Continuous catalyst activator

• US 8,114,353 B2
• Filed: 12/20/2007
• Issued: 02/14/2012
• 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): Griffin, Walter D
• Assistant Examiner(s): YOUNG, NATASHA E
• Application Number:
  US12/004,217
• Publication Number:
  US 20090164046A1
• Time in Patent Office: 1,517 Days
• Field of Search: 422/129, 422/131, 422/141, 422/146, 422/134, 422/138, 422/139, 422/142, 502/28, 502/38, 502/85, 502/104, 502/107, 700/266
• 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) continuous catalyst activator comprising a substantially horizontal fluidized bed vessel, and wherein the continuous catalyst activator further 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;

(c) a controller programmed with an algorithm to control a polymerization reactor process variable by adjusting a continuous catalyst activator process variable; and

further comprising at least one of;

(d1) a filter apparatus adapted to remove catalyst particles entrained in the fluidizing gas;

or

(d2) 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.

2. The polymerization system of claim 1, comprising sufficient baffles to cause an essentially plug flow profile through the fluidized bed vessel.

3. The polymerization system of claim 1, further comprising a reduction stage.

4. The polymerization system of claim 3, further comprising a reoxidizing stage.

5. The polymerization system of claim 1, further comprising an inlet titanation agent disperser.

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

7. The polymerization system of claim 1, further comprising a catalyst comprising chromium flowing through the continuous catalyst activator, wherein the catalyst is maintained at a hold temperature for an average hold time.

8. The polymerization system of claim 7, wherein the hold temperature is from about 300°

C. to about 1000°

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

9. The polymerization system of claim 7, further comprising at least one agent contacted with the catalyst within the fluidized bed vessel to convert at least a portion of the chromium from Cr(III) to Cr(VI) to produce a valence-converted catalyst.

10. The polymerization system of claim 9, further comprising a cooling system downstream from the fluidized bed vessel.

11. The polymerization system of claim 10, further comprising:

a first oxygenating agent contacted with the valence-converted catalyst in the cooling system, wherein the valent-converted catalyst is cooled in the presence of the first oxygenating agent; and

a first inert agent introduced into the cooling system to purge the valence-converted catalyst.

12. The polymerization system of claim 1, wherein the controller is configured to:

(a) monitor the polymerization reactor process variable;

(b) compare the polymerization reactor process variable with a reactor process variable set point; and

(c) adjust the continuous catalyst activator process variable based upon a comparison of the polymerization reactor process variable and the reactor process variable set point.

13. The polymerization system of claim 12, wherein the continuous catalyst activator process variable comprises a catalyst feedrate, a zone temperature, a catalyst residence time, an average catalyst hold time at a hold temperature, a fluidization gas flow rate, a fluidization bed height, or combinations thereof.

14. The polymerization system of claim 12, wherein the algorithm comprises a neural network, a partial least squares, a principle, a component regression, a first principles models, or combinations thereof to infer impending changes in a stream discharged from the continuous catalyst activator.

15. A polymerization system comprising:

(a) a polymerization reactor,

(b) continuous catalyst activator comprising a substantially horizontal fluidized bed vessel, and wherein the continuous catalyst activator further 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;

(c) a controller programmed with an algorithm to control a polymerization reactor process variable by adjusting a continuous catalyst activator process variable; and

(d) a reduction stage.

16. A polymerization system comprising:

(a) a polymerization reactor;

(b) continuous catalyst activator comprising a substantially horizontal fluidized bed vessel, and wherein the continuous catalyst activator further 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;

(c) a controller programmed with an algorithm to control a polymerization reactor process variable by adjusting a continuous catalyst activator process variable; and

(d) an inlet titanation agent disperser.

17. A polymerization system comprising:

(a) a polymerization reactor;

(b) continuous catalyst activator comprising a substantially horizontal fluidized bed vessel, and wherein the continuous catalyst activator further 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;

(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; and

(v) a chamber dividing wall that enables more than one catalyst to be prepared simultaneously; and

(c) a controller programmed with an algorithm to control a polymerization reactor process variable by adjusting a continuous catalyst activator process variable.

18. A polymerization system comprising:

(a) a polymerization reactor;

(b) continuous catalyst activator comprising a substantially horizontal fluidized bed vessel, and wherein the continuous catalyst activator further 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;

(c) a controller programmed with an algorithm to control a polymerization reactor process variable by adjusting a continuous catalyst activator process variable;

(d) a catalyst comprising chromium flowing through the continuous catalyst activator, wherein the catalyst is maintained at a hold temperature for an average hold time;

(e) at least one agent contacted with the catalyst within the fluidized bed vessel to convert at least a portion of the chromium from Cr(III) to Cr(VI) to produce a valence-converted catalyst; and

(f) a cooling system downstream from the fluidized bed vessel.

19. A polymerization system comprising:

(a) a polymerization reactor;

(b) continuous catalyst activator comprising a substantially horizontal fluidized bed vessel, and

(c) a controller programmed with an algorithm to control a polymerization reactor process variable by adjusting a continuous catalyst activator process variable, wherein the controller is configured to;

(i) monitor the polymerization reactor process variable;

(ii) compare the polymerization reactor process variable with a reactor process variable set point; and

(iii) adjust the continuous catalyst activator process variable based upon a comparison of the polymerization reactor process variable and the reactor process variable set point, wherein the algorithm comprises a neural network, a partial least squares, a principle, a component regression, a first principles models, or combinations thereof to infer impending changes in a stream discharged from the continuous catalyst activator.