Continuous catalyst activator

• US 8,790,579 B2
• Filed: 12/11/2012
• Issued: 07/29/2014
• Est. Priority Date: 12/20/2007
• Status: Active Grant

• Current Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Original Assignee: Chevron Phillips Chemical Company LP (Chevron Corp.)
• Inventors: Benham, Elizabeth A., McDaniel, Max P., Cymbaluk, Ted H., Newsome, Charles K., Nease, Charles R., Staffin, H. Kenneth, Parr, Thomas R.
• Primary Examiner(s): YOUNG, NATASHA E
• Application Number:
  US13/710,903
• Publication Number:
  US 20130109818A1
• Time in Patent Office: 595 Days
• Field of Search: 422108-111, 422/129, 422/131, 422/134, 422/138, 422/139, 422/141, 422/142, 422/146, 422/198, 422/211, 422/213, 422/219, 422/600, 422/630, 422/631, 422/634, 422/638, 422/644, 422/646, 422/649, 502/20, 502/100, 502102-104, 502/107, 526/59, 526/60, 526 64- 67, 526/72, 526 88- 90, 526/63, 700/90, 700/266, 700/268, 700/269
• US Class Current: 422/131
• CPC Class Codes: B01J 19/0033 Optimalisation processes, i.e. processes with adaptive control systems adaptive control systems per se G05B13/00
• CPC Class Codes: B01J 2208/0084 inside the bed, e.g. baffles
• CPC Class Codes: B01J 23/26 Chromium
• CPC Class Codes: B01J 23/92 of catalysts comprising metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/617 500-1000 m2/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/638 more than 1.0 ml/g
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/16 Reducing
• CPC Class Codes: B01J 38/10 using elemental hydrogen
• CPC Class Codes: B01J 38/30 in gaseous suspension, e.g. fluidised bed
• CPC Class Codes: B01J 8/006 by filtration
• CPC Class Codes: B01J 8/26 with two or more fluidised beds, e.g. reactor and regeneration installations
• CPC Class Codes: B01J 8/36 with fluidised bed through which there is an essentially horizontal flow of particles
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 2500/12 Melt flow index or melt flow ratio
• CPC Class Codes: C08F 4/24 : Oxides
• CPC Class Codes: Y02P 20/584 : Recycling of catalysts

Abstract

Methods and systems for preparing catalyst, such as chromium catalysts, are provided. The valence of at least a portion of the catalyst sent to an activator is changed from Cr(III) to Cr(VI). The catalyst is prepared or activated continuously using a fluidization bed catalyst activator.

Claims

1. A polymerization system comprising:

(a) a polymerization reactor,

(b) a continuous catalyst activator comprising;

a fluidized bed, wherein the continuous catalyst activator comprises;

(1) a substantially horizontal fluidized bed vessel;

(2) a gas distributor plate extending substantially horizontal within the fluidized bed vessel being arranged to allow passage of a fluidizing gas throughout the fluidized bed vessel;

(3) an inlet for introducing a catalyst into the fluidized bed vessel;

(4) at least one zone dividing wall for dividing the fluidized bed vessel into a plurality of zones, at least one of the zone dividing walls comprising a zone opening that allows the catalyst to be introduced into a next downstream zone, the plurality of zones being located substantially horizontal in relation to one another; and

(5) each zone comprising at least one baffle, each baffle defining a stage, each zone comprising a lower boundary that comprises at least a portion of the gas distributor plate, and

(c) a controller programmed with an algorithm to control a polymerization reactor process variable by adjusting a continuous catalyst activator process variable, and wherein at least one of the following conditions is satisfied;

the continuous catalyst activator further comprises a filter apparatus adapted to remove any catalyst particles entrained in the fluidizing gas; and

/or

the polymerization system further comprises an inlet titanation agent disperser.

2. The polymerization system of claim 1, wherein the continuous catalyst activator comprises sufficient baffles to cause an essentially plug flow profile through the fluidized bed vessel.

3. The polymerization system of claim 1, wherein the continuous catalyst activator comprises sufficient baffles to cause an essentially plug flow profile through the fluidized bed vessel.

4. The polymerization system of claim 1, wherein the continuous catalyst activator further comprises a reduction stage.

5. The polymerization system of claim 4, wherein the continuous catalyst activator further comprises a reoxidizing stage.

6. The polymerization system claim 1, wherein the continuous catalyst activator further comprises a cooling system wherein an oxidizing stage cools the catalyst with a first oxidizing ambient compound and a purge stage purges the catalyst with a first inert agent.

7. The polymerization system of claim 1, wherein the continuous catalyst activator further comprises a reduction stage.

8. The polymerization system of claim 7, wherein the continuous catalyst activator further comprises a reoxidizing stage.

9. The polymerization system of claim 1, further comprising a chamber dividing wall that enables more than one catalyst to be prepared simultaneously.

10. A method comprising;

(a) introducing a catalyst comprising chromium into a continuous catalyst activator;

(b) introducing a fluidizing gas into the continuous catalyst activator to yield a fluidized bed of the catalyst;

(c) heating the catalyst within the continuous catalyst activator while maintaining flow of the catalyst through the continuous catalyst activator such that the catalyst is maintained at a hold temperature for an average hold time;

(d) contacting the catalyst with at least one agent to convert at least a portion of the chromium from Cr(III) to Cr(VI) to produce a valence-converted catalyst;

(e) reducing at least a portion of the valence-converted catalyst from the Cr(VI) state to a Cr(II) state to produce a reduced valence-converted catalyst;

(f) discharging the valence-converted catalyst from the continuous catalyst activator, wherein discharging the valence-converted catalyst from the continuous catalyst activator comprises;

cooling the valence-converted catalyst in a presence of a first oxygenating agent in a separate cooling system downstream of the fluidized bed catalyst activator; and

purging the valence-converted catalyst in a presence of a first inert agent in the separate cooling system;

(g) introducing the valence-converted catalyst into a polymerization reactor system, or a combination of polymerization reactors;

(h) polymerizing a polyolefin product with the reduced valence-converted catalyst; and

(i) adjusting a process variable of the continuous catalyst activator based upon a comparison of a polymerization process variable associated with polymerizing the polyolefin product and a polymerization process variable set point.

11. The method of claim 10, wherein the valence-converted catalyst is reduced before the polymerizing.

12. The method of claim 11, wherein adjusting the process variable of the continuous catalyst activator comprises:

monitoring the polymerization process variable; and

comparing the polymerization process variable with the polymerization process variable set point.

13. The method of claim 11, wherein the hold temperature is from about 300°

C. to about 1000°

C. and the average hold time at the hold temperature is from about 1 minute to about 30 hours.

14. The method of claim 10, wherein the hold temperature is from about 300°

C. to about 1000°

C. and the average hold time at the hold temperature is from about 1 minute to about 30 hours.

15. The method of claim 10, further comprising titan titanating the catalyst prior to heating the catalyst.

16. The method of claim 10, further comprising, after reducing at least a portion of the valence-converted catalyst, reoxidizing at least a portion of the reduced valence-converted catalyst in the Cr(II) state to the Cr(VI) state.

17. The method of claim 10, further comprising discharging at least 2 different valence converted catalysts from the continuous catalyst activator.

18. The method of claim 10, wherein the continuous catalyst activator comprises;

(i) a gas distributor plate extending substantially horizontal within the fluidized bed vessel being arranged to allow passage of a fluidizing gas throughout the fluidized bed vessel;

(ii) an inlet, for introducing a catalyst into the fluidized bed vessel;

(iii) at least one zone dividing wall for dividing the fluidized bed vessel into a plurality of zones, at least one of the zone dividing walls comprising a zone opening that allows the catalyst to be introduced into a next downstream zone, the plurality of zones being located substantially horizontal in relation to one another; and

(iv) each zone comprising at least one baffle, each baffle defining a stage, each zone comprising a lower boundary that comprises at least a portion of the gas distributor plate.

19. The method of claim 18, wherein the continuous catalyst activator comprises sufficient baffles to cause an essentially plug flow profile through the fluidized bed vessel.

20. The method of claim 18, wherein the hold temperature is from about 300°

C. to about 1000°

C. and the average hold time at the hold temperature is from about 1 minute to about 30 hours.