Methods of preparing a catalyst utilizing hydrated reagents
A method comprising a) contacting a solvent, a carboxylic acid, and a peroxide-containing compound to form an acidic mixture wherein a weight ratio of solvent to carboxylic acid in the acidic mixture is from about 1:1 to about 100:1; b) contacting a titanium-containing compound and the acidic mixture to form a solubilized titanium mixture wherein an equivalent molar ratio of titanium-containing compound to carboxylic acid in the solubilized titanium mixture is from about 1:1 to about 1:4 and an equivalent molar ratio of titanium-containing compound to peroxide-containing compound in the solubilized titanium mixture is from about 1:1 to about 1:20; and c) contacting a chromium-silica support comprising from about 0.1 wt. % to about 20 wt. % water and the solubilized titanium mixture to form an addition product and drying the addition product by heating to a temperature in a range of from about 50° C. to about 150° C. and maintaining the temperature in the range of from about 50° C. to about 150° C. for a time period of from about 30 minutes to about 6 hours to form a pre-catalyst.
1. A pre-catalyst composition comprising: a titanium-containing compound comprising a carboxylic acid selected from a group consisting of a-hydroxy isobutyric acid, 2,6-pyridine dicarboxylic acid, mandelic acid, and a combination thereof, a peroxide-containing compound; a chromium-containing compound, a silica support and a solvent, wherein: (i) a weight ratio of solvent to carboxylic acid is from about 1:1 to about 100:1; and (ii) an equivalent molar ratio of titanium-containing compound to carboxylic acid is from about 1:1 to about 1:4.
2. The pre-catalyst composition of claim 1 wherein the silica support comprises from about 0.1 wt. % to about 20 wt. % water.
3. The pre-catalyst composition of claim 2 wherein the silica support is characterized by a surface area of from about 100 m 2 /gram to about 1000 m 2 /gram and a pore volume of from about 1.0 cm 3 /gram to about 2.5 cm 3 /gram.
4. The pre-catalyst composition of claim 3 wherein the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.
5. The pre-catalyst composition of claim 3 wherein the titanium-containing compound comprises a titanium alkoxyhalide having a general formula Ti(OR K ) n Q 4-n wherein R K may be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or a combination thereof; wherein Q may be a fluoride, a chloride, a bromide, an iodide, or a combination thereof; and wherein n may be an integer from 1 to 4.
6. The pre-catalyst composition of claim 5 wherein the titanium-containing compound is present in an amount of from about 0.01 wt. % to about 10 wt. % based on the total weight of the pre-catalyst composition.
7. The pre-catalyst composition of claim 2 wherein the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.
8. The pre-catalyst composition of claim 1 wherein the silica support is characterized by a surface area of from about 100 m 2 /gram to about 1000 m 2 /gram and a pore volume of from about 1.0 cm 3 /gram to about 2.5 cm 3 /gram.
9. The pre-catalyst composition of claim 8 wherein the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.
10. The pre-catalyst composition of claim 1 wherein the peroxide-containing compound comprises hydrogen peroxide, di-tert-butyl peroxide, benzoyl peroxide, dicumyl peroxide, cumene hydroperoxide, tert-butyl hydroperoxide, phthaloyl peroxide or a combination thereof.
11. The pre-catalyst composition of claim 1 wherein the titanium-containing compound comprises compounds having a general formula TiO(OR K ) 2 , TiO(OR K ) 2 (acac) 2 , Ti(OR K ) 2 (oxal), a combination thereof wherein R K may be ethyl, isopropyl, n-propyl, isobutyl, n-butyl, or a combination thereof.
12. The pre-catalyst composition of claim 1 wherein titanium-containing compound comprises titanium(IV) ethoxide, titanium(IV) isopropoxide, titanium(IV) n-propoxide, titanium(IV) n-butoxide, titanium(IV) 2-ethylhexoxide, or a combination thereof.
13. The pre-catalyst composition of claim 1 wherein an equivalent molar ratio of the titanium-containing compound to the peroxide-containing compound ranges from about 1.0:0.5 to about 1:50.
14. The pre-catalyst composition of claim 1 wherein the solvent comprises aqueous solvent, an alcohol, an organic solvent, a hydrocarbon, or a combination thereof.
15. A pre-catalyst composition comprising: a titanium-containing compound comprising (i) a carboxylic acid selected from a group consisting of a-hydroxy isobutyric acid, 2,6-pyridine dicarboxylic acid, mandelic acid, and a combination thereof, hydrogen peroxide; a chromium-containing compound, a silica support and a solvent, wherein: (i) a weight ratio of solvent to carboxylic acid is from about 1:1 to about 100:1; (ii) an equivalent molar ratio of titanium-containing compound to carboxylic acid is from about 1:1 to about 1:4; and (iii) the titanium-containing compound is present in an amount of from about 0.01 wt. % to about 10 wt. % based on the total weight of the pre-catalyst composition.
16. The pre-catalyst composition of claim 15 wherein an equivalent molar ratio of the titanium-containing compound to the hydrogen peroxide ranges from about 1.0:0.5 to about 1:50.
17. The pre-catalyst composition of claim 15 wherein the solvent comprises deionized water, distilled water, filtered water, or a combination thereof.
18. The pre-catalyst composition of claim 15 wherein the solvent comprises methanol, ethanol, n-propanol, isopropanol, n-butanol, isobutanol, pentanol, hexanol, cyclohexanol, heptanol, octanol, benzyl alcohol, phenol, ethyl acetate, propyl acetate, butyl acetate, isobutyl isobutyrate, methyl lactate, ethyl lactate, acetone, ethyl methyl ketone, methyl isobutyl ketone, methylene chloride, chloroform, carbon tetrachloride, dichloroethane, trichloroethane, benzene, toluene, ethylbenzene, xylenes, chlorobenzene, dichlorobenzene, or a combination thereof.
19. The pre-catalyst composition of claim 15 wherein the silica support comprises from about 0.1 wt. % to about 20 wt. % water.
20. The pre-catalyst composition of claim 19 having a pH of less than about 5.5.