Extruded Cu—Al—Mn hydrogenation catalyst

• US 10,639,616 B2
• Filed: 08/24/2015
• Issued: 05/05/2020
• Est. Priority Date: 09/12/2014
• Status: Active Grant

• Current Assignee: Clariant International AG (Clariant AG)
• Original Assignee: Clariant International AG (Clariant AG)
• Inventors: Paulus, Martin, Grossmann, Frank, Wegner, Oliver
• Primary Examiner(s): Li, Jun
• Application Number:
  US15/508,234
• Publication Number:
  US 20170252727A1
• Time in Patent Office: 1,716 Days
• CPC Class Codes: B01J 23/8892 Manganese
• CPC Class Codes: B01J 35/19 Catalysts containing parts with different compositions
• CPC Class Codes: B01J 35/30 characterised by their physical properties
• CPC Class Codes: B01J 35/31 Density
• CPC Class Codes: B01J 35/392 Metal surface area
• CPC Class Codes: B01J 35/40 characterised by dimensions, e.g. grain size in a colloidal state B01J35/23; crystallite size B01J35/77
• 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 35/66 Pore distribution
• CPC Class Codes: B01J 35/67 monomodal
• 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 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: B01J 37/0045 Drying a slurry, e.g. spray drying
• CPC Class Codes: B01J 37/03 Precipitation; Co-precipitation
• CPC Class Codes: B01J 37/031 Precipitation
• CPC Class Codes: B01J 37/04 Mixing B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/08 Heat treatment B01J37/0009, B01J37/0018 take precedence
• CPC Class Codes: B01J 37/16 Reducing
• CPC Class Codes: C07C 29/149 : with hydrogen or hydrogen-containing gases
• CPC Class Codes: C07C 31/125 : containing five to twenty-two carbon atoms

Abstract

The invention relates to Cu—Al—Mn shaped catalyst bodies in extruded form, and to a process for their preparation. The shaped catalyst body is suitable for the hydrogenation of organic compounds containing a carbonyl function, in particular for the hydrogenation of aldehydes, ketones and carboxylic acids and/or their esters. In particular, the shaped catalyst body is suitable for the hydrogenation of fatty acids or their esters, such as fatty acid methyl esters, to form the corresponding alcohols and dicarboxylic acid anhydrides, such as maleic anhydride, or esters of di-acids and di-alcohols, such as butane diol.

Claims

1. A shaped catalyst body, comprising Cu in an amount in the range of 20-43 wt %, Al in an amount in the range of 20-40 wt %, and Mn in an amount in the range of 1-10 wt %, based on the total weight of the shaped catalyst body,

wherein the shaped catalyst body has a pore volume in the range from 250 to 700 mm³/g, determined by mercury intrusion to DIN 66133, and

wherein the shaped catalyst body has a monomodal pore radius distribution and wherein 50% or more of the pore volume is formed by pores having a pore radius in the range from 7 to 40 nm, the pore radius distribution and the pore volume being determined by mercury intrusion to DIN 66133, and

wherein the shaped catalyst body in reduced form has a Cu metal surface, based on the amount of Cu in the shaped catalyst body, in the range from 20 m²/g_Cu to 60 m²/g_Cu, determined by N₂O pulse chemisorption, and

wherein the shaped catalyst body has a bulk density in the range from 300 to 800 g/L, determined to DIN ISO 903, and

wherein the shaped catalyst body is in the form of an calcined extrudate and has a side crushing strength, based on the length of the extrudates, in the range from 5 to 40 N/mm, the side crushing strength being determined to DIN EN 1094-5,

the shaped catalyst body being made by a process comprising

(a) providing a copper, manganese and aluminum-containing dried precipitate,

(b) forming a mixture of the dry precipitate of (a) with an aluminum-containing binder selected from the group consisting of boehmite and pseudoboehmite, the aluminum-containing binder being peptized by treatment with acid,

(c) extruding the mixture obtained in (b), to provide an extrudate, and

(d) calcining the extrudate obtained in (c), at a temperature in the range from 300 to 750°

C. to give a calcined extrudate.

2. The shaped catalyst body as claimed in claim 1, wherein the shaped catalyst body has a monomodal pore radius distribution and wherein 80% or more of the pore volume is formed by pores having a pore radius in the range from 7 to 40 nm, the pore radius distribution and the pore volume being determined by mercury intrusion to DIN 66133.

3. The shaped catalyst body as claimed in claim 1, having a bulk density in the range from 400 to 700 g/L, determined to DIN ISO 903.

4. The shaped catalyst body as claimed in claim 1, comprising at least one further metal selected from the group consisting of alkali metal, alkaline earth metal, rare earths, Fe, Ni, Cr, Co, Zn, and Zr.

5. The shaped catalyst body as claimed in claim 1, wherein the shaped body has a side crushing strength, based on the length of the extrudates, in the range from 10 to 30 N/mm, the side crushing strength being determined to DIN EN 1094-5.

6. The shaped catalyst body as claimed in claim 1, wherein the shaped body has a diameter in the range from 1 to 6 mm.

7. The shaped catalyst body as claimed in claim 1, wherein the shaped body has grooves in longitudinal direction having a depth in the range from 0.3 mm to 0.9 mm, and a width in the range from 1.0 to 1.5 mm.

8. The shaped catalyst body as claimed in claim 1, wherein the shaped catalyst body in reduced form has a Cu metal surface, based on the amount of Cu in the shaped catalyst body, in the range from 25 m²/g_Cu to 50 m²/g_Cu, determined by N₂O pulse chemisorption.

9. A process for producing an extruded shaped catalyst body according to claim 1, comprising the:

(a) combining (i) at least one aqueous solution of copper compounds, aluminum compounds, manganese compounds, and optionally transition metal compounds and (ii) at least one aqueous carbonate-containing solution to form a precipitate, isolating the precipitate, optionally washing the isolated precipitate, and drying the isolated precipitate to give a dried precipitate,

(b) forming a mixture of the dry precipitate obtained in (a) with an aluminum-containing binder selected from the group consisting of boehmite and pseudoboehmite, the aluminum-containing binder being peptized by treatment with acid,

(c) extruding the mixture obtained in step (b), to give an extrudate, and

(d) calcining the extrudate obtained in step (c), at a temperature in the range from 300 to 750°

C. to give a calcined extrudate.

10. The process as claimed in claim 9, wherein step (b) comprises:

(b1) calcining dried precipitate obtained in step (a) at a temperature in the range from 250°

C. to 900°

C. to give a calcined precipitate,

(b2) mixing dried precipitate obtained in step (a) with calcined precipitate obtained in step (b1) in a weight ratio of dried precipitate to calcined precipitate in the range from 2;

98 to 98;

2, to give a mixture, and

(b3) forming a mixture of the mixture obtained in step (b2) with an aluminum-containing binder selected from the group consisting of boehmite and pseudoboehmite, the aluminum-containing binder being peptized by treatment with acid.

11. The process as claimed in claim 9, wherein the aluminum-containing binder is peptized by addition of an acid before the aluminum-containing binder is mixed with the dry precipitate.

12. The process as claimed in claim 9, wherein the acid is selected from the group consisting of acetic acid and citric acid.

13. The process as claimed in claim 9, wherein the binder has a pore volume in the range of 300-700 mm³/g the pore volume being determined by mercury intrusion to DIN 66133.

14. A shaped catalyst body according to claim 1, wherein providing the copper, manganese and aluminum-containing dried precipitate

comprises combining (i) at least one aqueous solution of copper compounds, aluminum compounds, manganese compounds, and optionally transition metal compounds and (ii) at least one aqueous carbonate-containing solution to form a precipitate, isolating the precipitate, optionally washing the isolated precipitate, and drying the isolated precipitate to give a dried precipitate.

15. The shaped catalyst body according to claim 1, wherein Cu is present in an amount in the range of 24-42 wt %, Al is present in an amount in the range of 25-34 wt %, and Mn is present in the range of 2-8 wt %.

16. The shaped catalyst body according to claim 1, wherein the Cu is essentially in the form of copper oxide, copper-aluminum spinel, copper-manganese spinel, or any mixture of two or more thereof;

the Al is essentially in the form of aluminum oxide, copper-aluminum spinel, or a mixture thereof, and the Mn is essentially in the form of manganese oxide, copper-magnesium spinel, or a mixture thereof.

17. A shaped catalyst body, comprising Cu in an amount in the range of 24-42 wt %, Al in an amount in the range of 25-34 wt %, and Mn in an amount in the range of 2-8 wt %, based on the total weight of the shaped catalyst body,

wherein the shaped catalyst body has a pore volume in the range from 250 to 700 mm³/g, determined by mercury intrusion to DIN 66133, and

wherein the shaped catalyst body has a monomodal pore radius distribution and wherein 50% or more of the pore volume is formed by pores having a pore radius in the range from 7 to 40 nm, the pore radius distribution and the pore volume being determined by mercury intrusion to DIN 66133, and

wherein the shaped catalyst body is in the form of a calcined extrudate and has a side crushing strength, based on the length of the extrudates, in the range from 5 to 40 N/mm, the side crushing strength being determined to DIN EN 1094-5.

18. A shaped catalyst body according to claim 17, wherein the shaped catalyst body has a diameter in the range from 1 to 6 mm.

19. A shaped catalyst body in extruded form, comprising Cu in an amount in the range of 20-43 wt %, Al in an amount in the range of 20-40 wt %, and Mn in an amount in the range of 1-10 wt %, based on the total weight of the shaped catalyst body in extruded form,

wherein the shaped catalyst body has a pore volume in the range from 250 to 700 mm³/g, determined by mercury intrusion to DIN 66133, and

wherein the shaped catalyst body is in the form of a calcined extrudate and has a side crushing strength, based on the length of the extrudates, in the range from 5 to 40 N/mm, the side crushing strength being determined to DIN EN 1094-5, and

wherein the shaped catalyst body has a monomodal pore radius distribution and wherein 50% or more of the pore volume is formed by pores having a pore radius in the range from 7 to 40 nm, the pore radius distribution and the pore volume being determined by mercury intrusion to DIN 66133, and

wherein the shaped catalyst body is obtained by a process comprising:

(a) combining (i) at least one aqueous solution of copper compounds, aluminum compounds, manganese compounds, and optionally transition metal compounds and (ii) at least one aqueous carbonate-containing solution to form a precipitate, isolating the precipitate, optionally washing the isolated precipitate, and drying the isolated precipitate to give a dried precipitate,

(b1) calcining dried precipitate obtained in step (a) at a temperature in the range from 250°

C. to 900°

C. to give a calcined precipitate,

(b2) mixing dried, uncalcined precipitate obtained in step (a) with calcined precipitate obtained in step (b1) in a weight ratio of dried precipitate to calcined precipitate in the range from 2;

98 to 98;

2, to give a mixture, and

(b3) forming a mixture of the mixture obtained in step (b2) with an aluminum-containing binder selected from the group consisting of boehmite and pseudoboehmite, the aluminum-containing binder being peptized by treatment with acid,

(c) extruding the mixture obtained in step (b), to give an extrudate, and

(d) calcining the extrudate obtained in step (c), at a temperature in the range from 300 to 750°

C. to give the calcined extrudate.