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

Patent metadata

Field	Value
Publication number	US-2017158798-A1
Application number	US-201515323999-A
Country	US
Kind code	A1
Filing date	Jul 2, 2015
Priority date	Jul 7, 2014
Publication date	Jun 8, 2017
Grant date	—

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

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 is selected from the group consisting of
A) alkaline-treated zeolite catalysts, wherein the alkaline treatment of BEA zeolites is carried out in the presence of a pore-directing agent and of zeolites other than BEA zeolites is carried out in the presence or absence of a pore-directing agent,
and
B) acid-treated zeolite catalysts without any alkaline treatment preceding or following said acid treatment, wherein the acid treatment is effected with an organic acid with chelating function.

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 a 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 organic acid with chelating function is selected from the group consisting of ethylene diamine tetra acetic acid (EDTA), citric acid, oxalic acid and mixtures thereof.

4 . The process according to claim 3 , wherein said organic acid with chelating function is contacted with said at least one solid zeolite catalyst in the form of an aqueous solution of said organic acid with chelating function 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.

5 . 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.

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

7 . 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.

8 . 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.

9 . 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.

10 . The process according to claim 9 , 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.

11 . 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.

12 . The process according to claim 11 , 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.

13 . 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.

14 . The process according to claim 13 , 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.

15 . The Process according to claim 1 , wherein the respective treatment of alkaline-treated zeolite catalysts A) or of acid-treated zeolite catalysts B) is performed such that the zeolite catalyst obtained after completion of the respective 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.

16 . 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

• C08G12/08 Primary

  aromatic · CPC title

• B01J29/7007

  Zeolite Beta · CPC title

• B01J29/70

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

• B01J29/18

  of the mordenite type · CPC title

• C07C209/78 Primary

  from carbonyl compounds, e.g. from formaldehyde, and amines having amino groups bound to carbon atoms of six-membered aromatic rings, with formation of methylene-diarylamines · CPC title