High activity titania supported metal oxide DeNOx catalysts
View Patent ↗The present invention is directed to high activity titanium oxide DeNOx catalysts. In preferred embodiments, by depositing vanadium oxide on a titania supported metal oxide such as tungsten oxide, an improved catalyst may be generated. This catalyst may be used in the treatment of exhaust from sources such as automobiles and industrial plants.
1. A catalyst comprised of titanium oxide, vanadium oxide and a supported metal oxide, wherein said supported metal oxide is selected from the group consisting of oxides of tungsten, molybdenum, chromium, scandium, yttrium, lanthanum, zirconium, hafnium, niobium, tantalum, iron, ruthenium, manganese and mixtures thereof; said supported metal oxide is supported on said titanium oxide by combining said metal oxide or a precursor of said metal oxide with titanium oxide at an acidic pH, thereby forming a titania supported metal oxide having an isoelectric point of less than or equal to a pH of 3.75; said catalyst is formed by depositing said vanadium oxide on said titania supported metal oxide.
2. The catalyst of claim 1 , wherein the isoelectric point is less than or equal to a pH of 2.75.
3. The catalyst of claim 2 , wherein said titanium oxide is comprised of anatase titanium dioxide.
4. The catalyst of claim 3 , wherein the supported metal oxide comprises an oxide of tungsten.
5. The catalyst of claim 1 , wherein said vanadium oxide has a loading of less than or equal to 1.35% by weight or greater than or equal to 1.8% by weight.
6. The catalyst of claim 5 , wherein the vanadium oxide has a loading of less than or equal to 1.0% by weight.
7. The catalyst of claim 5 , wherein said supported metal oxide is comprised of an oxide of tungsten.
8. The catalyst of claim 5 , wherein said supported metal oxide has a loading of less than or equal to 20% by weight.
9. A process for making a titania supported vanadium catalyst of claim 1 , said process comprising combining vanadium oxide with a titania supported metal oxide, wherein said titania supported metal oxide has an isoelectric point of less than or equal to a pH of 3.75, prior to said combining.
10. The process according to claim 9 further comprising forming said titania supported metal oxide by:
a) combining (i) titania and (ii) a metal oxide or a metal oxide precursor to form a solution or a slurry; and
b) adding sulfate ions to said solution or said slurry to lower the isoelectric point to less than or equal to said pH of 3.75.
11. The process according to claim 9 further comprising forming said titania supported metal oxide by calcining titanium oxide and a metal oxide or metal oxide precursor, wherein said calcining occurs at a temperature of greater than or equal to 150° C.
12. The process according to claim 9 , wherein said isoelectric point is less than or equal to 2.75.
13. The process according to claim 12 , furthering comprising forming said titania supported metal catalyst by combining a metal oxide precursor with a titania oxide.
14. The process according to claim 13 , wherein said metal oxide precursor comprises a substance selected from the group consisting of tungsten, molybdenum, chromium, scandium, yttrium, lanthanum, zirconium, hafnium, niobium, tantalum, iron, ruthenium, manganese and mixtures thereof.
15. A process for forming the catalyst of claim 1 , said process comprising:
a) forming a slurry, wherein said slurry comprises titanium oxide and said slurry has a pH of 2 or lower;
b) adding a metal oxide or metal oxide precursor to said slurry;
c) obtaining a titania supported metal oxide; and
d) combining said titania supported metal oxide with vanadium oxide.
16. The process according to claim 15 , wherein said forming comprises combining sulfuric acid and said titania.
17. The process according to claim 15 , wherein said obtaining comprises filtering, drying and calcining.
18. The process according to claim 15 , wherein the isoelectric point of the titania supported metal oxide is less than or equal to a pH of 3.75.
19. The process according to claim 18 , wherein the isoelectric point of the titania supported metal oxide is less than or equal to a pH of 2.75.
20. The process according to claim 15 , wherein the metal oxide or metal oxide precursor comprises a substance selected from the group consisting of tungsten, molybdenum, chromium scandium, yttrium, lanthanum, zirconium, hafnium, niobium, tantalum, iron, ruthenium, manganese and mixtures thereof.
21. The process according to claim 15 , wherein b) comprises adding a metal oxide precursor and the metal oxide precursor is ammonia paratungstate.
22. A process for forming the catalyst of claim 1 , said process composing:
a) forming a slurry comprised of titanium oxide and a metal oxide or metal oxide precursor;
b) reducing the pH of the slurry to pH 2 or lower;
c) obtaining a titania supported metal oxide; and
d) combining said titania supported metal oxide with vanadium oxide.
23. The process according to claim 22 , wherein the reducing is accomplished by adding sulfuric acid.
24. The process according to claim 22 , wherein said obtaining comprises filtering, drying and calcining.
25. The process according to claim 22 , wherein a) comprises adding a metal oxide precursor and the metal oxide precursor comprises a substance selected from the group consisting of tungsten, molybdenum, chromium scandium, yttrium, lanthanum, zirconium, hafnium, niobium, tantalum, iron, ruthenium, manganese and mixtures thereof.
26. The process according to claim 25 , wherein the metal oxide precursor comprises ammonium paratungstate.
27. A method for treating noxious substances, said method comprising exposing nitrogen oxides to the catalyst of claim 1 .
28. A method for treating noxious substances, said method comprising exposing nitrogen oxides to the catalyst of claim 5 .
29. A process for forming a catalyst of claim 1 , said process comprising:
a) forming a titania supported metal oxide, wherein said forming comprises:
i) dissolving ammonium paratungstate in water at a temperature of at least 50° C.;
ii) combining said ammonium paratungstate in water with titania to form a slurry, wherein said slurry has a pH of less than or equal to 2;
iii) recovering titania and tungsten oxide from said slurry;
iv) drying said titania and tungsten oxide from said slurry;
v) calcining said titania and tungsten oxide at a temperature of greater than or equal to 500° C. for at least 6 hours to form a titania supported metal oxide, wherein said titania supported metal oxide has an isoelectric point of less than or equal to 2; and
b) associating vanadium oxide with said titanium supported metal oxide said associating comprising:
i) dissolving vanadium oxide or a vanadium oxide precursor in water and monoethanolamine to form a solution;
ii) combining said solution with said titania supported metal oxide;
iii) recovering vanadium oxide and said titania supported metal oxide;
iv) drying said vanadium oxide and said titania supported metal oxide at a first temperature of greater than 60° C. in a rotary evaporator and then at a second temperature of at least 100° C.; and
v) calcining said vanadium oxide and said titania supported metal oxide at a temperature of at least 600° C. for at least 6 hours to form said catalyst.
30. In the process of producing a catalyst comprised of titania and a supported metal oxide, the improvement of manipulating the isoelectric point of said catalyst to less than or equal to 3.75.