Support for catalysts, process for the manufacture of a precursor gel of a support for catalysts, catalyst for the polymerization of olefins and process for the polymerization of olefins by means of this catalyst

• US 5,849,852 A
• Filed: 01/29/1996
• Issued: 12/15/1998
• Est. Priority Date: 05/17/1993
• Status: Expired due to Fees

• Current Assignee: Solvay Polyolefins Europe-Belgium (Societe Anonyme)
• Original Assignee: Solvay Polyolefins Europe-Belgium SA
• Inventors: Koch, Benoit, Wijzen, Fabienne, Rulmont, Andre
• Primary Examiner(s): Nagumo, Mark
• Application Number:
  US08/553,326
• Time in Patent Office: 1,051 Days
• Field of Search: 423/306, 423/327.1, 423/305, 502/154, 502/172, 502/200, 502/201, 502/210, 502/214, 502/405, 526/96, 526/106, 526/113, 526/118, 526/130
• US Class Current: 526/96
• CPC Class Codes: B01J 21/12 Silica and alumina
• CPC Class Codes: B01J 27/16 containing oxygen , i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/617 500-1000 m2/g
• CPC Class Codes: B01J 35/638 more than 1.0 ml/g
• CPC Class Codes: B01J 37/033 Using Hydrolysis
• CPC Class Codes: B01J 37/036 to form a gel or a cogel
• 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 4/025 Metal oxides

Abstract

Support for catalysts, containing at least two constituents chosen from silica, alumina and aluminium phosphate, having a specific surface of 100 to 800 m² /g, a crystallization temperature greater than or equal to 700° C. and a pore volume of 1.5 to 4 cm³ /g, the specific surface (SS) and the pore volume (PV) corresponding to the relationship:

SS<(PV×564-358).

Process for the manufacture of such a support, according to which an alcohol, water, a silicon alkoxide and an acid are mixed under conditions such that gelling or precipitation of silica is prevented, an acidic solution of an aluminium compound and/or a solution of a source of phosphate ions are added thereto, a gelling agent is added thereto, a gel is recovered which is washed with water and then by means of an organic liquid, the gel is then dried until a powder is obtained, and the powder is calcined. Polymerization of olefins in the presence of a catalyst containing chromium on a support as described above.

Claims

1. A support for catalysts of homogeneous and amorphous structure, containing silica, aluminium phosphate, and optionally alumina, said support having a specific surface of 100 to 800 m² /g, a crystallization temperature greater than or equal to 700°

C. and a pore volume of 1.5 to 4 cm³ /g, the specific surface (SS) and the pore volume (PV) corresponding to the following relationship;

space="preserve" listing-type="equation">SS<

(PV×

564-358),

in which SS and PV respectively denote the numerical values of the specific surface, expressed in m² /g, and of the pore volume, expressed in cm³ /g.

2. The support according to claim 1, consisting of two constituents, one of which is silica (A) and the other (B) aluminium phosphate, in an (A):

(B) molar percentage of (10 to

     95);

(90 to

     5) based on the total moles of (A) and (B).

3. The support according to claim 1, wherein it contains silica (X), alumina (Y) and aluminium phosphate (Z), in an (X):

(Y);

(Z) molar percentage of (10 to

     95);

(1 to

     80);

(1 to

     85) based on the total moles of (X), (Y), and (Z).

4. The support according to claim 1, including titanium in an amount, expressed as TiO₂, of from 0.1 to 40 mol % based on the total moles of silica, aluminum phosphate, titanium dioxide, and optionally alumina.

5. The support according to claim 1, having a standard density of 50 to 500 kg/m³.

6. A catalyst for the polymerization of olefins containing chromium on a support in accordance with claim 1.

7. A process for the polymerization of olefins in the presence of a catalyst in accordance with claim 6.

8. The process according to claim 7, applied to the polymerization of ethylene.

9. A process for the preparation of the support as defined in claim 1, including:

preparing a precursor gel by means of a process comprising in a first stage, mixing an alcohol, water, a silicon alkoxide and an acid in amounts such that the water/silicon molar ratio is from 2 to 50 in order to form a hydrolysis medium, mixing an acidic solution of an aluminium compound and a solution of a source of phosphate ions, in a second stage, and, in a third stage, adding a gelling agent to the hydrolysis medium thus obtained in order to form a precursor gel, wherein the first stage is carried out at acid pH and comprises, on the one hand, the addition of water, acid, silicon alkoxide and alcohol, the temperature, during the addition, being less than or equal to 30°

C. and, on the other hand, a maturing of the hydrolysis medium thus obtained at a temperature at least equal to 20°

C. and lower than the boiling temperature of the medium, so as to substitute at least part of the alkoxy groups of the silicon alkoxide by hydroxyl group, without producing precipitation or gelling of silica,

washing the gel with water and then by means of an organic liquid,

drying said washed gel by distillation until a powder is obtained, and

calcining the powder to produce a support for catalysts of homogeneous and amorphous structure.

10. The process according to claim 9, wherein the organic liquid is an alcohol.

11. Process according to claim 10, characterized in that the organic liquid is isopropyl alcohol.

12. Process according to claim 9, characterized in that the drying is carried out by distillation of an azeotropic mixture of water and of the organic liquid until at least 98% of the water and part of the organic liquid have been removed, followed by a distillation of the other part of the organic liquid.

13. The process according to claim 9, wherein the silicon alkoxide is an aliphatic silicon alkoxide.

14. The process according to claim 13, wherein the silicon alkoxide is silicon tetraethoxide.

15. The process according to claim 9, wherein the acid used in the first stage is hydrochloric acid.

16. The process according to claim 9, including, in the first stage, a titanium alkoxide.

17. The process according to claim 9, wherein the titanium alkoxide is added during the maturing.

18. The process according to claim 9, including, in the first stage, titanium acetylacetonate.

19. The process according to claim 9, wherein the aluminium compound is an inorganic aluminium salt or an aluminium alkoxide.

20. The process according to claim 19, wherein the inorganic aluminium salt is aluminium nitrate or aluminum chloride.

21. The process according to claim 9, wherein the source of phosphate ions is phosphoric acid.

22. The process according to claim 9, wherein the gelling agent is an aqueous ammonium hydroxide solution.

23. The process according to claim 9, wherein, in the first stage, the maturing is carried out at a temperature of 50°

to 70°

C.

24. The process according claim 9, wherein the second stage is carried out at a temperature below or equal to 20°

C.

25. The process according to claim 9, wherein the third stage is carried out in a medium with a constant pH, the value of which is from 6 to 10, and at a temperature below or equal to 30°

C.

26. The process according to claim 9, wherein, on conclusion of the third stage, a gel is recovered which is subjected to a maturing.

27. The process according to claim 26, wherein the maturing of the gel is carried out at a temperature which can vary from room temperature to the boiling temperature of the maturing medium and at a pH greater than or equal to 6.

28. A process for the manufacture of a precursor gel of a support for a catalyst, including steps for, in a first stage, mixing an alcohol, water, a silicon alkoxide and an acid in amounts such that the water/silicon molar ratio is from 2 to 50, adding an acidic solution of an aluminium compound and/or a solution of a source of phosphate ions, in a second stage, and, in a third stage, adding a gelling agent to the hydrolysis medium thus obtained, the first stage being carried out at acid pH and the temperature during the addition of water, acid, silicon, alkoxide and alcohol being less than or equal to 30°

C. and, the first stage also including a maturing of the hydrolysis medium thus obtained at a temperature at least equal to 20°

C. and lower than the boiling temperature of the medium, so as to substitute at least part of the alkoxy groups of the silicon alkoxide by hydroxyl groups, without producing precipitation or gelling of silica.

29. The process according to claim 28, wherein the silicon alkoxide is an aliphatic silicon alkoxide.

30. The process according to claim 29, wherein the silicon alkoxide is silicon tetraethoxide.

31. The process according to claim 28, characterized in that the acid used in the first stage is hydrochloric acid.

32. The process according to claim 28, wherein, in the first stage, a titanium alkoxide is additionally used.

33. The process according to claim 32, wherein the titanium alkoxide is added during the maturing.

34. The process according to claim 28, including, in the first stage, titanium acetylacetonate.

35. The process according to claim 28, wherein the aluminium compound is selected from inorganic aluminium salts and aluminium alkoxides.

36. The process according to claim 35, wherein the inorganic aluminium salts are chosen from aluminium nitrate and chloride.

37. The process according to claim 28, wherein the source of phosphate ions is phosphoric acid.

38. The process according to claim 28, wherein the gelling agent is an aqueous ammonium hydroxide solution.

39. The process according to claim 28, wherein in the first stage, the maturing is carried out at a temperature of 50°

to 70°

C.

40. The process according to claim 28, wherein the second stage is carried out at a temperature below or equal to 20°

C.

41. The process according to claim 28, wherein the third stage is carried out in a medium with a constant pH, the value of which is from 6 to 10, and at a temperature below or equal to 30°

C.

42. The process according to claim 28, wherein on conclusion of the third stage, a gel is recovered which is subjected to a maturing.

43. The process according to claim 42, wherein the maturing of the gel is carried out at a temperature which can vary from room temperature to the boiling temperature of the maturing medium and at a pH greater than or equal to 6.