Surfactant as titanation ligand
A pre-catalyst composition comprising: a) a silica support comprising silica wherein an amount of silica is in a range of from about 70 wt. % to about 95 wt. % based upon a total weight of the silica support; b) a titanium-containing compound wherein an amount of titanium is in a range of from about 0.1 wt. % to about 10 wt. % based upon the total weight of the silica support; c) a chromium-containing compound wherein an amount of chromium is in a range of from about 0.1 wt. % to about 10 wt. % based upon the total weight of the silica support; d) a surfactant wherein the surfactant comprises a non-ionic surfactant, a cationic surfactant, or a combination thereof, e) a carboxylate wherein the carboxylate comprises a multi carboxylate, an alpha-hydroxy carboxylate, or a combination thereof, and f) a solvent.
1. 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 a surfactant, wherein the titanium-containing solution has a pH of less than about 5.5, wherein the surfactant comprises a water-insoluble component and a water-soluble component, and wherein the titanium-containing solution comprises from about 30 wt. % of the surfactant, based on a weight of the silica support.
2. The method of claim 1 wherein the silica support is selected from the group consisting of a silica xerogel, a silica hydrogel, solid silica, solid silica-alumina, and a combination thereof.
3. The method of claim 1 wherein the silica support has a surface area in a range of from about 100 m 2 /gram to about 1000 m 2 /gram.
4. The method of claim 1 wherein the silica support has a pore volume in a range of from about 1.0 cm 3 /gram to about 2.5 cm 3 /gram.
5. The method of claim 1 wherein the silica support has an average particle size in a range of from about 10 microns to about 500 microns.
6. The method of claim 1 wherein the titanium compound is a titanium (IV) compound.
7. The method of claim 1 wherein the titanium compound comprises compounds that have the general formula Ti(OR) 4 , TiO(OR) 2 , Ti(OR) 2 (acac) 2 , Ti(OR) 2 (oxal), or a combination thereof, wherein each R is independently ethyl, isopropyl, n-propyl, isobutyl, or n-butyl; “acac” is acetylacetonate; and “oxal” is oxalate.
8. The method of claim 1 wherein the titanium compound comprises a titanium (IV) alkoxide.
9. The method of claim 8 wherein the titanium (IV) alkoxide comprises titanium (IV) ethoxide, titanium (IV) isopropoxide, titanium (IV) n-propoxide, titanium (IV) n-butoxide, titanium (IV) 2-ethylhexoxide, or a combination thereof.
10. The method of claim 1 wherein the titanium compound comprises hydrous titania, titanium hydroxide, titanium dioxide, titanic acid, titanyl sulfate, titanium acetylacetonate, titanium oxyacetylacetonate, or a combination thereof.
11. The method of claim 1 wherein the titanium compound comprises titanium tetrachloride, titanium tetrabromide, titanium (IV) oxychloride, titanium (IV) oxybromide or a combination thereof.
12. The method of claim 1 wherein the titanium compound comprises a titanium alkoxyhalide having the general formula Ti(OR) n Q 4-n ; wherein each R independently is ethyl, isopropyl, n-propyl, isobutyl, or n-butyl; 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.
13. The method of claim 1 wherein the surfactant comprises a non-ionic surfactant, a cationic surfactant, an anionic surfactant, or a combination thereof.
14. The method of claim 13 wherein the nonionic surfactant comprises polyalkoxylates, polyethoxylates, glucosides, a polyethoxylated alcohol, a polyethoxylated mercaptan, or a combination thereof.
15. The method of claim 1 wherein the surfactant comprises alkyl sulfates, aryl sulfates, alkylaryl sulfates, alkyl sulfonates, aryl sulfonates, alkylaryl sulfonates, phosphates of alkali metals, ammonium salts of phosphates, alkylsulfonic acids, sulfosuccinate salts, fatty acid salts, ethoxylated alcohols, amphiphilic copolymers or a combination thereof.
16. The method of claim 1 further comprising contacting a chromium-containing compound with the silica support, the titanated silica support, or a combination thereof.
17. The method of claim 16 wherein the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, chromium sulfate, tertiary butyl chromate, biscyclopentadienyl chromium (II), chromium (III) acetylacetonate, or a combination thereof.
18. The method of claim 1 wherein the solvent is selected from the group consisting of water, alcohol, and a combination thereof.
19. 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 having the general formula Ti(OR) 4 , TiO(OR) 2 , Ti(OR) 2 (acac) 2 , Ti(OR) 2 (oxal), or a combination thereof, wherein each R is independently ethyl, isopropyl, n-propyl, isobutyl, or n-butyl; “acac” is acetylacetonate; and “oxal” is oxalate, a solvent, and a surfactant, wherein the titanium-containing solution has a pH of less than about 5.5, wherein the surfactant comprises a water-insoluble component and a water-soluble component, and wherein the titanium-containing solution comprises from about 10 wt. % to about 30 wt. % of the surfactant, based on a weight of the silica support.
20. The method of claim 19 further comprising contacting a chromium-containing compound with the silica support, the titanated silica support, or combinations thereof wherein the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, or a combination thereof.
21. The method of claim 20 wherein the surfactant comprises polyalkoxylates, polyethoxylates, glucosides, a polyethoxylated alcohol, a polyethoxylated mercaptan, or a combination thereof.