Methods of preparing a catalyst

1. A method of preparing a catalyst support comprising:

contacting an acid-soluble titanium-containing compound with an acid to form a first mixture;

contacting the first mixture with an alkali metal silicate to form a hydrogel which has a silica content of from about 18 wt. % to about 35 wt. % based on the total weight of the hydrogel;

contacting the hydrogel with an alkaline solution to form an aged hydrogel;

washing the aged hydrogel to form a washed hydrogel; and

drying the washed hydrogel to produce a titanium-containing-silica support wherein the support has a pore volume equal to or greater than about 1.4 cm 3 /g.

2. A method of preparing a catalyst comprising:

contacting an acid-soluble titanium-containing compound with an acid to form a first mixture;

contacting the first mixture with an alkali metal silicate to form a hydrogel which has a silica content of from about 18 wt. % to about 35 wt. % based on the total weight of the hydrogel;

contacting the hydrogel with an alkaline solution to form an aged hydrogel;

washing the aged hydrogel to form a washed hydrogel; and

drying the washed hydrogel to produce a titanium-containing-silica support;

wherein a chromium compound is included in the method to form a chrominated-titanium-containing silica, either through cogelation of the hydrogel in the presence of a chromium-containing compound or contacting the titanium-containing-support with a chromium-containing compound and wherein the support has a pore volume equal to or greater than about 1.4 cm 3 /g.

3. A method of preparing a catalyst comprising:

contacting an acid-soluble titanium-containing compound with an acid to form a first mixture;

contacting the first mixture with an alkali metal silicate to form a hydrogel which has a silica content of from about 18 wt. % to about 35 wt. % based on the total weight of the hydrogel;

contacting the hydrogel with an alkaline solution to form an aged hydrogel;

washing the aged hydrogel to form a washed hydrogel;

drying the washed hydrogel to produce a titanium-containing-silica support; and

impregnating the titanium-containing-support with a chromium-containing compound to form a chrominated-titanium-containing silica wherein the support has a pore volume equal to or greater than about 1.4 cm 3 /g.

4. A method of preparing a catalyst comprising:

contacting an acid-soluble titanium-containing compound with an acid to form a first mixture;

contacting the first mixture with an alkali metal silicate to form a hydrogel which has a silica content of from about 18 wt. % to about 35 wt. % based on the total weight of the hydrogel;

contacting the hydrogel with an alkaline solution to form an aged hydrogel;

washing the aged hydrogel to form a washed hydrogel; and

spray drying the washed hydrogel in the presence of a chromium-containing compound to produce a chrominated-titanium-containing silica wherein the support has a pore volume equal to or greater than about 1.4 cm 3 /g.

5. A method of preparing a catalyst comprising:

contacting an acid-soluble titanium-containing compound and a chromium-containing compound with an acid to form a first mixture;

contacting the first mixture with an alkali metal silicate to form a hydrogel which has a silica content of from about 18 wt. % to about 35 wt. % based on the total weight of the hydrogel;

contacting the hydrogel with an alkaline solution to form an aged hydrogel;

washing the aged hydrogel to form a washed hydrogel; and

drying the washed hydrogel to form a chrominated-titanium-containing silica wherein the support has a pore volume equal to or greater than about 1.4 cm 3 /g.

6. The method according to claim 1 wherein the contacting the first mixture with an alkali metal silicate to form a hydrogel is continuous.

7. The method according to claim 1 wherein the contacting the first mixture with an alkali metal silicate to form a hydrogel occurs at a pH of less than about 4.

8. The method according to claim 2 further comprising calcination of the chrominated-titanium-containing silica at a temperature of from about 400° C. to about 1,000° C. to form a polymerization catalyst.

9. The method of claim 8 wherein the polymerization catalyst has a surface area of from about 400 m 2 /g to about 1000 m 2 /g.

10. The method of claim 8 wherein the polymerization catalyst has pore volume equal to or greater than about 1.7 cm 3 /g.

11. The method of claim 1 wherein the acid-soluble titanium-containing compound comprises trivalent titanium, tetravalent titanium, titanic, or combinations thereof.

12. The method of claim 11 wherein the tetravalent titanium comprises TiCl 4 , TiOSO 4 , TiBr 4 , TiOCl 2 , TiOBr 2 , TiO 2 , TiO(oxylate) 2 , or combinations thereof.

13. The method of claim 11 wherein the trivalent titanium comprises Ti(SO 4 ) 3 , Ti(OAc) 3 , Ti(oxylate) 3 , Ti(NO 3 ) 3 , or combinations thereof.

14. The method of claim 2 wherein the chromium-containing compound comprises chromium trioxide, chromium acetate, chromium nitrate, chromium sulfate, tertiary butyl chromate, a diarene chromium (0) compound, biscyclopentadienyl chromium(II), chromium (III) acetylacetonate, or combinations thereof.

15. The method of claim 8 wherein the chromium is present in an amount of from about 0.01 wt. % to about 10 wt. % based on the total weight of the polymerization catalyst.

16. The method of claim 8 wherein the titanium is present in an amount of from 0.1 wt. % to about 10 wt. % based on the total weight of the polymerization catalyst.

17. The method of claim 1 wherein the alkali metal silicate comprises sodium silicate.

18. The method of claim 1 wherein the acid comprises a mineral acid.

19. The method of claim 1 wherein the alkaline solution comprises sodium hydroxide, ammonium hydroxide, sodium metasilicate, tetra-alkyl ammonium hydroxide, potassium hydroxide or combinations thereof.

20. The method of claim 1 wherein contacting with an alkaline solution occurs for a time period of from about 1 hour to about 24 hours.

21. The method of claim 1 wherein the washed hydrogel has an alkali metal present in an amount of less of than about 0.5 wt. % based on the total weight of washed hydrogel.

22. The method of claim 1 wherein the washed hydrogel is dried by spray drying, flash drying, or oven drying.

23. The method of claim 1 wherein an emission of a highly-reactive volatile organic compound during calcination is an amount of from about 0 wt. % to about 0.5 wt. % based on the weight of the silica.

24. The method of claim 1 wherein post-drying the support comprises less than about 0.3 wt. % carbon.

25. The method of claim 8 wherein the exotherm during calcination of the catalyst is less than about 100° C.

26. The method according to claim 1 wherein the contacting the first mixture with an alkali metal silicate to form a hydrogel occurs at a pH of less than about 4 and further comprising calcination of the chrominated-titanium-containing silica at a temperature of from about 400° C. to about 1,000° C. to form a polymerization catalyst, where the pore volume of the catalyst ranges from about 1.0 cm 3 /g to about 2.5 cm 3 /g.

27. The method according to claim 1 wherein the contacting the first mixture with an alkali metal silicate to form a hydrogel occurs at a pH of less than about 4 and further comprising calcination of the chrominated-titanium-containing silica at a temperature of from about 400° C. to about 1,000° C. to form a polymerization catalyst, where the activity of the catalyst as measured for ethylene polymerization in grams of polyethylene produced per gram catalyst per hour (g PE/g/h) is greater than about 3500.