dodecylsulfuric acid, or p-toluene sulfonic acid.

9. A cerium (IV) oxidic compound as defined by claim 7, each of said organic oxyacids comprising an alkanoic acid having 8 carbon atoms.

10. An organic solvent-soluble cerium (IV) oxidic compound as defined by claim 1.

11. A hydrocarbon-soluble cerium (IV) oxidic compound as defined by claim 10.

12. A cerium (IV) oxidic compound as defined by claim 1, comprising yellow crystalline solids.

13. A cerium (IV) oxidic compound as defined by claim 1, comprising a yellow liquid.

14. A cerium (IV) oxidic compound as defined by claim 1, the cerium of which comprising at least 90% cerium (IV).

15. A cerium (IV) oxidic compound as defined by claim 14, the cerium of which comprising at least 95% cerium (IV).

16. A cerium (IV) oxidic compound as defined by claim 15, the cerium of which comprising at least 99% cerium (IV).

17. A cerium (IV) oxidic compound as defined by claim 1, said cerium (IV) oxide compound being:

cerium (IV) oxidic acetate octoate,

cerium (IV) oxidic anthranilate octoate,

cerium (IV) oxidic dibehenate,

cerium (IV) oxidic dibenzoate,

cerium (IV) oxidic benzoate octoate,

cerium (IV) oxidic bis(2-ethylhexyl)phosphate,

cerium (IV) oxidic bis(2-ethylhexyl)phosphate octoate,

cerium (IV) oxidic dibutyrate,

cerium (IV) oxidic butyrate octoate,

cerium (IV) oxidic dicekanoate,

cerium (IV) oxidic di(cyclohexane carboxylate),

cerium (IV) oxidic di(2,2-dimethylbutyrate),

cerium (IV) oxidic didodecylsulfate,

cerium (IV) oxidic dodecylsulfate octoate,

cerium (IV) oxidic didodecylbenzenesulfonate,

cerium (IV) oxidic dodecylbenzenesulfonate octoate,

cerium (IV) oxidic di(2-ethylbutyrate),

cerium (IV) oxidic 2-ethylbutyrate octoate,

cerium (IV) oxidic diisobutyrate,

cerium (IV) oxidic isobutyrate octoate,

cerium (IV) oxidic isobutyrate₃.0 octoate₁.0,

cerium (IV) oxidic dimaleate,

cerium (IV) oxidic maleate octoate,

cerium (IV) oxidic di(2-methylbutyrate),

cerium (IV) oxidic 2-methylbutyrate octoate,

cerium (IV) oxidic di(2-methylpentanoate),

cerium (IV) oxidic dinaphthenate,

cerium (IV) oxidic dineodecanoate,

cerium (IV) oxidic dineoheptanoate,

cerium (IV) oxidic dineooctanoate,

cerium (IV) oxidic dioctoate,

cerium (IV) oxidic (octoate)₃ (EAA),

cerium (IV) oxidic diperfluorobutyrate,

cerium (IV) oxidic dipivalate,

cerium (IV) oxidic pivalate octoate,

cerium (IV) oxidic dipropionate,

cerium (IV) oxidic propionate octoate,

cerium (IV) oxidic di-p-tertbutylbenzoate,

cerium (IV) oxidic p-tertbutylbenzoate octoate,

cerium (IV) oxidic p-toluenesulfonate octoate,

cerium (IV) oxidic disebacate,

cerium (IV) oxidic sebacate octoate,

cerium (IV) oxidic diundecylenate, or

cerium (IV) oxidic undecylenate octoate.

18. A cerium (IV) oxidic compound as defined in claim 1 prepared by reacting a cerium (IV) salt with a salt of an organic oxyacid, or with admixture of salts of organic oxyacids.

19. A solvent solution containing a cerium (IV) oxidic compound as defined by claims 1 or 18 in an apolar solvent medium.

20. The solvent solution as defined by claim 19, said apolar solvent medium comprising a hydrocarbon.

21. A solvent solution containing a cerium (IV) oxidic compound as defined by claims 1 or 18, in a polar solvent medium.

22. The solvent solution as defined by claim 21, said polar solvent medium comprising a carboxylic acid, ether, alcohol, or halogenated hydrocarbon.

23. A hydrocarbon fuel containing a combustion-promoting amount of a cerium (IV) oxidic compound as defined by claims 1 or 18.

24. The hydrocarbon fuel as defined by claim 23 wherein said fuel a diesel fuel.

25. A solvent solution containing a cerium (IV) oxidic compound as defined by claims 1 or 18, in a concentration of greater than 10% of the total weight thereof.

26. The solvent solution as defined by claim 25 said cerium (IV) oxidic compound being present in a concentration of greater than 20% of the total weight thereof.

27. The solvent solution as defined by claim 26 said cerium (IV) oxidic compound being present in a concentration of at least 30% of the total weight thereof.

28. A cerium (IV) oxidic compound having the formula:

space="preserve" listing-type="equation">H.sub.6 Ce.sub.6 O.sub.8 (OH).sub.2 (RC00).sub.12

in which R is alkyl radical having from 3 to 9 carbon atoms, having an octahedral structure with the six cerium atoms at the apexes of the octahedron, the twelve carboxylate residues forming bidentate bridges between the cerium atoms along the edges of the octahedron, one triply bridging oxygen atom on each face of the octahedron and two unidentate hydroxyl ligands completing the coordination of two opposing cerium atoms.