Method for producing aminobenzoic acid or an aminobenzoic acid derivative product

Patent metadata

Field	Value
Publication number	US-11453897-B2
Application number	US-201915733917-A
Country	US
Kind code	B2
Filing date	Jun 5, 2019
Priority date	Jun 7, 2018
Publication date	Sep 27, 2022
Grant date	Sep 27, 2022

Abstract

The invention relates to a method for producing aminobenzoic acid or an aminobenzoic acid derivative using a fermentation process, in which (I) the aminobenzoic acid formed in the fermentation broth obtained by the fermentation is bound in part, or as much as possible based on the solubility equilibrium, as insoluble calcium-aminobenzoate, said insoluble calcium-aminobenzoate is then (II) either isolated as such or in a mixture with the microorganism used in the fermentation and transitioned into a water soluble form, while separating an insoluble calcium salt which is different from the calcium-aminobenzoate, and then (III) by introducing carbon dioxide under pressure into the aqueous solution from the precipitated calcium salt has been released, aminobenzoic acid is precipitated.

First claim

The invention claimed is:

1. A process for preparing aminobenzoic acid or an aminobenzoic acid conversion product, comprising:
(I) fermenting a raw material comprising:
a fermentable carbon-containing compound, and
a nitrogen-containing compound,
in a fermentation reactor using a microorganism and a calcium salt, wherein the microorganism contains a genetic modification to accumulate aminobenzoic acid in the fermentation reactor,
so as to obtain a mixture suspended in an aqueous fermentation solution, the mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate;

(II) (1) isolating the
(1)(i) precipitated calcium aminobenzoate or
(1)(ii) mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate
obtained in step (I) from the aqueous fermentation solution,
(2) converting the aminobenzoate bound in the calcium aminobenzoate to a water-soluble form to form a water-insoluble calcium salt other than calcium aminobenzoate by adding an aqueous phase containing cations that form water-soluble aminobenzoate salts and anions that form water-insoluble calcium salts to the isolated calcium aminobenzoate from (1)(i) or to the mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate from (1)(ii),
so as to obtain a suspension comprising
(2)(i) the precipitated water-insoluble calcium salt or
(2)(ii) a mixture comprising undissolved microorganisms and the water-insoluble calcium salt

in an aqueous solution of aminobenzoate, and
(3) separating the aqueous solution of aminobenzoate obtained in step (2) from the precipitated water-insoluble calcium salt from (2)(i) or from the mixture comprising undissolved microorganisms and the water-insoluble calcium salt from (2)(ii);

(III) introducing carbon dioxide at a pressure of greater than or equal to 1.50 bar (abs.) into the aqueous solution of aminobenzoate separated off in step (II)(3) to separate aminobenzoic acid out, so as to form a suspension containing aminobenzoic acid in an aqueous solution;
(IV) isolating the aminobenzoic acid separated out in step (III) by lowering the pressure with release of carbon dioxide to give a carbon dioxide-depleted aqueous solution that has been freed of aminobenzoic acid separated out;
(V) using the aqueous solution obtained in step (IV) that has been depleted of carbon dioxide and freed of aminobenzoic acid separated out as a constituent of the aqueous phase added in step (II)(2); and
(VI) optionally further converting the aminobenzoic acid separated off in step (IV) to an aminobenzoic acid conversion product, wherein step (VI) comprises:
(1) decarboxylating the aminobenzoic acid to give aniline;
(2) decarboxylating the aminobenzoic acid to give aniline, followed by acid-catalyzed reaction of the aniline with formaldehyde to form di- and polyamines of the diphenylmethane series;
(3) decarboxylating the aminobenzoic acid to give aniline, followed by acid-catalyzed reaction of the aniline with formaldehyde to form di- and polyamines of the diphenylmethane series, followed by reaction with phosgene to form di- and polyisocyanates of the diphenylmethane series;
(4) decarboxylating the aminobenzoic acid to give aniline, followed by conversion of the aniline to an azo compound;
(5) converting the aminobenzoic acid to an amide; or
(6) converting the aminobenzoic acid to a conductive polymer, the conductive polymer optionally comprising polyanthranilic acid.

2. The process as claimed in claim 1 , in which the calcium salt used in step (I) is selected from calcium carbonate, calcium hydrogencarbonate, calcium hydroxide, calcium oxide and mixtures thereof.

3. The process as claimed in claim 1 , in which the aqueous phase added in step (II)(2) comprises lithium, sodium, potassium and/or ammonium cations.

4. The process as claimed in claim 1 , in which the fermentation in step (I) is performed batchwise in fermentation cycles.

5. The process as claimed in claim 4 , in which, on conclusion of a fermentation cycle,
(A)
step (II)(1) is conducted by discharging the aqueous fermentation solution obtained in step (I) from the fermentation reactor while retaining the mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate suspended therein;
step (II)(2) is conducted by introducing the aqueous phase into the fermentation reactor so as to obtain a suspension containing a mixture comprising undissolved microorganisms and the water-insoluble calcium salt in an aqueous solution of aminobenzoate in the fermentation reactor; and
step (II)(3) is conducted by discharging the aqueous solution of aminobenzoate obtained in step (II)(2) from the fermentation reactor, while retaining the mixture comprising undissolved microorganisms and the water-insoluble calcium salt and making it available for the next fermentation cycle; or
(B)
step (II)(1) is conducted by discharging the aqueous fermentation solution obtained in step (I) from the fermentation reactor together with the mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate suspended therein and separating the mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate from the aqueous fermentation solution outside the fermentation reactor and recycling it into the fermentation reactor;
step (II)(2) is conducted by introducing the aqueous phase into the fermentation reactor so as to obtain a suspension containing a mixture comprising undissolved microorganisms and the water-insoluble calcium salt in an aqueous solution of aminobenzoate in the fermentation reactor; and
step (II)(3) is conducted by discharging the aqueous solution of aminobenzoate obtained in step (II)(2) from the fermentation reactor, while retaining the mixture comprising undissolved microorganisms and the water-insoluble calcium salt and making it available for the next fermentation cycle; or
(C)
step (II)(1) is conducted by discharging the aqueous fermentation solution obtained in step (I) from the fermentation reactor together with the mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate suspended therein and separating the mixture comprising undissolved microorganisms and precipitated calcium aminobenzoate from the aqueous fermentation solution outside the fermentation reactor and introducing it into a vessel other than the fermentation reactor;
step (II)(2) is conducted by introducing the aqueous phase into the vessel other than the fermentation reactor so as to obtain a suspension containing a mixture comprising undissolved microorganisms and the water-insoluble calcium salt in an aqueous solution of aminobenzoate in the vessel other than the fermentation reactor; and
after the separation of the aqueous solution of aminobenzoate obtained in step (II)(2) from the mixture comprising undissolved microorganisms and the water-insoluble calcium salt in step (II)(3), the mixture separated off is introduced back into the fermentation reactor in a step (II)(4) and made available for the next fermentation cycle.

6. The process as claimed in claim 5 , in which steps (I) and (II) are repeated until the desired amount of aminobenzoic acid is obtained in step (IV) or the microorganisms used in step (I) have to be replaced.

7. The process as claimed in claim 1 , in which the fermentation in step (I) is performed continuously.

8. The process as claimed in claim 7 , in which
(A)
mixture suspended in the aqueous fermentation solution and comprising undissolved microorganisms and precipitated calcium aminobenzoate is discharged continuously from the fermentation reactor and
after discharging, step (II)(1) is conducted by separating the insoluble microorganisms and precipit

Assignees

• Covestro Intellectual Property Gmbh & Co Kg

Inventors

• Jaeger Gernot
• Olf Guenter
• Beggel Franz
• Kloeckner Wolf
• Klaff Simon

Classifications

• C12N15/77

  for Corynebacterium; for Brevibacterium · CPC title

• C12P13/00

  Preparation of nitrogen-containing organic compounds · CPC title

• C12P13/04 Primary

  Alpha- or beta- amino acids {(other amino acids C12P13/005)} · CPC title

• C12P13/001 Primary

  Amines; Imines · CPC title

• C12Y204/02018

  Anthranilate phosphoribosyltransferase (2.4.2.18) · CPC title