Continuous preparation of calcined chemically-treated solid oxides

• US 9,289,739 B2
• Filed: 06/23/2009
• Issued: 03/22/2016
• Est. Priority Date: 06/23/2009
• 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.
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): Forrest, Michael
• Application Number:
  US12/489,613
• Publication Number:
  US 20100322836A1
• Time in Patent Office: 2,464 Days
• Field of Search: None
• US Class Current: 1/1
• CPC Class Codes: B01J 2208/00176 outside the reactor
• CPC Class Codes: B01J 2208/0053 Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
• CPC Class Codes: B01J 2208/00548 Flow
• CPC Class Codes: B01J 2208/0084 inside the bed, e.g. baffles
• CPC Class Codes: B01J 2208/00938 Flow distribution elements
• CPC Class Codes: B01J 2219/182 horizontal
• CPC Class Codes: B01J 2531/48 Zirconium
• CPC Class Codes: B01J 31/143 of aluminium
• CPC Class Codes: B01J 31/2295 Cyclic compounds, e.g. cyclopentadienyls
• CPC Class Codes: B01J 6/004 using hot gas streams in which the material is moved
• CPC Class Codes: B01J 8/1827 the fluidising gas being a reactant
• CPC Class Codes: B01J 8/1836 Heating and cooling the reactor B01J8/42 takes precedence
• CPC Class Codes: B01J 8/34 with stationary packing material in the fluidised bed, e.g. bricks, wire rings, baffles
• CPC Class Codes: B01J 8/36 with fluidised bed through which there is an essentially horizontal flow of particles

Abstract

The present invention discloses a continuous calcination vessel which can be used to prepare calcined chemically-treated solid oxides from solid oxides and chemically-treated solid oxides. A process for the continuous preparation of calcined chemically-treated solid oxides is also provided. Calcined chemically-treated solid oxides disclosed herein can be used in catalyst compositions for the polymerization of olefins.

Claims

1. A process for continuously preparing a calcined chemically-treated solid oxide comprising:

(a) (i) introducing a solid oxide into a continuous calcination vessel comprising a fluidized bed; and

contacting the solid oxide with a compound and a first agent at a calcination temperature for an average residence time to produce the calcined chemically-treated solid oxide;

or

 

(ii) introducing a chemically-treated solid oxide into a continuous calcination vessel comprising a fluidized bed; and

contacting the chemically-treated solid oxide with a first agent at a calcination temperature for an average residence time to produce the calcined chemically-treated solid oxide;

(b) contacting the calcined chemically-treated solid oxide with a second agent in the continuous calcination vessel, downstream of the continuous calcination vessel, or a combination thereof; and

(c) recycling a filtered portion of the solid oxide, the chemically-treated solid oxide, and/or the calcined chemically-treated solid oxide back to the same or an upstream location in the continuous calcination vessel, wherein less than 1% by weight of the respective solid oxide, chemically-treated solid oxide and/or the calcined chemically-treated solid oxide is lost overhead;

wherein the fluidized bed has a slope from horizontal in a range from about 5 degrees to less than about 15 degrees.

2. The process of claim 1, wherein:

the first agent comprises air, nitrogen, argon, hydrogen, oxygen, carbon monoxide, water, or any combination thereof; and

the second agent comprises helium, neon, argon, nitrogen, or any combination thereof.

3. The process of claim 1, wherein the solid oxide comprises silica, alumina, silica-alumina, aluminophosphate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any combination thereof.

4. The process of claim 1, wherein the calcined chemically-treated solid oxide comprises fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, sulfated silica-alumina, or any combination thereof.

5. The process of claim 1, wherein the compound comprises SO₃, ammonium sulfate, sulfuric acid, F₂, BF₃, hydrogen fluoride, silicon tetrafluoride, titanium tetrafluoride, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, Cl₂, hydrogen chloride, carbon tetrachloride, perchlorobenzene, chloromethane, dichloromethane, chloroform, trichloroethanol, a freon, or any combination thereof.

6. The process of claim 1, wherein contacting the calcined chemically-treated solid oxide with the second agent in step (b) reduces a residual oxygen content of the calcined chemically-treated solid oxide to less than about 100 ppm, a residual moisture content of the calcined chemically-treated solid oxide to less than about 100 ppm, or a combination thereof.

7. The process of claim 1, wherein:

the calcined chemically-treated solid oxide has an average bulk density in a range from about 0.2 g/mL to about 0.7 g/mL; and

a linear velocity of the first agent in the fluidized bed is in a range from 0.1 ft/sec to about 0.7 ft/sec.

8. The process of claim 1, wherein a flow of the solid oxide, the chemically-treated solid oxide, and/or the calcined chemically-treated solid oxide in the fluidized bed is substantially plug flow.

9. The process of claim 1, wherein:

contacting the calcined chemically-treated solid oxide with the second agent in step (b) reduces a residual oxygen content of the calcined chemically-treated solid oxide to less than about 100 ppm, a residual moisture content of the calcined chemically-treated solid oxide to less than about 100 ppm, or a combination thereof; and

the second agent comprises helium, neon, argon, nitrogen, or any combination thereof.

10. A process for continuously preparing a calcined chemically-treated solid oxide comprising:

(a) (i) introducing a solid oxide into a continuous calcination vessel comprising a fluidized bed; and

contacting the solid oxide with a compound and a first agent at a calcination temperature for an average residence time to produce the calcined chemically-treated solid oxide;

or

 

(ii) introducing a chemically-treated solid oxide into a continuous calcination vessel comprising a fluidized bed; and

contacting the chemically-treated solid oxide with a first agent at a calcination temperature for an average residence time to produce the calcined chemically-treated solid oxide; and

(b) contacting the calcined chemically-treated solid oxide with a second agent in the continuous calcination vessel, downstream of the continuous calcination vessel, or a combination thereof;

wherein the fluidized bed comprises at least one zone dividing wall for dividing the fluidized bed into a plurality of heating zones capable of independent temperature control and independent fluidizing gas control.

11. The process of claim 10, wherein the process further comprises a step of discharging the calcined chemically-treated solid oxide from the continuous calcination vessel and into a polymerization reactor or a catalyst preparation system vessel.

12. The process of claim 10, wherein the first agent comprises air, nitrogen, argon, hydrogen, oxygen, carbon monoxide, water, or any combination thereof.

13. The process of claim 10, wherein the second agent comprises helium, neon, argon, nitrogen, or any combination thereof.

14. The process of claim 10, wherein the solid oxide comprises silica, alumina, silica-alumina, aluminophosphate, titania, zirconia, magnesia, boria, zinc oxide, a mixed oxide thereof, or any combination thereof.

15. The process of claim 10, wherein the compound comprises SO₃, ammonium sulfate, sulfuric acid, F₂, BF₃, hydrogen fluoride, silicon tetrafluoride, titanium tetrafluoride, perfluorohexane, perfluorobenzene, fluoromethane, trifluoroethanol, Cl₂, hydrogen chloride, carbon tetrachloride, perchlorobenzene, chloromethane, dichloromethane, chloroform, trichloroethanol, a freon, or any combination thereof.

16. The process of claim 10, wherein the calcined chemically-treated solid oxide comprises fluorided alumina, chlorided alumina, sulfated alumina, fluorided silica-alumina, chlorided silica-alumina, sulfated silica-alumina, or any combination thereof.

17. The process of claim 10, wherein the calcination temperature is in a range from about 300°

C. to about 1000°

C. and the average residence time is in a range from about 5 minutes to about 24 hours.

18. The process of claim 10, wherein contacting the calcined chemically-treated solid oxide with the second agent in step (b) reduces a residual oxygen content of the calcined chemically-treated solid oxide to less than about 100 ppm, a residual moisture content of the calcined chemically-treated solid oxide to less than about 100 ppm, or a combination thereof.