Catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives and method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives using the same

Patent metadata

Field	Value
Publication number	US-11964259-B2
Application number	US-202017135515-A
Country	US
Kind code	B2
Filing date	Dec 28, 2020
Priority date	Dec 31, 2019
Publication date	Apr 23, 2024
Grant date	Apr 23, 2024

Abstract

A catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives is provided. The catalyst composition includes a carrier including aluminum oxide and magnesium oxide, a rhodium-ruthenium active layer loaded on the surface of the carrier, and a solvent including an organic amine. The weight percentage of magnesium oxide in the carrier is between 12% and 30%. A method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives using the catalyst composition is also provided.

First claim

What is claimed is:

1. A catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives, comprising:
a carrier comprising aluminum oxide and magnesium oxide, the carrier having a surface and an interior, wherein the magnesium oxide in the carrier has a weight percentage from 12% to 30%;
a rhodium-ruthenium active layer loaded on the surface of the carrier; and
a solvent comprising an organic amine.

2. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the magnesium oxide has a concentration which exhibits a decreasing gradient distribution from the surface to the interior of the carrier.

3. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the carrier has a specific surface area from 150 m 2 /g to 250 m 2 /g.

4. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the weight percentage of the magnesium oxide in the carrier is in a range from 14% to 25%.

5. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the interior of the carrier consists of the aluminum oxide, and the surface of the carrier consists of magnesium aluminum oxide.

6. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 5 , wherein magnesium oxide and aluminum oxide in the magnesium aluminum oxide have a weight ratio from 2:1 to 1:2.

7. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 5 , wherein the magnesium aluminum oxide in the carrier has a weight percentage from 20% to 50%.

8. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein rhodium and ruthenium in the rhodium-ruthenium active layer have a weight ratio from 40:60 to 10:90.

9. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the rhodium-ruthenium active layer and the carrier have a weight ratio from 1:24 to 1:16.

10. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the organic amine comprises aniline, cyclohexylamine, dicyclohexyl amine, o-toluidine, 2-methylaniline, 2-methylcyclohexylamine, 2,6-dimethylaniline, 2,6-dimethylcyclohexylamine, 2-ethyl-6-methyl aniline, 2-ethyl-6-methylcyclohexylamine, 4,4′-methyl ene bis(cyclohexylamine) derivatives, or a combination thereof.

11. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 10 , wherein the 4,4′-methylene bis(cyclohexylamine) derivatives are represented by formula (I):

wherein R1, R2, R3 and R4, independently, comprise H, CH 3 , C 2 H 5 or C 3 H 7 .

12. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the solvent further comprises tetrahydrofuran (THF).

13. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the solvent does not comprise tetrahydrofuran, alcohols or ethers.

14. The catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 , wherein the 4,4′-methylenedianiline derivatives comprise substituted or unsubstituted 4,4′-methylenedianiline.

15. A method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives, comprising:
placing a catalyst composition for hydrogenating 4,4′-methylenedianiline derivatives as claimed in claim 1 in a reactor; and
introducing 4,4′-methylenedianiline derivatives and hydrogen into the reactor to proceed a hydrogenation reaction to prepare 4,4′-methylene bis(cyclohexylamine) derivatives.

16. The method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives as claimed in claim 15 , wherein the reactor comprises a continuous reactor.

17. The method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives as claimed in claim 15 , wherein the reactor comprises a trickle-bed reactor, a bubble-cap column reactor, or a loop reactor.

18. The method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives as claimed in claim 15 , wherein the hydrogenation reaction has a hydrogen pressure from 60 bar to 80 bar.

19. The method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives as claimed in claim 15 , wherein the hydrogenation reaction has a temperature from 100° C. to 160° C.

20. The method for preparing 4,4′-methylene bis(cyclohexylamine) derivatives as claimed in claim 15 , wherein the 4,4′-methylenedianiline derivatives are represented by formula (II):

wherein R1, R2, R3 and R4, independently, comprise H, CH 3 , C 2 H 5 or C 3 H 7 .

Assignees

• Ind Tech Res Inst

Inventors

• Chen Chao-Huang
• Wu Jyun-Da
• Lu Tzong-Shyan
• Lee Ying-Chieh

Classifications

• B01J23/464 Primary

  Rhodium · CPC title

• B01J8/0242

  the fluid flow within the bed being predominantly vertical · CPC title

• B01J21/10

  Magnesium; Oxides or hydroxides thereof · CPC title

• B01J35/615

  100-500 m2/g · CPC title

• B01J37/0234

  Impregnation and coating simultaneously · CPC title