Copper catalyst for dehydrogenation application

• US 8,828,903 B2
• Filed: 04/15/2009
• Issued: 09/09/2014
• Est. Priority Date: 11/10/2008
• Status: Active Grant

• Current Assignee: BASF Corporation (BASF SE)
• Original Assignee: BASF Corporation (BASF SE)
• Inventors: Chen, Jianping
• Primary Examiner(s): Mayes, Melvin C
• Assistant Examiner(s): NGUYEN, COLETTE B
• Application Number:
  US12/424,014
• Publication Number:
  US 20100121080A1
• Time in Patent Office: 1,973 Days
• Field of Search: 502/300, 502/346, 502/348, 502/355
• US Class Current: 502/244
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B01J 35/66 Pore distribution
• 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: C07D 307/33 in position 2, the oxygen atom being in its keto or unsubstituted enol form

Abstract

Disclosed are catalytic compositions having from about 35% to about 75% of Cu by weight, from about 15% to about 35% of Al by weight, and about 5% to about 20% of Mn by weight. The catalytic compositions are bulk homogeneous compositions formed from extruding and calcinating a powder formed from a precipitation reaction of Cu(NO₃)₂, Mn(NO₃)₂, Na₂Al₂O₃. The catalytic compositions have one or more crystalline phases of one or more of CuO and Cu_xMn_(3-x)O₄, where x is from about 1 to about 1.5, or both. The catalytic compositions are useful for the conversion of 1,4-butane-di-ol to γ-butyrolactone by a dehydrogenation reaction.

Claims

1. A catalytic composition for converting 1,4-butanediol to γ

-butyrolactone comprising from about 35% to about 75% by weight of Cu, from about 15% to about 35% by weight of Al, and from about 5% to about 25% by weight of Mn, wherein the catalytic composition has two or more crystalline phases and has an x-ray diffraction pattern with peaks at the following 2-theta values when measured using Cu Kα

radiation;

18.5° and

63.4°

.

2. The catalytic composition of claim 1, wherein the catalytic composition does not contain an inert support phase.

3. The catalytic composition of claim 1, having an x-ray diffraction pattern with peaks at the following 2-theta values when measured using Cu Kα

radiation;

18.5°

, 57.7° and

63.4°

.

4. The catalytic composition of claim 1, wherein the bulk density is from about 0.4 to about 0.8 g/mL.

5. The catalytic composition of claim 1 wherein, the catalytic composition comprises from about 40% to about 65% by weight of Cu, from about 20% to about 35% by weight of Al, and from about 10% to about 20% by weight of Mn and having an x-ray diffraction pattern as shown in FIG. 1.

6. A method for converting 1,4-butanediol to γ

-butyrolactone, comprising;

contacting a catalytic composition of comprising from about 35% to about 75% by weight of Cu, from about 15% to about 35% by weight of Al, and from about 5% to about 25% by weight of Mn, wherein the catalytic composition has two or more crystalline phases and has an x-ray diffraction pattern with peaks at the following 2-theta values when measured using Cu Kα

radiation;

18.5° and

63.4°

, with 1,4-butanediol; and

recovering γ

-butyrolactone.

7. The method of claim 6, wherein 1,4-butanediol is contacted in the gas phase at a pressure from about 20 to about 200 psig and a temperature from about 150 to about 300°

C.

8. The method of claim 6, wherein at least about 90% of 1,4-butanediol is converted to γ

-butyrolactone.

9. The method of claim 6, further comprising supplying 1,4-butanediol in a liquid phase and vaporizing the liquid 1,4-butanediol prior to contacting the 1,4-butanediol with the catalytic composition, wherein the liquid 1,4-butanediol is supplied at a LHSV from about 0.1 to about 3 h⁻

1.

10. The method of claim 9, wherein the 1,4-butanediol is supplied at a LHSV from about 0.75 to about 2 h⁻

1 and at least about 95% of the 1,4-butanediol is converted into γ

-butyrolactone.

11. The method of claim 9, wherein the 1,4-butanediol is supplied at a LHSV from about 1 to about 2 h⁻

1 and at least about 98% of the 1,4-butanediol is converted into γ

-butyrolactone.

12. The method of claim 9, wherein the 1,4-butanediol is supplied at a LHSV from about 0.75 to about 1 h⁻

1 and at least about 99% of the 1,4-butanediol is converted into γ

-butyrolactone.

13. The method of claim 9, wherein the method is associated with an observed kinetic rate constant that is calculated from the LHSV of supplied 1,4-butanediol and the percent of 1,4-butanediol is converted to γ

-butyrolactone (BDO %_conversion) according Formula I;

14. The method of claim 13, wherein the change in the observed rate constant is less than about 0.05% per hour.

15. A method for producing a copper catalyst, comprising:

co-precipitating a solid catalyst composition from solutions containing a soluble copper salt, a soluble manganese salt, and a soluble aluminum compound at a pH of about at about 6 to about 8.5; and

calcining the solid catalyst composition under air from about 400 to about 700°

C. for a time period from about 2 to about 5 hours;

wherein the solid catalyst composition comprises from about 35% to about 75% by weight of Cu, from about 15% to about 35% by weight of Al, and from about 5% to about 25% by weight of Mn;

wherein the catalytic composition has two or more crystalline phases and has an x-ray diffraction pattern with peaks at the following 2-theta values when measured using Cu Kα

radiation;

18.5° and

63.4°

.

16. The method of claim 15, wherein the co-precipitation is performed by adding an aqueous solution comprising copper (II) nitrate and manganese (II) nitrate, an aqueous solution comprising sodium aluminate, and an aqueous solution comprising sodium carbonate to an aqueous media at a controlled rate.

17. The method of claim 15, further comprising optionally drying the catalytic composition, adding water to the catalytic composition to form a mixture of catalytic composition plus water, mixing the mixture of catalytic composition plus water until densification occurs, and extruding the mixture of catalytic composition plus water to form a smooth extrudate before calcining the catalytic composition.

18. The method of claim 17, further comprising performing an additional calcining of the catalytic composition before mixing the catalytic composition to densification, wherein the additional calcining is performed under air from about 400 to about 700°

C. for a time period from about 2 to about 5 hours.