阅读说明：本技术 制备苯胺或苯胺衍生产物的方法 (Process for preparing aniline or aniline derived products ) 是由 J·朗安克 F·贝格尔 G·耶格尔 W·克洛克纳 V·米歇尔 T·弗斯辛 于 2019-07-24 设计创作，主要内容包括：本发明涉及制备苯胺或苯胺衍生产物的方法,其中氨基苯甲酸在苯胺中的溶液在165℃至500℃的温度下在不存在体系外催化剂的情况下经受热脱羧,使得氨基苯甲酸转化为苯胺,其中基于氨基苯甲酸和苯胺的总质量计,苯胺在所述溶液中的质量比例为20%至85%。所得苯胺可转化为衍生产物,例如二苯基甲烷系列的二胺和多胺。(The present invention relates to a process for the preparation of aniline or an aniline-derived product, wherein a solution of aminobenzoic acid in aniline is subjected to thermal decarboxylation at a temperature of 165 ℃ to 500 ℃ in the absence of an out-of-system catalyst, such that aminobenzoic acid is converted into aniline, wherein the mass proportion of aniline in the solution is 20% to 85% based on the total mass of aminobenzoic acid and aniline. The resulting aniline can be converted into derivative products, such as di-and polyamines of the diphenylmethane series.)

1. A process for preparing aniline or an aniline derived product comprising the steps of:

(I) providing a solution of aminobenzoic acid in aniline, wherein the mass proportion of aniline in the solution, based on the total mass of aminobenzoic acid and aniline, is set to 20% to 85%;

(II) converting aminobenzoic acid contained in the solution provided in step (I) to aniline in a reactor by thermal decarboxylation in the absence of an out-of-system catalyst at a temperature of 165 ℃ to 500 ℃;

(III) optionally, converting the aniline obtained in step (II) to an aniline derivative product.

2. The process according to claim 1, wherein aminobenzoic acid and aniline are mixed in a mixer operated batchwise or continuously for carrying out step (I).

3. The process of claim 2, wherein the mixer of step (I) and the reactor of step (II) are run continuously.

4. The process according to claim 2, wherein for carrying out step (I) a plurality of, in particular two, intermittently operated mixers connected in parallel are used and the reactor of step (II) is operated continuously, wherein at each point in time of the continuous operation of the reactor of step (II) an aminobenzoic acid solution is introduced into the reactor of step (II) from one of the mixers used in step (I) while mixing aminobenzoic acid into aniline in the other of these mixers.

5. The process according to any one of the preceding claims, wherein the thermal decarboxylation of aminobenzoic acid is a first sub-step (II) (1) of step (II), followed by a second sub-step (II) (2), the aniline formed in sub-step (II) (1) being purified in second sub-step (II) (2).

6. The process according to claim 5, wherein the aniline used in step (I) is taken from

Aniline formed in sub-step (II) (1),

aniline purified in substep (II) (2)

Or

Aniline formed in substep (II) (1) and aniline purified in substep (II) (2).

7. The process according to any one of the preceding claims, wherein in step (I) aminobenzoic acid is dissolved in aniline at a temperature of-6 ℃ to 120 ℃.

8. The process according to claim 7, wherein aminobenzoic acid and aniline are first mixed at a temperature of-6 ℃ to 100 ℃ and then heated to a temperature of > 100 ℃ to 120 ℃ in an inert gas atmosphere.

9. The process of any one of the preceding claims, wherein the thermal decarboxylation in step (II)At 4.0 bar_(Absolute)To 30 bar_(Absolute)Under pressure of (c).

10. The process according to any one of claims 5 to 9, wherein a liquid aniline-containing stream and a gaseous carbon dioxide-and gaseous aniline-containing stream are continuously withdrawn from the reactor of step (II), wherein the gaseous stream is passed through a condenser in which the gaseous aniline is liquefied and from which carbon dioxide is discharged in gaseous form, wherein the liquid aniline obtained in the condenser is fed into sub-step (II) (1) and/or sub-step (II) (2).

11. The process of any one of the preceding claims, wherein providing a solution of aminobenzoic acid in aniline in step (I) comprises chemically preparing aminobenzoic acid.

12. The process according to any one of claims 1 to 10, wherein providing a solution of aminobenzoic acid in aniline in step (I) comprises the sub-steps of:

(I) (1) fermenting a feedstock comprising at least

A fermentable carbon-containing compound and

the nitrogen-containing compound is a compound selected from the group consisting of,

obtaining a fermentation broth containing aminobenzoate and/or aminobenzoic acid in a fermentation reactor using a microorganism,

obtaining aminobenzoic acid from the fermentation broth;

and

(I) (2) dissolving aminobenzoic acid obtained from the fermentation broth in step (I) (1) in aniline.

13. The method of claim 12, wherein the microorganism used in step (I) (1) comprises a species selected from the group consisting of:escherichia coli, Pseudomonas putida, Corynebacterium glutamicum, Ashbya gossypii, Pichia pastoris, Hansenula polymorpha, Pseudomonas putida, Corynebacterium glutamicum, kluyveromyces marxianus, yarrowia lipolytica, Zygosaccharomyces bailiiAndsaccharomyces cerevisiae。

14. The process according to any one of the preceding claims, wherein the aminobenzoic acid used for providing the solution of aminobenzoic acid in aniline in step (I) comprises a mass proportion of water of from 0.1% to 40% based on the total mass of aminobenzoic acid and water.

15. The method according to any one of the preceding claims, comprising step (III), wherein step (III) comprises one of the following transformations:

(III) (1) acid catalyzed reaction of aniline with formaldehyde to form di-and polyamines of the diphenylmethane series;

(III) (2) acid catalyzed reaction of aniline with formaldehyde followed by conversion with phosgene to form di-and polyisocyanates of the diphenylmethane series;

(III) (3) converting aniline into an azo compound.

Examples

The chemicals used were:

2-aminobenzoic acid, CAS 118-92-3 (hereinafter, referred to as oAB), purity of 98% or more, Sigma-Aldrich Chemie GmbH.

Aniline, CAS 62-53-3 (hereinafter: ANL), with purity not less than 99%, Sigma-Aldrich Chemie GmbH.

VE water (hereinafter referred to as H)₂O) purity "HPLC grade", Sigma-Aldrich Chemie GmbH.

2-amino-N-phenylbenzamide CAS 4424-17-3 (hereinafter referred to as amide) with purity not less than 98% and Sigma-Aldrich Chemie GmbH.

Methanol, CAS 67-56-1 (hereinafter: MeOH): purity "HPLC grade", Sigma-Aldrich Chemie GmbH.

Phosphoric acid "ACS reagent", CAS 7664-38-2 (hereinafter referred to as H)₃PO₄) Purity ≥ 85%, Sigma-Aldrich Chemie GmbH.

Catalyst (for comparative example):

CBV 600 (CAS 1318-02-1), Zeolyst International, Inc., surface area 660 m²G, pore diameter of 2.43 nm, and Si/Al ratio of 2.5. Before use, the catalyst is emptiedCalcining at 300 deg.C for 3 hr.

General experimental procedure for experiments with catalyst (comparative examples):

1.33 g of OAB, 2 mL of ANL and 0.08 g of catalyst were placed in a 10 mL pressure reactor, purged with argon as a blanket gas and the reactor was closed. Then 3 bar of argon pressure was applied, stirring was carried out at 800 rpm for 2 minutes and the pressure was released to 1 bar. This process was repeated 3 more times before the reactor was brought to the reaction temperature (see table 1). After the corresponding reaction time (see table 1), the pressure reactor was cooled from the reaction temperature to room temperature in an ice bath and then the pressure was released. The catalyst was separated from the reaction mixture by means of centrifugation (5 min, 5000 rpm). The composition of the liquid supernatant was checked by means of HPLC analysis (data see table 1).

General experimental procedure for experiments without catalyst (working examples):

the reaction was carried out similarly to the "general experimental protocol for experiments with catalyst" except that it was operated without catalyst, thus omitting the experimental steps relating to the catalyst.

HPLC measurement:

high Pressure Liquid Chromatography (HPLC) analysis was performed to quantitatively determine oAB, ANL and amide in the reaction mixture. HPLC analysis used an Agilent device with UV detection (DAD, measured at 254.4 nm). An Agilent column (Eclipse XDB-C18; 5 μm; 4.6 x 150 mm) was used for the separation. MeOH and H were used₂Mixture of O as eluent (ratio 40:60, pH = 3, with H₃PO₄Adjusted) flow rate was 0.7 mL/min. The column box temperature was 25 ℃. Samples were diluted in MeOH at a ratio of 1:10, with an injection volume of 1 μ L. The retention times of the individual components ANL, oAB and amide were:

● ANL = 2.87 min;

● oAB = 6.00 min;

● amide = 18.67 min.

The peak area is converted to area percent (a%). The individual components can be quantified in mass percent (mass%) based on the reaction mixture by calibration beforehand with pure substances. All product compositions for the working examples and comparative examples are listed in table 1 for a given reaction time.

Determination of reaction speed:

to determine the reaction rate, the rate constant k (in min) for the conversion of oAB was determined^-1In units). To this end, the pseudo-first order conversion kinetics of oAB were used as a basis and oAB conversions were determined experimentally for different reaction times. To calculate k, the natural logarithm of the relative oAB concentration was plotted against the reaction time (in minutes) and a linear fit was performed. The slope of the equation of the line thus obtained corresponds to k in min^-1Is a unit. In table 1, all k values of the working examples and comparative examples are listed.