Zirconium phosphate and method for its preparation

• US 4,826,663 A
• Filed: 05/13/1986
• Issued: 05/02/1989
• Est. Priority Date: 05/15/1985
• Status: Expired due to Fees

• Current Assignee: Eniricerche S.P.A. (Eni Petroleum Company Incorporated)
• Original Assignee: Eniricerche S.P.A. (Eni Petroleum Company Incorporated)
• Inventors: Constantino, Umberto, Bartoli, Francesco, Di Gregorio, Francesco, Valentini, Claudio, Alberti, Giulio
• Primary Examiner(s): Doll, John
• Assistant Examiner(s): Langel, Wayne A.
• Application Number:
  US06/862,809
• Time in Patent Office: 1,085 Days
• Field of Search: 423/309, 423/311, 423/308, 423/157, 423/181, 423/659, 502/208, 556/24, 556/26
• US Class Current: 423/157
• CPC Class Codes: B01J 39/09 Inorganic material
• CPC Class Codes: C01B 25/372 of titanium, vanadium, zirconium, niobium, hafnium or tantalum
• CPC Class Codes: C07D 453/04 having a quinolyl-4, a substituted quinolyl-4 or a alkylenedioxy-quinolyl-4 radical linked through only one carbon atom, attached in position 2, e.g. quinine

Abstract

The invention relates to a zirconium phosphate in particles having sizes comprised within the range of from 1 to 100 μm, a lamellar structure with interlayer distance, in the anhydrous state, comprised within the range of from 7.9 to 8.2 Å and a surface area comprised within the range of from 9 to 20 m² /g.

The method consists in altering the lamellar structure of a zirconium phosphate with layer structure of alpha type by intercalating into it an organic substance containing a proton-acceptor group and water and by a treatment with ultrasounds, in regenerating the hydrogen form of said zirconium phosphate by an acid and in washing the same with diluted acids and/or water.

Claims

1. Particulate zirconium acid phosphate of modified lamellar structure having a particle size of from 1 to 100 μ

m, a lamellar structure with interlayer of distance in the anhydrous state of from 7.9 Å

to 8.2 Å and

a surface area of from 9 to 20 m² /g.

2. Zirconium phosphate according to claim 1 which upon hydration shows an increase of the interlayer distance, which reaches the value of 10.1 Å

under conditions of relative humidity of 92%.

3. A method for the preparation of the zirconium phosphate according to claim 1 comprising

(1) intercalating, into crystalline zirconium phosphate α

-Zr(HPO₄)₂.H₂ O having interplanar distance of 7.6 Å

, an organic substance containing a proton-acceptor group and water until a stable colloidal aqueous suspension of intercalated zirconium phosphate is prepared,

(2) treating the colloidal suspension with ultrasounds,

(3) thereafter treating the suspension with non-zirconium-complexing acid until a precipitate of zirconium acid phosphate with modified lamellar structure is formed,

(4) recovering the precipitate and washing it with dilute acid and/or water.

4. A method according to claim 3 wherein the acids are mineral acids.

5. A method according to claim 4, wherein the mineral acids are selected from HCl, H₂ SO₄ and HNO₃.

6. A method according to claim 3, wherein the acid treatment of the colloidal suspension is carried out at a pH of from 0 to 3.

7. A method according to claim 6, wherein the pH is 1.

8. A method accoridng to claim 3, wherein the treatment with ultrasounds is continued until the optical density of the suspension remains constant.

9. A method according to claim 3, wherein the organic substance is an amine.

10. A method according to claim 9, wherein the amine is selected from methylamine and n-propylamine.

11. A method according to claim 10, wherein the intercalary amine is n-propylamine and is added in an amount ranging from 25% to 75% of the number of gramatoms of the acidic protons present in the amount of zirconium phosphate α

-Zr(HPO₄).H₂ O used.

12. A method according to claim 11, wherein the intercalary n-propylamine is added in an amount equal to 50% of the number of gram-atoms of the acidic protons present in the zirconium phosphate.

13. A method according to claim 3, wherein the stale colloidal aqueous suspension of intercalated zirconium phosphate is obtained by first intercalating the zirconium phosphate in a non-aqueous medium, and then dispersing it in water.

14. A method according to claim 13, wherein the zirconium phosphate is intercalated with n-propylamine.

15. A method according to claim 13, wherein the non-aqueous medium is an alcohol.

16. A method according to claim 15, wherein the alcohol is methanol.

17. A method according to claim 3, wherein zirconium phosphate with modified lamellar structure is recovered by filtration.

18. A method according to claim 3, wherein zirconium phosphate with modified lamellar structure is dried after the recovery and washing with dilute acid and/or water.

19. A method according to claim 18, wherein the drying is carried out in air at room temperature.

20. A method according to claim 18, wherein the drying is carried out in an oven.

21. A method according to claim 18, wherein the drying is carried out by spray-drying.

22. A method according to claim 18, wherein the drying is carried out by freeze-drying.

23. A process comprising the step of intercalating proton-acceptor organic substances having molecular weights up to 500 Daltons, wherein the zirconium phosphate according to claim 1 is the intercalan.

24. A process for recovering Cs⁺ and Ba⁺⁺ ions by ion exchange, wherein the zirconium phosphate according to claim 1 or 2 is the ion exchanger.

25. A process comprising the step of using the zirconium phsophate according to claim 1 or 2 as a catalyst or catalyst support.