Process for the production of di- and polyamines of the diphenylmethane series

Patent metadata

Field	Value
Publication number	US-10239984-B2
Application number	US-201515323999-A
Country	US
Kind code	B2
Filing date	Jul 2, 2015
Priority date	Jul 7, 2014
Publication date	Mar 26, 2019
Grant date	Mar 26, 2019

Abstract

The invention relates to a production process for polyamines through condensation of aromatic amines with formaldehyde employing at least one solid zeolite catalyst partially or fully ion-exchanged to the protonic form which has been
A) alkaline-treated, wherein the alkaline treatment is in case of BEA zeolites carried out in the presence of a pore-directing agent and in case of zeolites other than BEA zeolites in the presence or absence of a pore-directing agent,

or
B) acid-treated without any alkaline treatment preceding or following said acid treatment, wherein the acid treatment is effected with an organic acid with chelating function.

First claim

The invention claimed is:

1. A process for the preparation of di- and polyamines of the diphenylmethane series comprising rearranging a condensation product, wherein said condensation product is formed by reacting aniline and a methylene group-supplying agent, and wherein said condensation product is reacted in the presence of at least one solid zeolite catalyst which is partially or fully ion-exchanged to the protonic form and comprises
A) at least one alkaline-treated zeolite catalyst, wherein the alkaline treatment of BEA zeolites is carried out in the presence of a pore-directing agent and the alkaline treatment of zeolites other than BEA zeolites is carried out in the presence or absence of a pore-directing agent.

2. The process according to claim 1 , wherein said alkaline-treated zeolite catalyst A) is selected from the group consisting of:
(i) zeolites other than BEA zeolites which have been alkaline-treated in the presence or absence of a pore-directing agent;
(ii) BEA zeolites which have been alkaline-treated in the presence of a pore-directing agent;
(iii) zeolites which have been acid-treated in a first step and alkaline-treated in a second step;
(iv) zeolites which have been alkaline-treated in a first step and acid-treated in a second step;
(v) zeolites which have been acid-treated in a first step, alkaline treated in a second step and acid-treated in a third step;
and
(vi) mixtures thereof.

3. The process according to claim 1 , wherein said pore-directing agent comprises an alkylammonium cation having the general molecular formula + NR i 4 , wherein the four R i substituents can be the same or different and can be selected from the group consisting of organic substituents and hydrogen.

4. The process according to claim 1 , wherein said at least one-solid zeolite catalyst comprises a FAU type zeolite.

5. The process according to claim 2 , wherein said alkaline-treated zeolite catalyst A) comprises (i) a zeolite other than a BEA zeolite in which the alkaline treatment is carried out in a pH range of 10 to 15 using an alkali metal hydroxide solution at a temperature of from 10° C. to 100° C. for a period of from 0.1 minutes to 180 minutes with a zeolite loading of 5 g L −1 to 400 g L −1 , in which “L” refers to the volume of the total reaction mixture.

6. The process according to 2 , wherein said alkaline-treated zeolite catalyst A) comprises (ii) a BEA zeolite in which the alkaline treatment is carried out in a pH range of 10 to 15 using an alkali metal hydroxide solution at a temperature of from 10° C. to 100° C. for a period of from 0.1 minutes to 180 minutes with a zeolite loading of 5 g L −1 to 400 g L −1 , in which “L” refers to the volume of the total reaction mixture.

7. The process according to claim 2 , wherein said alkaline-treated zeolite catalyst A) comprises (iii) a zeolite in which the acid treatment is carried out using an aqueous solution of an organic acid with chelating function or an aqueous solution of a mineral acid having a concentration of 0.01 mol L −1 to 1 mol L −1 at a temperature of from 10° C. to 100° C for a period of from 0.25 hours to 100 hours.

8. The process according to claim 7 , wherein said alkaline-treated zeolite catalyst A) comprises (iii) a zeolite in which the alkaline treatment following the acid treatment is carried out in a pH range of 10 to 15 using an alkali metal hydroxide solution at a temperature of from 10° C. to 100° C. for a period of from 0.1 minutes to 180 minutes with a zeolite loading of 5 g L −1 to 400 g L −1 , in which “L” refers to the volume of the total reaction mixture.

9. The process according to claim 2 , wherein said alkaline-treated zeolite catalyst A) comprises (iv) a zeolite in which the alkaline treatment is carried out in a pH range of 10 to 15 using an alkali metal hydroxide solution at a temperature of from 10° C. to 100° C. for a period of from 0.1 minutes to 180 minutes with a zeolite loading of 5 g L −1 to 400 g L −1 , in which “L” refers to the volume of the total reaction mixture.

10. The process according to claim 9 , wherein said alkaline-treated zeolite catalyst A) comprises (iv) a zeolite in which the acid treatment following the alkaline treatment is carried out using an aqueous solution of an organic acid with chelating function or an aqueous solution of a mineral acid having a concentration of 0.01 mol L −1 to 1 mol L −1 at a temperature of from 10° C. to 100° C. for a period of from 0.25 hours to 100 hours.

11. The process according to claim 2 , wherein said alkaline-treated zeolite catalyst A) comprises (v) a zeolite in which both acid treatments are carried out using an aqueous solution of an organic acid with chelating function or an aqueous solution of a mineral acid having a concentration of 0.01 mol L −1 to 1 mol L −1 at a temperature of from 10° C. to 100° C. for a period of from 0.25 hours to 100 hours.

12. The process according to claim 11 , wherein said alkaline-treated zeolite catalyst A) comprises (v) a zeolite in which the alkaline treatment between the acid treatments is carried out in a pH range of 10 to 15 using an alkali metal hydroxide solution at a temperature of from 10° C. to 100° C. for a period of from 0.1 minutes to 180 minutes with a zeolite loading of 5 g L −1 to 400 g L −1 , in which “L” refers to the volume of the total reaction mixture.

13. The process according to claim 1 , wherein the treatment of alkaline-treated zeolite catalysts A) is performed such that the zeolite catalyst obtained after completion of the treatment has a crystallinity as determined by X-ray diffraction analysis of at least 50% when compared to the parent zeolite catalyst before the respective treatment.

14. The process of claim 1 , wherein said methylene group supplying agent is selected from the group consisting of aqueous formaldehyde solution, gaseous formaldehyde, para-formaldehyde, trioxane and mixtures thereof.

Assignees

• Covestro Deutschland Ag

Inventors

• Arras Jürgen
• Wershofen Stefan
• Pérez-Ramirez Javier
• Keller Tobias Caesar

Classifications

• C07C211/50

  with at least two amino groups bound to carbon atoms of six-membered aromatic rings of the carbon skeleton · CPC title

• B01J29/08

  of the faujasite type, e.g. type X or Y · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• B01J29/70

  of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 · CPC title

• B01J29/7007

  Zeolite Beta · CPC title