Process for hydrogenating 4,4′-methylenedianiline

Patent metadata

Field	Value
Publication number	US-9873658-B2
Application number	US-201415103789-A
Country	US
Kind code	B2
Filing date	Dec 10, 2014
Priority date	Dec 11, 2013
Publication date	Jan 23, 2018
Grant date	Jan 23, 2018

Abstract

The present invention relates to a process for hydrogenating 4,4′-methylenedianiline and/or polymeric MDA with hydrogen in the presence of a catalyst comprising ruthenium on a zirconium oxide support material, and also to the use of a catalyst comprising ruthenium on a zirconium oxide support material for hydrogenating 4,4′-methylenedianiline and/or polymeric MDA.

First claim

The invention claimed is:

1. A process for hydrogenating at least one of 4,4′-methylenedianiline and polymeric methylenedianiline, the process comprising:
hydrogenating at least one of 4,4′-methylenedianiline and polymeric methylenedianiline with hydrogen in the presence of a catalyst,
wherein
the catalyst comprises ruthenium on a zirconium oxide support material, and
the zirconium oxide support material has a BET surface area of from 73 to 300 m 2 /g.

2. The process according to claim 1 , which is carried out in suspension or in a fixed bed.

3. The process according to claim 2 , wherein the zirconium oxide support material of the catalyst, present as a fixed bed catalyst, has a pore size distribution where more than 50% of the pores present are formed by mesopores having a diameter of from 2 nm to 50 nm and the remainder to 100% are formed by macropores having a diameter of >50 nm.

4. The process according to claim 2 , wherein the catalyst, present as a fixed bed catalyst, has a pore size distribution where more than 50% of the pores present are formed by mesopores having a diameter of from 2 nm to 50 nm and the remainder to 100% are formed by macropores having a diameter of >50 nm.

5. The process according to claim 2 , wherein the zirconium oxide support material of the catalyst, present as a suspension catalyst, has a pore size distribution where more than 40% of the pores present are macropores having a diameter of >50 nm and the remainder to 100% are formed by mesopores having a diameter of from 2 nm to 50 nm.

6. The process according to claim 2 , wherein the catalyst, present as a suspension catalyst, has a pore size distribution where more than 40% of the pores present are formed by macropores having a diameter of >50 nm and the remainder to 100% are formed by mesopores having a diameter of from 2 nm to 50 nm.

7. The process according to claim 1 , which is carried out as a continuous operation or batchwise.

8. The process according to claim 2 , which is carried out in a fixed bed at a temperature of from 50 to 190° C.

9. The process according to claim 2 , which is carried out in suspension at a temperature of from 50 to 190° C.

10. The process according to claim 1 , which is carried out at a pressure of from 60 to 300 bar.

11. The process according to claim 1 , wherein the catalyst comprises ruthenium in an amount of from 0.05 to 20 wt % based on the whole catalyst.

12. The process according to claim 1 , wherein the zirconium oxide support material is present in at least one of a monoclinic phase, a tetragonal phase, a cubic phase and an amorphous phase.

13. The process according to claim 1 , wherein the zirconium oxide support material is present in at least one of a monoclinic phase and a tetragonal phase.

14. The process according to claim 1 , wherein the zirconium oxide support material has
a pore volume of from 0.1 to 1 cm 3 /g, and
a tamped density of from 500 to 2000 kg/m 3 .

15. The process according to claim 1 , wherein the catalyst has
a BET surface area of from 78 to 300 m 2 /g,
a pore volume of from 0.1 to 1 cm 3 /g, and
a tamped density of from 500 to 2000 kg/m 3 .

16. The process according to claim 1 , wherein the reaction time of said hydrogenating is from 10 to 400 min.

17. The process according to claim 1 , wherein said hydrogenating is carried out in an organic solvent.

18. The process according to claim 1 ,
wherein a mixture is obtained from said hydrogenating and comprises
isomers of 4,4′-diaminodicyclohexylmethane when 4,4′-methylenedianiline is hydrogenated, and
oligomeric or polymeric ring-hydrogenated compounds when the polymeric methylenedianiline is hydrogenated;

wherein the isomers of 4,4′-diaminodicyclohexylmethane comprise trans, trans isomer of 4,4′-diaminodicyclohexylmethane in an amount of from 10 to 30 wt %, cis, trans isomer of 4,4′-diaminodicyclohexylmethane in an amount of from 30 to 55 wt %, and cis, cis isomer of 4,4′-diaminodicyclohexylmethane in an amount of from 10 to 50 wt %, based on a total amount of all isomers present; and
wherein the oligomeric or polymeric ring-hydrogenated compounds comprise trans, trans isomeric unit of 4,4′-diaminodicyclohexylmethane in an amount of from 10 to 30 wt %, cis, trans isomeric unit of 4,4′-diaminodicyclohexylmethane in an amount of from 30 to 55 wt %, and cis, cis isomeric unit of 4,4′-diaminodicyclohexylmethane in an amount of from 10 to 50 wt %, based on a total amount of all isomeric repeating units.

19. The process according to claim 1 , wherein a mixture obtained from said hydrogenating
comprises isomers of 4,4′-diaminodicyclohexylmethane when 4,4′-methylenedianiline is hydrogenated and oligomeric or polymeric ring-hydrogenated compounds when the polymeric methylenedianiline is hydrogenated, and
has a melting point of less than 40° C.

20. A method of making a compound, the method comprising
reacting a mixture obtained by the process of claim 18 to obtain the compound, which is a surfactant, a medicament, a crop protection agent, a stabilizer, a polymer, a polyimide, an isocyanate, a hardener for an epoxy resin, a catalyst for polyurethane synthesis, an intermediate for preparing a quaternary ammonium compound, a plasticizer, a corrosion inhibitor, a synthetic resin, an ion exchanger, a textile auxiliary, a dye, a vulcanization accelerant, an emulsifier, or a starter for urea or polyurea synthesis.

Assignees

• Basf Se

Inventors

• Weickgenannt Andreas
• Schaack Bernd Bastian
• Wucher Barbara
• Panchenko Alexander
• Hettche Frank
• Bock Martin
• Tan Aik Meam
• Dahmen Kirsten

Classifications

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• B01J37/08

  Heat treatment {(B01J37/0009, B01J37/0018 take precedence)} · CPC title

• B01J37/18

  with gases containing free hydrogen · CPC title

• B01J37/0236

  Drying, e.g. preparing a suspension, adding a soluble salt and drying · CPC title

• B01J37/0225

  of metal substrates · CPC title