EXTRUDED Cu-Al-Mn HYDROGENATION CATALYST

• US 20170252727A1
• Filed: 08/24/2015
• Published: 09/07/2017
• 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
• Granted Patent: US 10,639,616 B2
• Time in Patent Office: 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 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.

2. The shaped catalyst body as claimed in claim 1, 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.

3. The shaped catalyst body as claimed in claim 1, having a bulk density in the range from 300 to 800 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 5 to 40 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 20 m²/gCu to 60 m²/gCu, determined by N₂O pulse chemisorption.

18. A hydrogenated carbonyl compounds compound manufactured using a shaped catalyst body as claimed in claim 1.

9. A process for producing an extruded shaped catalyst body, comprising the steps of:

(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) mixing the dry precipitate obtained in step (a) with an aluminum-containing binder selected from the group consisting of boehmite and pseudoboehmite,

(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 an extruded shaped catalyst body.

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) mixing the mixture obtained in step (b2) with an aluminum-containing binder selected from the group consisting of boehmite and pseudoboehmite.

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

12. The process as claimed in claim 11, wherein the organic acid is selected from the group consisting of acetic acid and citric acid.

13. The process as claimed in claim 9, wherein the mixture obtained from step (b) or step (b3) is admixed, prior to extrusion, with a lubricant in an amount in the range from 0.1 to 5 wt %, based on the total weight of the material to be extruded.

14. 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.

15. The process as claimed in claim 9, wherein the binder has a particle size D₅₀ in the range from 10 to 40 μ

m, determined by the laser diffraction method to DIN ISO 13320.

16. The process as claimed in claim 9, comprising the step of:

(e) reducing the extruded shaped catalyst body obtained in step (d) to give a reduced shaped catalyst body.

17. A shaped catalyst body obtained by a the process as claimed in claim 9.