Single reaction synthesis of texturized catalysts

• US 9,079,164 B2
• Filed: 03/15/2013
• Issued: 07/14/2015
• Est. Priority Date: 03/26/2012
• Status: Active Grant

• Current Assignee: Brigham Young University (The Church of Jesus Christ of Latter-Day Saints)
• Original Assignee: Brigham Young University (The Church of Jesus Christ of Latter-Day Saints)
• Inventors: Woodfield, Brian F., Smith, Stacey, Selck, David, Bartholomew, Calvin H., Ma, Xuchu, Xu, Fen, Olsen, Rebecca E., Astle, Lynn
• Primary Examiner(s): MCDONOUGH, JAMES E
• Application Number:
  US13/836,985
• Publication Number:
  US 20130267411A1
• Time in Patent Office: 851 Days
• Field of Search: 502/303, 502/100, 502/102, 502/104, 502/107
• US Class Current: 1/1
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 21/063 Titanium; Oxides or hydroxides thereof
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 23/44 Palladium
• CPC Class Codes: B01J 23/63 with rare earths or actinides
• CPC Class Codes: B01J 23/745 Iron
• CPC Class Codes: B01J 23/78 with alkali- or alkaline earth metals
• CPC Class Codes: B01J 23/83 with rare earths or actinides
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/33 Electric or magnetic properties
• CPC Class Codes: B01J 35/393 Metal or metal oxide crystallite size
• CPC Class Codes: B01J 35/615 100-500 m2/g
• CPC Class Codes: B01J 35/633 less than 0.5 ml/g
• CPC Class Codes: B01J 35/635 0.5-1.0 ml/g
• CPC Class Codes: B01J 35/647 2-50 nm
• CPC Class Codes: B01J 37/0236 Drying, e.g. preparing a suspension, adding a soluble salt and drying
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: C10G 2/33 characterised by the catalyst used
• CPC Class Codes: C10G 2/332 of the iron-group

Abstract

Methods are described for making a texturized catalyst. The textural promoter may be a high-surface area, high-porosity, stable metal oxide support. The catalyst is manufactured by reacting catalyst precursor materials and support materials in a single, solvent deficient reaction to form a catalyst. The catalyst may be particles or a coating or partial coating of a support surface.

Claims

1. A single-mixture mix and bake method for preparing a texturally promoted catalyst system, comprising:

mixing at least one catalyst metal salt and at least one textural promoter metal salt with a base to form a solvent deficient precursor mixture;

allowing the catalyst metal salt, textural promoter metal salt and the base to react in the solvent deficient precursor mixture to form a precursor catalyst intermediate nanoparticle material; and

heating the intermediate material to yield a stable highly porous textural promoter metal oxide having a textural promoter pore structure phase and a metal catalyst phase on the surface of the pore structure;

wherein the textural promoter metal oxide has a mean pore diameter of from about 1 nm - 55 nm.

2. A method as in claim 1, wherein the molar ratio of catalyst metal salt to textural promoter metal salt is in a range from about 1:

2 to 1;

100.

3. A method as in claim 1, wherein both the mean diameter and surface area of the metal oxide catalyst are lower by at least a factor of 1.5 to 10 than the mean pore diameter and surface area of the textural promoter metal oxide material.

4. A method as in claim 1, wherein the heating is carried out at a temperature equal to or greater than about 250°

C. for a period of at least about 30 minutes, to 1 day and for which the temperature ramp may vary from 0.05 to 10.

5. A method of claim 1 wherein the metal oxide textural promoter has a mean pore diameter of about 1 to 40 nm. including 3 to 4 nm for noble metals catalysts and 10 to 30 nm for Fischer-Tropsch catalysts.

6. A method as in claim 1 , wherein the anion of the textural promoter metal salt is selected to produce a desired pore size in the pore structure.

7. A method as in claim 1 , wherein the water in the solvent deficient precursor mixture forms a slurry with the metal salts.

8. A method as in claim 7, wherein the water is included with an aluminum alkoxide in a molar ratio of water:

alkoxide in a range from about 1;

1 to 1;

10.

9. A method as in claim 1, further comprising including an additive that increases the thermal or hydrothermal stability of the textural promoter metal oxide, wherein the concentration of the additive in the precursor mixture is in a range from 1% to 40% by weight and is present in the final catalyst in the range from 0.5% to 40% by weight.

10. A method as in claim 9, wherein the textural promoter, and/or stabilizing additive is/are selected from the group consisting of Al, Si, Ti, Zr, Ca, Ba, Mg, Mn, Cu, Zn, Ce, La, oxides thereof, and combinations thereof.

11. A method as in claim 1 further comprising addition of a salt to the reaction mixture of a metal selected from the group consisting of Na, K, Cs, Ba, Mn, La, Ce, Cu, Ag, Au, Pd, Pt, Re Ni, and Rh.

12. A method as in claim 1, wherein the pore diameter of the textural promoter metal oxide material is in a range from 2-50 nm and the distribution of the pore diameter is in a range of ±

10% to ±

200% of the average pore diameter.

13. A method as in claim 1, wherein the pore structure of the textural promoter metal oxide material has a BET surface area in a range from 50 m²/g to 800 m²/g;

and/or a pore diameter in a range from 2 nm to 50 nm. and wherein the pore volume of the textural promoter metal oxide is in a range from 0.5-1.8 cm³/g.

14. A method as in claim 1, wherein the textural promoter metal salt includes an aluminum salt and the resulting stable metal oxide textural promoter material includes γ

-alumina stabilized by one or more additives.

15. A method as in claim 1, wherein the textural promoter metal salt includes a titanium metal salt and the resulting stable metal oxide textural promoter includes primarily titania in the rutile or anatase phase.

16. The method of claim 1 wherein the metal catalyst material includes an iron salt, a copper salt and a potassium salt and the textural promoter salt is from the group consisting of an aluminum salt, a titanium salt and combinations thereof.

17. The method of claim 16 wherein the iron salt includes Fe(NO₃)₃·

xH₂O, the copper salt includes Cu(NO)₃·

xH₂O, the potassium salt includes KHCO₃ and the base includes NH₄HCO₃.

18. A method of claim 1 wherein water present in the solvent deficient mixture is at least in part provided by a metal salt hydrate.

19. A method of claim 2 wherein the molar ratio of catalyst metal salt to textural promoter metal salt is in a range from about 1:

4 to 1;

33.

20. A method of claim 3 wherein the textural promoter has mean pore diameters of 3-4 nm where noble metal catalyst nanoparticles are 1-2 nm in diameter and the textural promoter has mean pore diameters of 10-30 nm with Fischer-Tropsch catalyst nanoparticles of 6-10 nm diameter.

21. A method of claim 1 wherein the catalyst metal salt includes a cobalt salt in combination with Pt, Ru, and/or Pd salts and the textural promoter metal salt is from the group consisting of an aluminum salt, a titanium salt and combinations thereof.