Amino acid chelates of titanium and use thereof in aqueous titanation of polymerization catalysts
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 titanium compound, a solvent, and an amino acid. The method further comprising drying the titanated silica support to form a pre-catalyst composition; contacting a chromium-containing compound with the silica support, the titanated silica support, the pre-catalyst composition, or combinations thereof; and calcining the pre-catalyst composition to form an olefin polymerization catalyst.
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 a presence of air in the 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 % based upon a total weight of the olefin polymerization catalyst;
wherein the titanium-containing solution comprises a titanium compound, a solvent, an amino acid, and a carboxylate;
wherein the titanium compound comprises a titanium (IV) compound;
wherein the silica support has an average particle size of from about 10 microns to about 500 microns;
wherein the amino acid comprises a threonine a serine, or combination thereof;
wherein the titanium-containing solution has a pH of from about 2.5 to about 5.5; and wherein the titanium-containing solution comprises a molar ratio of amino acid to the titanium compound in a range of 0.1 to 10.
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 a 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(IV) compound comprising an alkoxide group.
10. The method of claim 1 , wherein the titanium (IV) compound comprises Ti(OH) 4 , TiO(OH) 2 , TiO 2 , TiO(oxalate) 2 , or a combination thereof.
11. The method of claim 1 , wherein the titanium-containing solution further comprises a peroxide.
12. The method of claim 11 , 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.
13. The method of claim 1 , wherein the carboxylate comprises a multi carboxylate, an alpha-hydroxy carboxylate, or a combination thereof.
14. The method of claim 1 , wherein the carboxylate is provided by a carboxylic acid selected from the group consisting of acetic acid, formic acid, citric acid, gluconic acid, glycolic acid, glyoxylic acid, lactic acid, malic acid, malonic acid, oxalic acid, propionic acid, phosphonoacetic acid, tartaric acid, and combinations thereof.
15. The method of claim 1 wherein the silica support comprises from about 1 wt.% to about 20 wt.% water based on a total weight of the silica support.
16. The method of claim 2 , wherein the titanium (IV) compound comprises Ti(OH) 4 , TiO(OH) 2 , TiO 2 , TiO(oxalate) 2 , or a combination thereof.
17. The method of claim 2 , wherein the chromium is present in a range of from about 0.01 wt.% to about 10 wt.% based on a total weight of the polymerization catalyst.