Granted Patent B2

US 12,515,202 · App. 18/242,799 · Granted Jan 6, 2026

Inventors: Jeremy M. Praetorius (Bartlesville, OK); Eric D. Schwerdtfeger (Bartlesville, OK); Max P. McDaniel (Bartlesville, OK); Ted H. Cymbaluk (Seabrook, TX); Connor D. Boxell (Tulsa, OK); Alan L. Solenberger (Bartlesville, OK); Kathy S. Clear (Bartlesville, OK)

Assignee: Chevron Phillips Chemical Company LP

B01J23/26B01J21/08B01J35/615B01J35/617B01J35/638B01J37/0203B01J37/0236B01J37/08C08F10/02C08F110/02

Abstract

Claims (29)

1 . A method comprising:

a) drying a silica support at a temperature in a range of from about 150° C. to about 220° C. to form a dried support;

b) contacting the dried support with a chromium-containing compound to form a chrominated support;

c) contacting the chrominated support with a solvent to form a slurried support;

d) cooling the slurried support to a temperature of less than about 60° C. to form a cooled support;

e) contacting the cooled support with a titanium-containing compound to form a titanated support;

f) thermally treating the titanated support by increasing a temperature of the titanated support to a boiling point of the solvent;

g) prior to removing all of the solvent, contacting the titanated support with water in an amount ranging from about 0.1 moles to about 10 moles per mole of titanium to produce a mixture;

h) thermally treating the mixture by heating the mixture to a temperature of about 150° C. for a time period of from about 5 hours to about 30 hours to form a precatalyst; and

i) calcining the precatalyst at a temperature in a range of from about 400° C. to about 1000° C. for a time period of from about 30 minutes to about 24 hours to form a polymerization catalyst.

2 . The method of claim 1 wherein the solvent comprises methanol having less than about 0.1 wt. % water.

3 . The method of claim 2 wherein the titanium-containing compound comprises titanium n-propoxide.

4 . The method of claim 3 wherein the chromium-containing compound comprises basic chromium acetate.

5 . The method of claim 4 wherein the slurried support is cooled to a temperature of less than about 50° C. to form the cooled support.

6 . The method of claim 4 wherein the slurried support is cooled to a temperature of less than about 40° C. to form the cooled support.

7 . The method of claim 6 wherein step (e) is performed under vigorous mixing conditions suitable to provide for efficient dispersal of the titanium-containing compound.

8 . The method of claim 7 wherein the solvent is present in an amount ranging from about 2 times to about 3 times weight of the dried support.

9 . The method of claim 8 wherein the silica support is dried in an inert atmosphere.

10 . The method of claim 2 wherein the solvent is present in an amount ranging from about 2 times to about 3 times weight of the dried support.

11 . The method of claim 10 wherein the silica support is dried for a time period ranging from about 5 hours to about 24 hours.

12 . The method of claim 1 wherein the titanium-containing compound comprises titanium n-propoxide.

13 . The method of claim 1 wherein the chromium-containing compound comprises basic chromium acetate.

14 . The method of claim 1 wherein step (e) is performed under vigorous mixing conditions suitable to provide for efficient dispersal of the titanium-containing compound.

15 . The method of claim 1 wherein step (c) is repeated from about 2 to about 10 times.

16 . The method of claim 1 wherein the silica support contains greater than about 50% silica and the silica support is characterized by a surface area of from about 250 m 2 /g to about 1000 m 2 /g and a pore volume of from about 1.0 cm 3 /gram to about 2.5 cm 3 /gram.

17 . The method of claim 1 wherein calcining the precatalyst is in air, oxygen, inert gases, carbon monoxide or a combination thereof.

18 . The method of claim 1 wherein the amount of water added in step g) is from about 2 moles to about 5 moles per mole of titanium.

19 . The method of claim 1 wherein an amount of volatile organic compounds (VOC) emitted during the calcining is reduced by from about 50% to about 100% when compared to the amount of VOC emitted during calcining of a similar precatalyst prepared without the addition of water to the titanated slurried support.

20 . The method of claim 1 wherein an amount of volatile organic compounds (VOC) emitted during calcining is less than about 2 wt. %.

Assignments (1)

Continuity (4)

References Cited (182)