METHOD AND APPARATUS FOR PRODUCTION OF A COMPOUND HAVING SUBMICRON PARTICLE SIZE AND A COMPOUND PRODUCED BY THE METHOD

• US 20080026929A1
• Filed: 12/23/2003
• Published: 01/31/2008
• Est. Priority Date: 12/23/2003
• Status: Abandoned Application

• Current Assignee: Aalborg Universitet
• Original Assignee: Aalborg Universitet
• Inventors: Jensen, Henrik, Sogaard, Erik Gydesen, Iversen, Steen Brummerstedt
• Application Number:
  US10/584,301
• Publication Number:
  US 20080026929A1
• Time in Patent Office: Days
• US Class Current: 501/87
• CPC Class Codes: B82Y 30/00 Nanotechnology for materials or surface science, e.g. nanocomposites
• CPC Class Codes: C01F 7/36 from organic aluminium salts
• CPC Class Codes: C01G 1/02 Oxides
• CPC Class Codes: C01G 23/053 Producing by wet processes, e.g. hydrolysing titanium salts
• CPC Class Codes: C01P 2002/04 Compounds with a limited amount of crystallinty, e.g. as indicated by a crystallinity index
• CPC Class Codes: C01P 2002/72 by d-values or two theta-values, e.g. as X-ray diagram
• CPC Class Codes: C01P 2002/77 by unit-cell parameters, atom positions or structure diagrams
• CPC Class Codes: C01P 2004/64 Nanometer sized, i.e. from 1-100 nanometer
• CPC Class Codes: C01P 2006/12 Surface area
• CPC Class Codes: Y02P 20/54 using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention relates to an improved method of manufacturing a compound having a sub-micron primary particle size such as a metal compound such as metal oxides, metaloxy hydroxides metal hydroxides, metal carbides, metal nitrides, metal carbonitrides, metal borides, electroceramics and other such compound, said method comprising the steps of: introducing a solid reactor filling material in a reactor, introducing a metal-containing precursor, a semi-metal-containing precursor, a metal-containing oxide or a semi-metal-containing oxide in said reactor, introducing a reactant or a substitution source into the said reactor, and introducing a supercritical solvent into the said reactor. These steps result in the formation of said compound in the proximity of the said solid reactor filling material.

Claims

1. Method of manufacturing a metal and/or semi-metal compound such as metal and/or semi-metal oxides, metaloxy and/or semi-metaloxy hydroxides metal and/or semi-metal hydroxides, metal and/or semi-metal carbides, metal and/or semi-metal nitrides, metal and/or semi-metal carbonitrides, metal and/or semi-metal borides, electroceramics and other such compound, said compound having a sub-micron primary particle size, comprising the steps of:

introducing a solid reactor filling material in a reactor,

introducing a metal- and/or semi-metal-containing precursor or a substitution source in said reactor,

introducing a reactant into said reactor,

introducing a supercritical solvent into the said reactor, thereby

establishing a contact between the metal- and/or semi-metal-containing precursor and the co-solvent, thus

resulting in the formation of said compound in the proximity of the said solid reactor filling material.

6. Method according to claims 1, wherein the formation of said compound takes place by a process involving at least a sol-gel reaction.

7. Method according to claim 1, wherein the metal and/or semi-metal compound is/are substantially crystalline.

9. Method according to claim 1, wherein the metal and/or semi-metal compound is/are substantially amorphous.

11. Method according to claim 1, wherein the metal and/or semi-metal compound is/are a mixture of several different phases.

13. Method according to any of claims 1-5, wherein the introduction of the solid reactor filling material, the metal-containing precursor, alternatively the semi-metal precursor, the possible co-solvent, and the supercritical solvent into the said reactor is done in arbitrary order.

15. Method according to any of claims 1-5, wherein at least one of the solid reactor filling material, the metal-containing precursor, alternatively the semi-metal-containing precursor, the possible co-solvent or the supercritical solvent is mixed with at least one of the solid reactor filling material, the metal-containing precursor, alternatively the semi-metal-containing precursor, the possible co-solvent or the supercritical solvent before introduction into the said reactor.

17. Method according to any of claims 1-5, where the reactant comprises at least one of the following components:

water, ethanol, methanol, hydrogenperoxid and isopropanol.

18. Method according to any of claims 1-5, where the substitution source comprises at least one of the following components:

carbon, nitrogen, boron and/or any combination of these.

24. Method according to any of claims 15, wherein a temperature in the reactor during the formation of said compound is performed at a temperature profile being an arbitrary combination at least two of the temperature profiles:

a fixed temperature, an increasing temperature, a decreasing temperature.

29. Method according to any of claim 1-5, wherein a pressure in the reactor during the formation of said compound is performed at a pressure profile being an arbitrary combination at least two of the pressure profiles:

a fixed pressure, an increasing pressure, a decreasing pressure.

30. Method according to any of claims 15, wherein the supercritical solvent is CO₂, and wherein the pressure in the reactor during the formation of said compound is minimum 74 bar, more alternatively minimum 80 bar, even more alternatively minimum 90 bar, and most alternatively minimum 100 bar and wherein the temperature in the reactor during the formation of said compound is minimum 31°

C., alternatively 43°

C., alternatively minimum 100°

C., alternatively minimum 200°

C., alternatively minimum 300°

C., alternatively minimum 400°

C. alternatively minimum 500°

C., alternatively minimum 600°

C., alternatively minimum 700°

C., alternatively minimum 800°

C.

32. Method according to any of claims 1, wherein the supercritical solvent is isopropanol, and wherein the pressure in the reactor during the formation of said compound is minimum 47 bar, more alternatively minimum 80 bar, even more alternatively minimum 90 bar, and most alternatively minimum 100 bar and wherein the temperature in the reactor during the formation of said compound is minimum 235°

C., more alternatively minimum 250°

C., even more alternatively minimum 270°

C., most alternatively minimum 300°

C., and even and most alternatively minimum 400°

C.

36. Method according to any of claims 15, wherein the time of the formation of said compound is maximum 1 hour, preferably maximum 0.75 hour, and most preferably maximum 0.5 hour.

39. Method according to any of claims 1 -5 wherein a plurality of different metal- and/or semi-metal-containing precursors is/are introduced in said reactor.

43. Method according to any of claims 1 -5, wherein the metal containing or semi-metal containing precursor is a metal alkoxide or a semi-metal alkoxide.

92. Method according to any of claims 1-5, wherein the solid reactor filling material comprises any combination of metal oxide, semi-metal oxide, metal oxidhydroxide, semi-metal oxidhydroxide, metal hydroxide, semi-metal hydroxide, metal carbide, semi-metal carbide, metal nitride, semi-metal nitride, metal carbonitride, semi-metal carbonitride, metal boride and semi-metal boride identical to at least one compound resulting from the formation in said reactor.

93. Method according to any of claims 1-5, wherein the solid reactor filling material functions as seed material for the formation of said compound and/or as a collecting agent for the said compound.

97. Method according to any if claims 1-5, wherein said compound is separable from the solid reactor filling material in a way that allows the solid reactor filling material to be reused as solid reactor filling material.

98. Method according to any of claims 1-5, wherein said compound is separable from the solid reactor filling material by flushing the solid reactor filling material in a fluid or by vacuum means or by blowing means or by ultrasonic means.

103. Metal compound such as metal and/or semi oxide, metal and/or semi oxidhydroxide, metal and/or semi hydroxide, metal and/or semi carbide, metal and/or semi nitride, metal and/or semi carbonitride or metal and/or semi boride compound being manufactured by the method according to any of claims 1-5, wherein the metal and/or semi oxide, metal and/or semi oxidhydroxide, metal and/or semi hydroxide, metal and/or semi carbide, metal and/or semi nitride, metal and/or semi carbonitride or metal and/or semi boride compound is in the form of aggregates of primary particles with an average primary particle size of 100 nm, preferably maximum 50 nm, more preferably maximum 20 nm, and most preferably maximum 10 nm.

2-5. -5. (canceled)

8. (canceled)

10. (canceled)

25. Method according to claim 10, wherein the temperature in the reactor during the formation of said compound is maximum 400°

C., more preferably maximum 300°

C., even more preferably maximum 200°

C., most preferably maximum 100°

C., and even and most preferably maximum 50°

C.

12. (canceled)

14. (canceled)

16. (canceled)

19-23. -23. (canceled)

26-28. -28. (canceled)

31. (canceled)

33-35. -35. (canceled)

37. (canceled)

38. (canceled)

40-42. -42. (canceled)

44-50. -50. (canceled)

53-91. -91. (canceled)

94-96. -96. (canceled)

99-102. -102. (canceled)

104-111. -111. (canceled)

112. Apparatus for manufacturing a metal and/or semi-metal compound such as metal and/or semi-metal oxides, metaloxy and/or semi-metaloxy hydroxides metal and/or semi-metal hydroxides, metal and/or semi-metal carbides, metal and/or semi-metal nitrides, metal and/or semi-metal carbonitrides, metal and/or semi-metal borides, electroceramics and other such compound, said compound having a sub-micron primary particle size, comprising the following components:

means for introducing a solid reactor filling material in a reactor,

means for introducing a metal- and/or semi-metal-containing precursor in said reactor,

means for introducing a reactant in said reactor,

means for introducing a supercritical solvent into the said reactor,

said reactor intended as a space for establishing a contact between the metal- and/or semi-metal-containing precursor and the reactant and

said reactor intended as a space for the formation of said compound in the proximity of the said solid reactor filling material.

113. (canceled)

114. Apparatus for manufacturing a metal and/or semi-metal compound such as metal and/or semi-metal oxides, metaloxy and/or semi-metaloxy hydroxides, metal and/or semi-metal hydroxides, metal and/or semi-metal carbides, metal and/or semi-metal nitrides, metal and/or semi-metal carbonitrides, metal and/or semi-metal borides, electroceramics and other such compound, said compound having a sub-micron primary particle size, comprising the following components:

means for introducing a solid reactor filling material in a reactor,

means for introducing a metal- and/or semi-metal-containing oxide in said reactor,

means for introducing a substitution source mi said reactor,

means for introducing a supercritical solvent into the said reactor,

said reactor intended as a space for establishing a contact between the metal- and/or semi-metal-containing oxide and the substitution source and

said reactor intended as a space for the formation of said compound in the proximity of the said solid reactor filling material.

115. (canceled)