Method for producing aniline or an aniline conversion product

Patent metadata

Field	Value
Publication number	US-10703709-B2
Application number	US-201716311205-A
Country	US
Kind code	B2
Filing date	Jun 27, 2017
Priority date	Jun 29, 2016
Publication date	Jul 7, 2020
Grant date	Jul 7, 2020

Abstract

The invention relates to a method for producing aniline or products that are obtained by further chemical reaction of aniline (aniline derivatives), involving decarboxylation of aminobenzoic acid, particularly ortho-aminobenzoic acid, in which one portion of the previously formed crude aniline is recirculated in the decarboxylation step. The aminobenzoic acid is obtained enzymatically or chemically, preferably enzymatically.

First claim

The invention claimed is:

1. A method for producing aniline or an aniline conversion product, comprising:
(I) decarboxylating aminobenzoic acid to aniline in a reactor in the presence of a catalyst, wherein a stream containing aniline is withdrawn from the reactor;
(II) purifying a portion of the stream containing aniline withdrawn in step (I) to obtain aniline;
(III) recirculating another portion of the stream containing aniline withdrawn in step (I) into the reactor of step (I); and
(IV) optionally further reacting the aniline purified in step (II) to give an aniline conversion product.

2. The method of claim 1 , in which a further aniline stream of purified aniline is fed to the reactor of step (I) in addition to the stream containing aniline recirculated in step (III), wherein the aniline additionally fed in the further aniline stream accounts for at most 60% of the total aniline fed to the reactor of step (I).

3. The method of claim 2 , in which the concentration of aniline is monitored in the stream comprising aniline which is withdrawn from the reactor of step (I), and when a shortfall in the concentration of aniline of a previously set value is detected, the proportion of the further aniline stream of purified aniline additionally fed to the reactor is increased to a value of at most 60% of the aniline fed in total to the reactor of step (I).

4. The method of claim 1 , in which the stream containing aniline withdrawn from the reactor of step (I) is divided into two streams in a ratio by mass in the range from 9.0:1 to 1:9.0, of which one stream is fed to the recirculation of step (III) and the other stream is fed to the purification of step (II).

5. The method of claim 1 , in which step (I) is conducted at a temperature in the range from 140° C. to 240° C. and at an absolute pressure in the range from 1.00 bar to 20.0 bar.

6. The method of claim 1 , in which the reactor of step (I)
is a slurry phase reactor, and the catalyst is used at a concentration in the range from 0.100% by mass to 50.0% by mass, based on the total mass of the liquid reaction mixture
or
is a stirred tank reactor,
or
is a tubular reactor having a catalyst bed.

7. The method of claim 1 , in which the catalyst used in step (I) is a zeolite catalyst.

8. The method of claim 1 , in which the aminobenzoic acid to be decarboxylated in step (I) is provided by the following step (I-0) carried out prior to step (I):
(I-0) fermentation of a raw material, which comprises at least
one fermentable carbon-containing compound and
one nitrogen-containing compound,
in a fermentation reactor using microorganisms to obtain a fermentation broth; which is then optionally followed by the following work-up steps:
(α) removing the microorganism from the fermentation broth
and/or
(β) decolorizing the fermentation broth or, in the case of step (α) being carried out, the fermentation broth depleted of microorganisms obtained in step (α).

9. The method of claim 8 , in which the following step is carried out after step (I-0) and prior to step (I):
(I-0) (a) enrichment of the aminobenzoic acid by:
(1) evaporation of the fermentation broth, or
(2) precipitation by acid treatment combined with at least partial removal of the aminobenzoic acid that separates out from the acid-treated fermentation broth.

10. The method of claim 9 , in which step (I-0) (a) is carried out according to variant (2) and comprises:
(i) treating the fermentation broth obtained in step (I-0), optionally after carrying out step (α) and/or step (β), in a reactor with acid such that aminobenzoic acid separates out from the fermentation broth;
(ii) at least partially removing the aminobenzoic acid that separates out in step (I-0) (a) (i) from the acid-treated fermentation broth; and
(iii) optional further purification of the aminobenzoic acid obtained in step (I-0) (a) (ii).

11. The method of claim 10 , in which the acid used in step (I-0) (a) (i) comprises hydrochloric acid, sulfuric acid and/or phosphoric acid.

12. The method of claim 8 , in which the microorganisms used in step (I-0) comprise a species selected from the group consisting of Escherichia coli, Pseudomonas putida, Corynebacterium glutamicum, Ashbya gossypii, Pichia pastoris, Hansenula polymorpha, Yarrowia lipolytica, Zygosaccharomyces bailii and Saccharomyces cerevisiae.

13. The method of claim 1 , wherein solid or dissolved or suspended aminobenzoic acid is added to the stream containing aniline recirculated in step (III) into the reactor of step (I).

14. The method of claim 9 , wherein solid or dissolved or suspended aminobenzoic acid is added to the stream containing aniline recirculated in step (III) into the reactor of step (I).

15. The method of claim 14 , wherein sold or dissolved or suspended aminobenzoic acid is added to the stream containing aniline recirculated in step (III) into the reactor of step (I), wherein the solid or dissolved or suspended aminobenzoic acid originates from step (I-0) (a) and contains water.

16. The method of claim 1 , wherein the stream containing aniline recirculated in step (III) and the aminobenzoic acid to be decarboxylated are fed to the reactor of step (I) via separate feed units.

17. The method of claim 1 , wherein step (IV) is carried out.

18. The method of claim 17 , wherein step (IV) includes one of the following reactions:
(IV-1) acid-catalyzed reaction of aniline with formaldehyde to form di- and polyamines of the diphenylmethane series;
(IV-2) acid-catalyzed reaction of aniline with formaldehyde, followed by reaction with phosgene to form di- and polyisocyanates of the diphenylmethane series; or
(IV-3) reacting aniline to give an azo compound.

Assignees

• Covestro Deutschland Ag

Inventors

• Jäger Gernot
• Hamedinger Thomas
• Lolli Giulio
• Moussa Amgad Salah
• Olf Guenter

Classifications

• C07C209/68 Primary

  from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton · CPC title

• C07C209/78

  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

• C12P13/001

  Amines; Imines · CPC title

• C07C211/46

  Aniline · CPC title