Aqueous titanation of Cr/silica catalysts by the use of acetylacetonate and another ligand
A method comprising contacting a silica support with a titanium-containing solution to form a titanated silica support, wherein the titanium-containing solution comprises a solvent; a ligand comprising a glycol, a carboxylate, a peroxide, or a combination thereof; and a titanium compound having the formula Ti(acac) 2 (OR) 2 , wherein “acac” is acetylacetonate and wherein each R independently is ethyl, isopropyl, n-propyl, isobutyl, or n-butyl.
1. A method for making an olefin polymerization catalyst comprising
(a) contacting a silica support with a titanium-containing solution to form a titanated silica support;
(b) drying the titanated silica support by heating the titanated silica support to a temperature in a range of from about 50° C. to about 200° C. and maintaining the temperature of the titanated silica support in the range of from about 50° C. to about 200° C. for a time period of from about 30 minutes to about 6 hours to form a pre-catalyst composition; and
(c) calcining the pre-catalyst composition to a temperature in a range of from 400° C. to about 1000° C. and maintaining the temperature of the pre-catalyst composition in the presence of air in a range of from 400° C. to about 1000° C. for a time period of from about 1 minute to about 24 hours to produce the olefin polymerization catalyst having titanium present in an amount from about 0.01 wt. % to about 10 wt. %;
wherein the titanium-containing solution comprises a solvent, a ligand and a titanium compound having the formula Ti(acac)2(OR)2, wherein “acac” is acetylacetonate and wherein each R independently is ethyl, isopropyl, n-propyl, isobutyl, or n-butyl;
wherein the ligand comprises a glycol, a carboxylate, a peroxide, or a combination thereof; and
wherein the titanium-containing solution has a pH of from about 2.5 to about 5.5.
2. The method of claim 1 , further comprising contacting a chromium-containing compound with the silica support, the titanated silica support, the pre-catalyst composition, or combinations thereof.
3. The method of claim 1 , wherein the silica support comprises chromium.
4. The method of claim 1 , wherein the silica support is simultaneously contacted with the titanium-containing solution and a chromium-containing compound.
5. The method of claim 4 , wherein the titanium-containing solution further comprises the chromium-containing compound.
6. The method of claim 2 , wherein the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, chromium sulfate, tertiary butyl chromate, biscyclopentadienyl chromium(II), chromium(III) acetylacetonate, or combinations thereof.
7. The method of claim 1 , wherein the solvent is selected from the group consisting of water, alcohol, and combinations thereof.
8. The method of claim 1 , wherein the solvent is an aqueous solvent.
9. The method of claim 1 , wherein the titanium compound is formed by contact of acetylacetone and a titanium precursor having the formula Ti(OR) 4 , wherein each R independently is ethyl, isopropyl, n-propyl, isobutyl, or n-butyl; and wherein the ligand comprises a carboxylate.
10. The method of claim 1 , wherein the titanium compound comprises titanium (IV) bis-acetylacetonate diisopropoxide.
11. The method of claim 1 , wherein an equivalent molar ratio of the ligand to the titanium compound is greater than or equal to one.
12. The method of claim 1 , wherein the glycol comprises ethylene glycol, glycerol, diethylene glycol, a sugar, a diol, or a combination thereof.
13. The method of claim 1 , wherein the carboxylate is a mono-carboxylate which comprises formic acid, acetic acid, propanoic acid, glyoxylic acid, or a combination thereof.
14. The method of claim 1 , wherein the peroxide comprises hydrogen peroxide, dicumyl peroxide, benzoyl peroxide, t-butyl hydroperoxide, di-t-butyl peroxide, a peroxyacid, a per-carboxylic acid, a perester, or a combination thereof.
15. The method of claim 1 , wherein the carboxylate comprises a multi-carboxylate, an alpha-hydroxy carboxylate, or a combination thereof, and wherein an equivalent molar ratio of the carboxylate to the titanium compound is less than or equal to one.
16. The method of claim 15 , wherein the multi-carboxylate comprises oxalic acid, citric acid, malic acid, gluconic acid, tartaric acid, or a combination thereof.
17. The method of claim 15 , wherein the alpha-hydroxy carboxylate comprises glycolic acid, lactic acid, 2-hydroxy isobutyric acid, mandelic acid or a combination thereof.
18. The method of claim 1 , wherein the silica support has 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.