HYDROGENATION OF AROMATIC AMINES FROM PU DECOMPOSITION PROCESSES

Abstract

A process for catalytic hydrogenation of aromatic amines can be performed. The aromatic amines can be methylenedianiline and/or tolylenediamine. The ring-hydrogenated equivalents can be obtained by contacting an input product, which have the aromatic amines and impurities, such as, alcohols, glycols, polyols, organic acids and/or water, with hydrogen in the presence of a catalyst. The catalyst can be platinum, palladium, rhodium, ruthenium, nickel, cobalt and/or iron. The catalyst is applied to a support, wherein the input product that has aromatic amines result from a PU decomposition process and contains impurities from this decomposition process.

Claims

1. A process for catalytic hydrogenation of aromatic amines, to afford their ring-hydrogenated equivalents, the process comprising: contacting an input product, which comprises the aromatic amines and up to 25% by weight of impurities, with hydrogen in the presence of a catalyst applied to a support, wherein the input product comprising aromatic amines results from a polyurethane decomposition process and contains impurities from this decomposition process.

2. The process according to claim 1, wherein the catalyst comprises rhodium and/or ruthenium.

3. The process according to claim 2, wherein rhodium and ruthenium are employed together and a weight ratio of rhodium to ruthenium is 1 to 20 parts of rhodium per part of ruthenium.

4. The process according to claim 2, wherein the support is a lithium aluminate support.

5. The process according to claim 4, wherein a weight ratio of ruthenium to lithium aluminate is 2 to 8 parts by weight of ruthenium per 100 parts by weight of lithium aluminate.

6. The process according to claim 1, wherein a catalyst system is a physical mixture of rhodium on lithium aluminate and ruthenium on lithium aluminate.

7. The process according to claim 3, wherein a weight ratio of rhodium to ruthenium in the catalyst system is 6 to 15 parts by weight of rhodium per part by weight of ruthenium.

8. The process according to claim 1, wherein ruthenium supported on aluminum oxide (Al.sub.2O.sub.3) is employed as the catalyst.

9. The process according to claim 8, wherein a weight ratio of ruthenium to aluminum oxide is 4 to 25 parts by weight of ruthenium per 100 parts by weight of aluminum oxide.

10. The process according to claim 1, wherein the hydrogenation is performed in the presence of a solvent.

11. The process according to claim 1, wherein a hydrogenation pressure is 1.48 MPa to 27.68 MPa.

12. The process according to claim 1, wherein the polyurethane decomposition process comprises: a) depolymerizing a polyurethane by hydrolysis in the presence of a base and at least one catalyst selected from the group consisting of quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms to produce aromatic amines, b) separating an organic phase comprising the aromatic amines from an aqueous phase, c) optionally separating the aromatic amines from the organic phase, and d) optionally reusing the separated aqueous phase in the depolymerization of a polyurethane by hydrolysis according to a).

13. The process according to claim 12, wherein the depolymerization of the polyurethane in a) is effected using a base having a pK.sub.b at 25? C. of 1 to 10 and at least one catalyst selected from the group consisting of quaternary ammonium salts containing an ammonium cation comprising 6 to 30 carbon atoms and organic sulfonates containing at least 7 carbon atoms.

14. The process according to claim 12, wherein the depolymerization of the polyurethane in a) is carried out using a base having a pK.sub.b at 25? C. of <1 and at least one catalyst selected from the group consisting of quaternary ammonium salts containing an ammonium cation having 6 to 14 carbon atoms when the ammonium cation does not comprise a benzyl radical and quaternary ammonium salts containing an ammonium cation having 6 to 12 carbon atoms when the ammonium cation does comprise a benzyl radical.

15. The process according to claim 1, wherein the polyurethane to be decomposed in the PU decomposition process comprises a polyurethane foam.

16. The process according to claim 1, wherein the aromatic amines comprise methylenedianiline and/or tolylenediamine.

17. The process according to claim 1, wherein the impurities are at least one selected from the group consisting of alcohols, glycols, polyols, organic acids, tertiary amines, quaternary amines, aldehydes, and water.

18. The process according to claim 1, wherein the catalyst is ruthenium.

19. The process according to claim 10, wherein the solvent is used in an amount from 100 parts by weight based on 100 parts by weight of the aromatic amine introduced into the reaction.

20. The process according to claim 10, wherein the solvent is employed in amounts from about 200 to about 600 parts by weight based on 100 parts by weight of the aromatic amine introduced into the reaction.

Description

EXAMPLES

Example 1 According to the Invention

[0074] A 1 L hydrogenation autoclave with a sparging stirrer was filled with a mixture of 121.7 g of recycled tolylenediamine* and 278.6 g of THF (INEOS, >99.9% purity). The reactor was inerted with nitrogen by three-fold pressure swing, whereafter 3.48 g of a ruthenium catalyst (15% Ru on aluminum oxide) were added to the stirred solution (1000 rpm) through an airlock. After renewed inerting by pressure swing the reactor was pressurized with 80 bar of hydrogen (Evonik Operations GmbH, >99.95% purity).

[0075] The reaction was commenced by increasing the temperature of the reactor to 185? C. over a period of 90 minutes. Over this time the reactor pressure increased to about 100 bar. This pressure was subsequently maintained through hydrogen control.

[0076] Samples were taken from the reaction through a sample tube after 60, 180, 300, 420 and 1380 min, without interrupting the reaction. The samples were analyzed by gas chromatography. The conversions and GC yields of methylcyclohexyldiamine (MCDA) achieved are shown in table 1.

Recycled Tolylenediamine*:

[0077] The recycled tolylenediamine resulted from a PU decomposition process, based on a hydrolysis, performed according to claims 12 and 13 (after WO2022042909A1). The tolylenediamine produced according to claims 12 and 13 had a purity of 96.9% (GC %) (main secondary component 0.82% polyol).

Example 2 According to the Invention

[0078] A 1 L hydrogenation autoclave with a sparging stirrer was filled with a mixture of 125.0 g of recycled tolylenediamine* and 280.9 g of THF (INEOS, >99.9% purity). The reactor was inerted with nitrogen by three-fold pressure swing, whereafter 3.50 g of a ruthenium catalyst (15% Ru on aluminum oxide) were added to the stirred solution (1000 rpm) through an airlock. After renewed inerting by pressure swing the reactor was pressurized with 80 bar of hydrogen (Evonik Operations GmbH, >99.95% purity)

[0079] The reaction was commenced by increasing the temperature of the reactor to 185? C. over a period of 90 minutes. Over this time the reactor pressure increased to about 100 bar. This pressure was subsequently maintained through hydrogen control.

[0080] Samples were taken from the reaction through a sample tube after 60, 180 and 1380 min, without interrupting the reaction. The samples were analyzed by gas chromatography. The conversions and GC yields of methylcyclohexyldiamine (MCDA) achieved are shown in table 1.

Recycled Tolylenediamine*:

[0081] The recycled tolylenediamine resulted from a PU decomposition process, based on a hydrolysis, performed according to claims 12 and 13 (after WO2022042909A1). The tolylenediamine produced according to claims 12 and 13 had a purity of 91.29% (main secondary components: 0.79% polyol, 4.0% tributylamine).

Comparative Example 1

[0082] A 1 L hydrogenation autoclave with a sparging stirrer was filled with a mixture of 96.5 g of 2,4-diaminotoluene (Sigma-Aldrich, 98% purity), 24.3 g of 2,6-diaminotoluene (Sigma-Aldrich, 97% purity) and 281.2 g of THF (INEOS, >99.9% purity). The reactor was inerted with nitrogen by three-fold pressure swing, whereafter 3.51 g of a ruthenium catalyst (15% Ru on aluminum oxide) were added to the stirred solution (1000 rpm) through an airlock. After renewed inerting by pressure swing the reactor was pressurized with 80 bar of hydrogen (Evonik Operations GmbH, >99.95% purity).

[0083] The reaction was commenced by increasing the temperature of the reactor to 185? C. over a period of 90 minutes. Over this time the reactor pressure increased to about 100 bar. This pressure was subsequently maintained through hydrogen control.

[0084] Samples were taken from the reaction through a sample tube after 60, 180, 360 and 1380 min, without interrupting the reaction. The samples were analyzed by gas chromatography. The conversions and GC yields of methylcyclohexyldiamine achieved are shown in table 1.

TABLE-US-00001 TABLE 1 Conversion of TDA (tolylenediamine) and yield of MCDA of inventive and comparative example Inventive example 1 Inventive example 2 Comparative example Conver- Yield of Conver- Yield of Conver- Yield of Time sion MCDA sion MCDA sion MCDA [min] [GC %] [GC %] [GC %] [GC %] [GC %] [GC %] 0 3.12 0.09 0.15 0.11 0.19 0.04 60 15.16 11.66 7.14 6.47 13.10 11.53 180 65.44 56.99 53.40 45.58 68.36 60.74 300 84.68 74.12 nd nd nd 360 nd nd nd 93.89 83.81 420 94.11 82.69 nd nd nd 1380 99.99 86.90 100 83.92 99.99 87.38 nd = not determined