Methods of preparing a catalyst

Patent metadata

Field	Value
Publication number	US-11976142-B2
Application number	US-202217579777-A
Country	US
Kind code	B2
Filing date	Jan 20, 2022
Priority date	Dec 29, 2016
Publication date	May 7, 2024
Grant date	May 7, 2024

Abstract

A hydrogel comprising water, and a plurality of titanium-silica-chromium nanoparticle agglomerates, wherein each titanium-silica-chromium nanoparticle agglomerate is an agglomeration of titanium-silica-chromium nanoparticles, the agglomerates having an average titanium penetration depth designated x with a coefficient of variation for the average titanium penetration depth of less than about 1.0 wherein a silica content of the hydrogel is of from about 10 wt. % to about 35 wt. % based on a total weight of the hydrogel.

First claim

What is claimed is:

1. A polymerization catalyst prepared by
(a) forming a hydrogel comprising (i) water and (ii) an agglomeration of titanium-silica-chromium nanoparticle, wherein each titanium-silica-chromium nanoparticle agglomerate is an agglomeration of titanium-silica-chromium nanoparticles, the agglomerates having an average titanium penetration depth designated x with a coefficient of variation for the average titanium penetration depth of less than about 1.0 wherein a silica content of the hydrogel is of from about 18 wt. % to about 35 wt. % based on a total weight of the hydrogel; wherein the titanium content is from about 0.15 wt. % to about 1.5 wt. % based on the total weight of the hydrogel; wherein the chromium content is from about 0.15 wt. % to about 1.2 wt. % based on the total weight of the hydrogel and wherein the pH of the solution at gelation is from about 2 to about 5;
(b) alkaline aging the hydrogel to form an aged hydrogel;
(c) washing the aged hydrogel to form a washed hydrogel;
(d) spray-drying the washed hydrogel to form a precatalyst; and
(e) calcining the precatalyst to form the polymerization catalyst having a pore volume of equal to or greater than about 1.67 mL/g.

2. The polymerization catalyst of claim 1 having a ratio of titanium X-ray photoelectron spectroscopy 2P signal to silicon X-ray photoelectron spectroscopy 2P signal of equal to or less than about 0.04.

3. The polymerization catalyst of claim 1 having a ratio of titanium X-ray photoelectron spectroscopy 2P signal to silicon X-ray photoelectron spectroscopy 2P signal of equal to or less than about 0.025.

4. The polymerization catalyst of claim 1 having a pore volume that is increased by equal to or greater than about 44% when compared to a polymerization catalyst prepared from a hydrogel having less than about 18 wt. % to about 35 wt. % silica content based on a total weight of the hydrogel.

5. The polymerization catalyst of claim 1 having less than about 1 wt. % highly reactive volatile organic compounds emitted during catalyst preparation based on the total weight of the silica.

6. The polymerization catalyst of claim 1 having titanium present in greater than about 80% of the catalyst particle.

7. The polymerization catalyst of claim 1 having a macroparticle size distribution of from about 0.1 μm to about 400 μm.

8. The polymerization catalyst of claim 1 having a S s :S 1 ratio of from about 0.8 to about 1.2.

9. The polymerization catalyst of claim 1 having a Ti o /Ti c ratio of about 1.

10. The polymerization catalyst of claim 1 wherein the catalyst is sieved to provide i) a polymerization catalyst group A comprising a smallest 10% of catalyst particles and ii) a polymerization catalyst group B comprising a largest 10% of catalyst particles.

11. A polymerization catalyst prepared by
(a) forming a hydrogel comprising (i) water and (ii) an agglomeration of titanium-silica-chromium nanoparticle, wherein each titanium-silica-chromium nanoparticle agglomerate is an agglomeration of titanium-silica-chromium nanoparticles, the agglomerates having an average titanium penetration depth designated x with a coefficient of variation for the average titanium penetration depth of less than about 1.0 wherein a silica content of the hydrogel is of from about 18 wt. % to about 35 wt. % based on a total weight of the hydrogel; wherein the titanium content is from about 0.15 wt. % to about 1.5 wt. % based on the total weight of the hydrogel; wherein the chromium content is from about 0.15 wt. % to about 1.2 wt. % based on the total weight of the hydrogel and wherein the pH of the solution at gelation is from about 2 to about 5;
(b) alkaline aging the hydrogel to form an aged hydrogel;
(c) washing the aged hydrogel to form a washed hydrogel;
(d) vacuum oven-drying the washed hydrogel to form a precatalyst; and
(e) calcining the precatalyst to form the polymerization catalyst having a pore volume of equal to or greater than about 1.33 mL/g.

12. The polymerization catalyst of claim 11 having less than about 1 wt. % highly reactive volatile organic compounds emitted during catalyst preparation based on the total weight of the silica.

13. The polymerization catalyst of claim 11 having titanium present in greater than about 80% of the catalyst particle.

14. The polymerization catalyst of claim 11 wherein calcining the precatalyst is carried out in a temperature range of from about 400° C. to about 1000° C.

15. The polymerization catalyst of claim 11 having a macroparticle size distribution of from about 0.1 μm to about 400 μm.

16. The polymerization catalyst of claim 11 having a S s :S 1 ratio of from about 0.8 to about 1.2.

17. The polymerization catalyst of claim 11 having a S s :S 1 ratio of about 1.

18. The polymerization catalyst of claim 11 having a Ti o /Ti c ratio of about 1.

19. The polymerization catalyst of claim 11 having a ratio of titanium X-ray photoelectron spectroscopy 2P signal to silicon X-ray photoelectron spectroscopy 2P signal of equal to or less than about 0.04.

20. The polymerization catalyst of claim 11 having a ratio of titanium X-ray photoelectron spectroscopy 2P signal to silicon X-ray photoelectron spectroscopy 2P signal of equal to or less than about 0.025.

21. The polymerization catalyst of claim 11 wherein the catalyst is sieved to provide i) a polymerization catalyst group A comprising a smallest 10% of catalyst particles and ii) a polymerization catalyst group B comprising a largest 10% of catalyst particles.

22. The polymerization catalyst of claim 11 having a pore volume that is increased by equal to or greater than about 35% when compared to a polymerization catalyst prepared from a hydrogel having less than about 18 wt. % to about 35 wt. % silica content based on a total weight of the hydrogel.

23. A polymerization catalyst prepared by
(a) forming a hydrogel comprising (i) water and (ii) an agglomeration of titanium-silica-chromium nanoparticle, wherein each titanium-silica-chromium nanoparticle agglomerate is an agglomeration of titanium-silica-chromium nanoparticles, the agglomerates having an average titanium penetration depth designated x with a coefficient of variation for the average titanium penetration depth of less than about 1.0 wherein a silica content of the hydrogel is from about 18 wt. % to about 35 wt. % based on a total weight of the hydrogel; wherein the titanium content is from about 0.15 wt. % to about 1.5 wt. % based on the total weight of the hydrogel; wherein the chromium content is from about 0.15 wt. % to about 1.2 wt. % based on the total weight of the hydrogel and wherein the pH of the solution at gelation is from about 2 to about 5;
(b) alkaline aging the hydrogel to form an aged hydrogel;
(c) washing the aged hydrogel to form a washed hydrogel;
(d) drying the washed hydrogel by azeotropic distillation to form a precatalyst; and
(e) calcining the precatalyst to form the polymerization catalyst having a pore volume of equal to or greater than about 2.87 mL/g.

24. The polymerization catalyst of claim 23 having a pore volume that is increased by equal to or greater than about 11% when compared to a polymerization catalyst prepared from a hydrogel having less than about 18 wt. % to about 35 wt. % silica content based on a total weight of the hydrogel.

25. The polymerization catalyst of claim 23 having less than about 1 wt. % highly reactive volatile organ

Assignees

• Chevron Phillips Chemical Co Lp

Inventors

• Mcdaniel Max P
• Schwerdtfeger Eric D
• Praetorius Jeremy M

Classifications

• C08F110/02 Primary

  Ethene · CPC title

• C08F4/18

  Oxides · CPC title

• C08F4/24

  Oxides · CPC title