Preparation and use of non-chrome catalysts for Cu/Cr catalyst applications

• US 6,455,464 B1
• Filed: 09/18/1998
• Issued: 09/24/2002
• Est. Priority Date: 03/21/1996
• Status: Expired due to Term

• Current Assignee: Engelhard Corporation (BASF SE)
• Original Assignee: Engelhard Corporation (BASF SE)
• Inventors: Chen, Jianping
• Primary Examiner(s): Wood, Elizabeth D.
• Application Number:
  US09/142,987
• Time in Patent Office: 1,467 Days
• Field of Search: 502/344, 502/346, 502/355
• US Class Current: 502/346
• CPC Class Codes: B01D 53/86 Catalytic processes
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 23/002 Mixed oxides other than spinels, e.g. perovskite
• CPC Class Codes: B01J 23/005 Spinels
• CPC Class Codes: B01J 23/72 Copper
• CPC Class Codes: B01J 23/755 Nickel
• 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 23/8892 Manganese
• CPC Class Codes: B01J 2523/00 Constitutive chemical elements of heterogeneous catalysts
• CPC Class Codes: B01J 2523/17 Copper
• CPC Class Codes: B01J 2523/31 Aluminium
• CPC Class Codes: B01J 2523/3712 Cerium
• CPC Class Codes: B01J 2523/67 Chromium
• CPC Class Codes: B01J 35/60 characterised by their surface properties or porosity
• CPC Class Codes: B01J 35/613 10-100 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 35/651 50-500 nm
• CPC Class Codes: B01J 35/69 : bimodal
• CPC Class Codes: B01J 37/0009 : Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• CPC Class Codes: B01J 37/03 : Precipitation; Co-precipitation
• CPC Class Codes: B01J 37/031 : Precipitation
• CPC Class Codes: B01J 37/038 : to form slurries or suspensions, e.g. a washcoat
• CPC Class Codes: C01B 17/78 : characterised by the catalyst used
• CPC Class Codes: C07C 1/22 : by reduction
• CPC Class Codes: C07C 209/36 : by reduction of nitro groups bound to carbon atoms of six-membered aromatic rings in presence of hydrogen-containing gases and a catalyst
• CPC Class Codes: C07C 209/48 : by reduction of nitriles
• CPC Class Codes: C07C 231/065 : By hydration using metals or metallic ions as catalyst
• CPC Class Codes: C07C 2521/04 : Alumina
• CPC Class Codes: C07C 2523/72 : Copper
• CPC Class Codes: C07C 29/149 : with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 29/154 : containing copper, silver, gold, or compounds thereof
• CPC Class Codes: C07C 31/04 : Methanol
• CPC Class Codes: C07C 31/125 : containing five to twenty-two carbon atoms
• CPC Class Codes: C07C 37/16 : by condensation involving hydroxy groups of phenols or alcohols or the ether or mineral ester group derived therefrom
• CPC Class Codes: C07C 39/06 : Alkylated phenols
• CPC Class Codes: C07C 39/07 : containing only methyl groups, e.g. cresols, xylenols
• CPC Class Codes: C07D 301/32 : Separation; Purification
• CPC Class Codes: Y02P 20/52 : using catalysts, e.g. selective catalysts

Abstract

A non-chrome, copper-containing catalyst, Cu—Al—O and method of preparing the same are provided wherein the Cu—Al—O catalyst is prepared by the co-precipitation of copper nitrate (Cu(NO₃)₂) and sodium aluminate (Na₂Al₂O₄) solutions using sodium carbonate (Na₂CO₃) as a precipitant. the precipitate is filtered, washed to remove excess sodium, and dried. The dried product, to be used in a powder form, is calcined at a preferred temperature of approximately 700 to 900° C. for approximately 1 to 4 hours. The dry powder, to be tableted or extruded, is calcined at a temperature of approximately 400 to 700° C. The activity of the Cu—Al—O catalyst can be promoted in hydrogenolysis applications by the addition of various agents. The Cu—Al—O catalyst can be employed in applications in place of Cu/Cr, or other copper-based catalysts.

Claims

1. A catalyst having a homogeneous bulk composition, the catalyst consisting essentially of oxides of copper and aluminum, less than 60% of the catalyst by weight comprising a spinel structure, the catalyst having less than about 10% leachable copper ions as determined by reacting 100 ml 10% acetic acid with 10 g of powder catalyst for one hour with continuous stirring.

3. The catalyst of claim 1 having a calculated alumina content of about 20% to about 90% by weight and a calculated copper oxide content of about 80% to about 10% by weight.

4. The catalyst of claim 3 wherein the calculated alumina content is about 30% to about 60% by weight, and the calculated CuO content is about 70% to about 40% by weight.

5. The catalyst of claim 1 wherein at least a part of the alumina content and a part of the CuO content are CuAl₂O₄ in a spinel crystal structure, the spinel structure comprising less than 60% of the catalyst by weight.

7. The catalyst of claim 1 wherein the catalyst has less than about 5% leachable copper ions.

8. The catalyst of claim 1 wherein the catalyst is substantially free of chromium.

9. The catalyst of claim 1 further comprising a promoter, the promoter being present in an amount no greater than about 25% by weight of the catalyst.

10. The catalyst of claim 9 wherein the promoter is chosen from the group consisting of salts and oxides of Ce, Ba, Mn, Co, Zn, Ni, alkaline, and alkaline earth metals.

11. The catalyst of claim 10 wherein the promoter is chosen from the group consisting of salts and oxides of Ce, Mn, Ba and Ni.

14. The catalyst of claim 1 having the formula nCuO.Al₂O₃ wherein n is between 0.14 and 5.13.

25. The catalyst of claim 1 wherein the calculated CuO content is 61±

20%.

26. The catalyst of claim 1 having a surface area of about 15 to about 250 m²/g.

27. The catalyst of claim 26 having a surface area of from about 15 to about 170 m²/g.

2. A solid catalyst comprising a compressed homogeneous Cu—

Al—

O powder substantially free of chromium, the solid catalyst having a bimodal pore size distribution centering around 100 Å and

around 500 Å

to 2000 Å

.

6. The catalyst of claim 2 wherein the calculated CuO content is 61±

20%.

12. The catalyst of claim 2 having a surface area of about 15 to about 250 m²/g.

13. The catalyst of claim 12 having a surface area of from about 15 to about 170 m²/g.

15. The catalyst of claim 2 wherein the catalyst is a tablet formed with 0-8% lubricant.

16. The solid catalyst of claim 2 wherein the catalyst is a calcined extrudate of a Cu—

Al—

O powder.

17. The catalyst of claim 2 having a pore volume of approximately 0.15 ml/g to approximately 0.6 ml/g.

18. The solid catalyst of claim 2 having a bulk density of approximately 0.6 g/ml to approximately 1.5 g/ml.

19. The catalyst of claim 2 made from a powder having a homogeneous bulk composition, the catalyst consisting essentially of oxides of copper and aluminum, the catalyst having less than about 10% leachable copper ions as determined by reacting 100 ml 10% acetic acid with 10 g of powder catalyst for one hour with continuous stirring.

20. The catalyst of claim 2 further comprising a promoter, the promoter being present in an amount no greater than about 25% by weight of the catalyst.

28. The catalyst of claim 2 having a calculated alumina content of about 20% to about 90% by weight and a calculated copper oxide content of about 80% to about 10% by weight.

29. The catalyst of claim 28 wherein the calculated alumina content is about 30% to about 60% by weight, and the calculated CuO content is about 70% to about 40% by weight.

30. The catalyst of claim 2 wherein the catalyst is substantially free of chromium.

31. The catalyst of claim 20 wherein the promoter is chosen from the group consisting of salts and oxides of Ce, Ba, Mn, Co, Zn, Ni, alkaline, and alkaline earth metals.

32. The catalyst of claim 31 wherein the promoter is chosen from the group consisting of salts and oxides of Ce, Mn, Ba and Ni.

33. The catalyst of claim 2 having the formula nCuO.Al₂O₃ wherein n is between 0.14 and 5.13.

21. A solid extrudate of a catalyst having a homogeneous bulk composition, the catalyst consisting essentially of oxides of copper and aluminum, the extrudate being substantially free of binder and peptizer.

22. The extrudate of claim 21 further comprising a promoter, the promoter being present in an amount no greater than about 25% by weight of the catalyst.

23. The extrudate of claim 22 wherein the promoter is chosen from the group consisting of salts and oxides of Ce, Ba, Mn, and Ni.

24. The extrudate of claim 21 having a surface area of about 15 to about 250 m²/g.

34. The extrudate of claim 21 having the formula nCuO.Al₂O₃ wherein n is between 0.14 and 5.13.

35. The extrudate of claim 21 having a pore volume of approximately 0.15 ml/g to approximately 0.6 ml/g.

36. The extrudate of claim 21 having a bulk density of approximately 0.6 g/ml to approximately 1.5 g/ml.

37. The extrudate of claim 21 made from a powder having a homogeneous bulk composition, the catalyst consisting essentially of oxides of copper and aluminum, the catalyst having less than about 10% leachable copper ions as determined by reacting 100 ml 10% acetic acid with 10 g of powder catalyst for one hour with continuous stirring.

38. The extrudate of claim 21 wherein the catalyst has a bimodal pore size distribution centering around 100 Å

and around 500 Å

to 2000 Å

.