Process for hydrogenating 4,4'-methylenedianiline

Patent metadata

Field	Value
Publication number	US-2016326094-A1
Application number	US-201415103789-A
Country	US
Kind code	A1
Filing date	Dec 10, 2014
Priority date	Dec 11, 2013
Publication date	Nov 10, 2016
Grant date	—

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

1 : A process for hydrogenating at least one of 4,4′-methylenedianiline and polymeric MDA, comprising:
hydrogenating at least one of 4,4′-methylenedianiline and polymeric MDA with hydrogen in the presence of a catalyst, wherein the catalyst comprises ruthenium on a zirconium oxide support material.

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

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

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

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

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

7 : 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.

8 : 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.

9 : 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.

10 : The process according to claim 1 , wherein the zirconium oxide support material has
a BET surface area of from 30 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 .

11 : The process according to claim 1 , wherein the catalyst has
a BET surface area of from 30 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 .

12 : 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.

13 : 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.

14 : 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.

15 : 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.

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 - 21 . (canceled)

22 : The process according to claim 1 , wherein a mixture obtained from said hydrogenating comprises isomers of 4,4′-diaminodicyclohexylmethane, polymeric MDA comprising isomeric units of 4,4′-diaminodicyclohexylmethane repeating units, or a combination thereof,
i) wherein said mixture comprises the trans, trans isomer of 4,4′-diaminodicyclohexylmethane in an amount of from 10 to 30 wt %,
the cis, trans isomer of 4,4′-diaminodicyclohexylmethane in an amount of from 30 to 55 wt %, and
the cis, cis isomer of 4,4′-diaminodicyclohexylmethane in an amount of from 10 to 50 wt %, in each case based on the total amount of all isomers present, and
the sum of the isomers present in the mixture is 100 wt %;
ii) wherein said mixture comprises polymeric MDA, where the trans, trans isomeric unit of 4,4′-diaminodicyclohexylmethane is present in an amount of from 10 to 30 wt %,
the cis, trans isomeric unit of 4,4′-diaminodicyclohexylmethane is present in an amount of from 30 to 55 wt %, and
the cis, cis isomeric unit of 4,4′-diaminodicyclohexylmethane is present in an amount of from 10 to 50 wt %, in each case based on the total amount of all isomers present where the sum of the isomeric units present in the mixture is 100 wt %, or
iii) a combination of i) and ii).

23 : The process according to claim 1 , wherein a mixture obtained from said hydrogenating comprises isomers of 4,4′-diaminodicyclohexylmethane in monomeric or polymeric form, wherein the mixture has a melting point of less than 40° C.

24 : A method of making a compound, comprising
reacting a mixture obtained by the process of claim 22 to obtain a compound, wherein said compound is a surfactant, a medicament, a crop protection agent, a stabilizer, a polymer, a polyamide, 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 as a starter for urea and 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