Methods Of Synthesizing Hydrous Zirconium Oxide And Other Oxides

• US 20130190168A1
• Filed: 03/13/2013
• Published: 07/25/2013
• Est. Priority Date: 10/26/2010
• Status: Active Grant

• Current Assignee: Fresenius Medical Care Holdings Incorporated (Fresenius SE & Co. KGaA)
• Original Assignee: Fresenius Medical Care Holdings Incorporated (Fresenius SE & Co. KGaA)
• Inventors: Wong, Raymond J., Fontenelle, Lucas
• Granted Patent: US 10,857,280 B2
• Time in Patent Office: Days
• US Class Current: 502/308
• CPC Class Codes: A61M 1/1654 Dialysates therefor
• CPC Class Codes: A61M 1/1696 with dialysate regeneration
• CPC Class Codes: B01J 20/06 comprising oxides or hydroxides of metals not provided for in group B01J20/04
• CPC Class Codes: B01J 20/28057 Surface area, e.g. B.E.T specific surface area
• CPC Class Codes: B01J 20/28071 being less than 0.5 ml/g
• CPC Class Codes: B01J 20/28083 being in the range 2-50 nm, i.e. mesopores
• CPC Class Codes: B01J 2220/62 In a cartridge
• CPC Class Codes: B01J 45/00 Ion-exchange in which a complex or a chelate is formed; Use of material as complex or chelate forming ion-exchangers; Treatment of material for improving the complex or chelate forming ion-exchange properties ion-exchange chromatography processes B01D15/36

Abstract

The present invention relates to sol gel hydrous metal oxide particles, such as hydrous zirconium oxide particles, their manufacture, and their use in such applications as sorbent dialysis.

Claims

1. Hydrous metal oxide particles comprising:

at least one hydrous metal oxide; and

at least one oxygen-containing additive;

wherein the oxygen-containing additive comprises at least one polar group or a charged group or both; and

wherein the oxygen-containing additive is present as a soluble ligand that forms a complex with a metal ion of the hydrous metal oxide.

2. The hydrous metal oxide particles of claim 1, wherein a metal ion of the hydrous metal oxide comprises a zirconium ion, a hafnium ion, a titanium ion, a tin ion, or a lead ion.

3. The hydrous metal oxide particles of claim 1, wherein the metal ion is a zirconium ion.

4. The hydrous metal oxide particles of claim 1, wherein the oxygen-containing additive comprises a molecular weight from about 50 to about 500 Da.

5. The hydrous metal oxide particles of claim 1, wherein the oxygen-containing additive comprises a surfactant.

6. The hydrous metal oxide particles of claim 1, wherein the oxygen-containing additive comprises a dispersant.

7. The hydrous metal oxide particles of claim 6, wherein the dispersant is tartaric acid.

8. The hydrous metal oxide particles of claim 1, wherein the oxygen-containing additive comprises acetic acid, soda ash, polyvinyl alcohol, tartaric acid, EDTA, glycerol, sodium dodecyl sulfate, or any combination thereof.

9. The hydrous metal oxide particles of claim 1, wherein the hydrous metal oxide particles have a particle size range of from about 2 to about 200 microns.

10. The hydrous metal oxide particles of claim 1, wherein the hydrous metal oxide particles have a particle size distribution of less than 25% in the range of less than about 25 microns, less than 5% in the range of more than about 100 microns, and more than 70% in the range of from about 25 microns to about 100 microns.

11. The hydrous metal oxide particles of claim 1 having a pore volume of at least 0.09 mL/g, or a monolayer volume of at least 37 mL/g (STP), or a 20-80 nm pore size content of at least 10%.

12. The hydrous metal oxide particles of claim 1, wherein the hydrous metal oxide particles have an average BET surface area of at least 100 m²/g.

13. The hydrous metal oxide particles of claim 1, wherein the hydrous metal oxide is capable of binding at least one anion that is phosphate, sulfate, nitrate or any combination thereof.

14. The hydrous metal oxide particles of claim 1, wherein the hydrous metal oxide is capable of binding one or more waste product comprising creatinine, uric acid, NH4+, beta-2 micro-globulin, bilirubin, citrate, phenol, methanol, or any combination thereof.

15. The hydrous metal oxide particles of claim 1, wherein the oxygen-containing additive forms a temporary complex with the metal ion of the hydrous metal oxide.

16. The hydrous metal oxide particles of claim 1, wherein the oxygen-containing additive forms a permanent complex with the metal oxide of the hydrous metal oxide.

17. A dialysis system comprising a cartridge that contains the hydrous metal oxide particles of claim 1.

18. A portable dialysis system comprising a container that contains the hydrous metal oxide particles of claim 1.

20. A method of making hydrous metal oxide particles according to claim 1 comprising:

combining at least one oxygen-containing additive with at least one water soluble metal salt in an aqueous solvent to form a first solution wherein the oxygen-containing additive forms a complex with metal ions in the first solution; and

combining the first solution with at least one precipitant to obtain hydrous metal oxide particles by sol gel precipitation.

21. The method of claim 20, wherein the metal ion of the hydrous metal oxide particles comprises a zirconium ion, a hafnium ion, a titanium ion, a tin ion, or a lead ion.

22. The method of claim 20, wherein the metal ion is a zirconium ion and the water soluble metal salt is a zirconium salt.

23. The method of claim 20, wherein the water soluble metal salt is zirconium oxychloride.

24. The method of claim 20, wherein the precipitant has a molarity of from about 5 moles/L to about 25 moles/L.

25. The method of claim 20, wherein the precipitant is an alkali solution.

26. The method of claim 25, wherein the alkali solution is sodium hydroxide.

27. The method of claim 20, wherein the water soluble metal salt is zirconium oxychloride and the zirconium oxychloride and precipitant are introduced at a molar ratio of metal salt to precipitant of from about 0.1:

1 to about 0.5;

1.

28. The method of claim 20, wherein the water soluble metal salt is zirconium oxychloride and the zirconium oxychloride is present in the aqueous solvent at a concentration of from about 0.5 to about 2.0 g/ml.

29. The method of claim 20, wherein the aqueous solvent is deionized water or reverse osmosis water.

30. The method of claim 20, wherein the water soluble metal salt is dissolved in the aqueous solvent and then the oxygen-containing additive is added to form the first solution.

31. The method of claim 20, wherein the water soluble metal salt is present in the aqueous solvent at a saturation concentration.

32. The method of claim 20, wherein the oxygen-containing additive is dissolved in the aqueous solvent and then the water soluble metal salt is added to form the first solution.

33. The method of claim 20, wherein the oxygen-containing additive is present in the first solution in a molar amount sufficient to prevent gelation of the particles.

34. The method of claim 20, wherein the oxygen-containing additive forms a soluble complex with the metal ion of the hydrous metal oxide.

35. The method of claim 20, wherein the oxygen-containing additive forms a temporary complex with the metal ion of the hydrous metal oxide in the solution such that the additive is removable from the particles with a washing step after precipitation.

36. The method of claim 20, wherein the oxygen-containing additive forms a permanent complex with the metal ion of the hydrous metal oxide.

37. The method of claim 20, wherein the first solution and the precipitant are combined by providing the precipitant in an aqueous solution and adding at least part of the first and at least part of the precipitant solution simultaneously to a reaction vessel so that the concentration of precipitant is kept constant in the reaction vessel during a period of time that the precipitant is added to the reaction vessel.

38. The method of claim 20, wherein said first solution is simultaneously added with a diluted solution of precipitant to the reaction vessel.

39. The method of claim 38, wherein the reaction vessel includes an agitator.

40. The method of claim 20, wherein a slurry containing at least a hydrous metal oxide gel precipitate is formed, and wherein the slurry is agitated.

41. The method of claim 40, further comprising filtering the slurry after mixing.

42. The method of claim 40, further comprising washing the slurry with deionized water (alkaline wash).

43. The method of claim 42, further comprising forming a filter cake.

44. The method of claim 43, further comprising transferring the filter cake back to deionized water to form a second slurry.

45. The method of claim 44, further comprising titrating the second slurry to lower pH to a value in a range of from about pH 2 to about pH 8 by addition of acid to remove precipitant cations (acid wash).

46. The method of claim 45, further comprising filtering the titrated or acid-washed slurry and drying the product until the moisture of the product is from about 10% to about 40% LOD in the form of free-flowing powder.

47. The method of claim 20, further comprising isolating and drying the resulting hydrous metal oxide particles to obtain a free flowing powder.

48. The method of claim 20, wherein the first solution is in the form of droplets before it is combined with the precipitant.

49. The method of claim 20, wherein the first solution obtained and the precipitant solution are combined so that metal ions and precipitant are present in a molar ratio of from about 0.1 to about 1 of metal to precipitant.

50. A method of making hydrous metal oxide particles having a controlled particle size comprising:

forming hydrous metal oxide particles by sol gel precipitation by the method of claim 1, and controlling at least one of the following parameters to affect particle size or particle size distribution of the hydrous metal oxide particles;

rate at which the solution of soluble metal salt is added to the reaction vessel, rate at which the precipitant solution is added to the reaction vessel, pH of the precipitant solution, concentration of soluble metal salt and precipitant in the reaction vessel, or speed of the agitator, or any combination thereof.

53. A composition comprising hydrous metal oxide particles, wherein the particles are formed by the method of claim 1.

54. The hydrous metal oxide particles of claim 1, further comprising at least one functional group attached to said hydrous metal oxide particles.

55. The hydrous metal oxide particles of claim 54, wherein said at least one functional group comprises at least one polar functional group.

56. The hydrous metal oxide particles of claim 54, wherein said functional group comprises a surfactant, an acid, an amine, a sulfate, or any combination thereof.

57. The hydrous metal oxide particles of claim 54, wherein said functional group is EDTA, sulfonic acid, hydroxy amine, lauryl sulfate, hydroxyl benzene sulfonic acid, or any combination thereof.

66. The hydrous metal oxide particle of claim 1, wherein said hydrous metal oxide particle has at least one of the following characteristics:

a) a sulfate adsorption capacity of 5 mg/g;

b) a BET surface area of at least 100 m²/g;

c) a total pore volume of at least 0.09 mL/g;

d) a pore size of at least 6 nm;

or any combination thereof.

67. The hydrous metal oxide particles of claim 66, wherein said hydrous metal oxide particles have at least one functional group attached thereto.

19. A hydrous zirconium oxide composition comprising a water-soluble hydrous zirconium oxide polymer in an aqueous solution, wherein the polymer is formed by combining, in an aqueous solvent, zirconium oxychloride with at least one oxygen-containing additive that is capable of forming a complex with zirconium ions, wherein the hydrous zirconium oxide composition, when dried, has a particle size distribution of less than 25% in the range of less than about 25 microns, less than 5% in the range of more than about 100 microns, and more than 70% in the range of from about 25 microns to about 100 microns.

51. A method of making hydrous zirconium oxide particles comprising:

combining at least one oxygen-containing additive with zirconium oxychloride in an aqueous solvent to form a first solution wherein the oxygen-containing additive forms a complex with zirconium ions in the solution; and

combining the first solution with precipitant to obtain hydrous zirconium oxide particles by sol gel precipitation, wherein the oxygen-containing additive is a surfactant, acetic acid, soda ash, polyvinyl alcohol, tartaric acid, EDTA, glycerol, sodium dodecyl sulfate, or any combination thereof.

52. A method of making hydrous zirconium oxide particles comprising:

adding a solution of zirconium oxychloride and a precipitant solution simultaneously to a reaction vessel to obtain hydrous zirconium oxide particles by sol gel precipitation.

58. A hydrous metal oxide particle, wherein said hydrous metal oxide particle has at least one of the following characteristics:

a) a sulfate adsorption capacity of 5 mg/g;

b) a BET surface area of at least 100 m²/g;

c) a total pore volume of at least 0.09 mL/g;

d) a pore size of at least 6 nm;

or any combination thereof.

59. The hydrous metal oxide particles of claim 58, wherein said hydrous metal oxide particles have at least one functional group attached thereto.

60. The hydrous metal oxide particles of claim 58, wherein the hydrous metal oxide particles have a particle size range of from about 2 to about 200 microns.

61. The hydrous metal oxide particles of claim 58, wherein the hydrous metal oxide particles have a particle size distribution of less than 25% in the range of less than about 25 microns, less than 5% in the range of more than about 100 microns, and more than 70% in the range of from about 25 microns to about 100 microns.

62. The hydrous metal oxide particles of claim 58 having a pore volume of at least 0.09 mL/g, or a monolayer volume of at least 37 mL/g (STP), or a 20 to 80 nm pore size content of at least 10%.

63. The hydrous metal oxide particles of claim 59, wherein said at least one functional group comprises at least one polar functional group.

64. The hydrous metal oxide particles of claim 59, wherein said functional group comprises a surfactant, an acid, an amine, a sulfate, or any combination thereof.

65. The hydrous metal oxide particles of claim 59, wherein said functional group is EDTA, sulfonic acid, hydroxy amine, lauryl sulfate, hydroxyl benzene sulfonic acid, or any combination thereof.