Method for hydrogenating nitriles in the presence of a ruthenium catalyst carried on ZrO.SUB.2

Abstract

The present invention relates to a process for hydrogenating nitriles with hydrogen in the presence of a ZrO.sub.2-supported ruthenium catalyst.

Claims

1. A process, comprising hydrogenating at least one nitrile compound in the presence of hydrogen and a fixed-bed ruthenium catalyst supported on ZrO.sub.2, wherein the fixed-bed ruthenium catalyst comprises 0.05 to 20 wt % of ruthenium, based on the total weight of the fixed-bed ruthenium catalyst.

2. The process according to claim 1, wherein the process is operated continuously.

3. The process according to claim 1, wherein the at least one nitrile compound comprises a dinitrile compound.

4. The process according to claim 1, wherein the nitrile compound is selected from the group consisting of a cyanoethylated single alcohol, a cyanoethylated multiple alcohol, a cyanoethylated amine and an alpha-aminonnitrile.

5. The process according to claim 1, wherein the hydrogenating does not occur in the presence of an added solvent.

6. The process according to claim 1, wherein the hydrogenating occurs in the presence of ammonia.

7. The process according to claim 1, wherein hydrogenation takes place at a temperature in the range from 20 to 200° C. and a pressure in the range from 20 to 300 bar.

8. The process according to claim 7, wherein the process is operated continuously.

9. The process according to claim 8, wherein the at least one nitrile compound comprises a dinitrile compound.

10. The process according to claim 9, wherein the nitrile compound is selected from the group consisting of a cyanoethylated single alcohol, a cyanoethylated multiple alcohol, a cyanoethylated amine and an alpha-aminonnitrile.

11. The process according to claim 10, wherein the hydrogenating does not occur in the presence of an added solvent.

12. The process according to claim 11, wherein the hydrogenating occurs in the presence of ammonia.

13. The process according to claim 1, wherein the fixed-bed ruthenium catalyst comprises 0.05 to 15 wt % of ruthenium, based on the total weight of the fixed-bed ruthenium catalyst.

14. The process according to claim 1, wherein the at least one nitrile compound comprises a dinitrile compound, wherein the hydrogenating does not occur in the presence of an added solvent, wherein the hydrogenating occurs in the presence of ammonia, and wherein the fixed-bed ruthenium catalyst comprises 0.05 to 15 wt % of ruthenium, based on the total weight of the fixed-bed ruthenium catalyst.

15. The process according to claim 1, wherein the fixed-bed ruthenium catalyst supported on ZrO.sub.2 does not undergo significant deactivation when used continuously over 960 hours compared to a fixed-bed cobalt catalyst or a fixed-bed ruthenium catalyst supported on Al.sub.2O.sub.3.

Description

EXAMPLE 1

(1) Continuous Hydrogenation of N,N-bis(cyanoethyl)methylamine (BCEMA) to N,N-bisaminopropylmethylamine (BAPMA) Over a Fixed-Bed Co and Ru Catalyst

(2) Pumped hourly through a vertical tube reactor (diameter: 0.5 cm, fill level 100 cm) operated at 170 bar and filled with 24.6 ml of a ruthenium catalyst (3 mm strands, described in WO-A2 2015/086639) or 20.8 ml of a cobalt catalyst (4 mm strands, described in EP636409) were 4.2 or 5.4 g of N,N-Bis(cyanoethyl)methylamine and 10.3-13.4 g of liquid ammonia (molar ratio 20). Passed through the reactor at the same time were 15-20 NL/h hydrogen.

(3) After the reactor had been let down to atmospheric pressure, the hydrogenation discharge was analyzed by gas chromatography.

(4) The temperature was selected so as to attain a conversion rate at the start of the experiment of approximately 99% (140° C. for the Co catalyst, 150° C. for the Ru catalyst).

(5) TABLE-US-00001 Run Bis- Sum of time Space velocity BAPMA BAPMA residual nitrile Conversion [h] Entry [kg.sub.nitrile/L.sub.cat.*h] [GC area %] [GC area %] [GC area %] [%] Co cat. 1 1 0.2 78.8 9.84 0.8 99.2 96 h 2 0.2 73.4 8.4 6.1 93.9 Ru cat. 1 3 0.2 92.0 0.9 0.7 99.3 96 h 4 0.2 91.3 1.1 0.8 99.2

(6) The increase in the nitrile with the run time using the Co catalyst shows that under identical conditions, the ruthenium catalyst undergoes deactivation more slowly than the cobalt catalyst.

EXAMPLE 2

(7) Batchwise Hydrogenation of 3-{2-[2-(2-cyanoethoxy)ethoxy]ethoxy}propanenitrile (Biscyanoethyldiethylene Diglycol) to 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propan-1-amine (TTD) Over a Co Catalyst and an Ru Catalyst

(8) A 270 ml autoclave with baffles and a disk stirrer was charged with 5.0 g of the appropriate catalyst (a cobalt catalyst in the form of 4 mm strands, described in EP636409, or a ruthenium catalyst in the form of 4 mm strands, described as in WO-A2 2015/086639) and 30 g of ammonia were injected. The autoclave is heated to 100° C. and hydrogen is injected up to a total pressure of 140 bar. The appropriate nitrile (6.0 g in 54 g of THF) was metered in over the course of 15 minutes. The reaction mixture was stirred under the reaction conditions for a further 60 minutes. The composition of the hydrogenation discharges obtained after letdown, determined by gas chromatography, are compiled in table 4.

(9) TABLE-US-00002 Biscyanoethyl- TTD diethylene glycol [GC area %] [GC area %] Co catalyst 51.9 25.7 Comparative example 5% Ru/ZrO.sub.2 72.8 7.03 Inventive example

EXAMPLE 3

(10) Continuous Hydrogenation of 3-{2-[2-(2-cyanoethoxy)ethoxy]ethoxy}propanenitrile (Biscyanoethyldiethylene Diglycol) to 3-{2-[2-(3-aminopropoxy)ethoxy]ethoxy}propan-1-amine (TTD) Over a Fixed-Bed Ru Catalyst

(11) Pumped hourly through a vertical tube reactor (diameter: 0.5 cm, fill level 100 cm) filled with 37.2 ml of a ruthenium catalyst (3 mm strands) and operated at 170 bar were 13.5 g of 3-{2-[2-(2-cyanoethoxy)ethoxy]ethoxy}propanenitrile and 33.5 g of liquid ammonia (molar ratio 20). At the same time, 20 NL/h hydrogen were passed through the reactor.

(12) After letdown to atmospheric pressure, the hydrogenation discharge was analyzed by gas chromatography.

(13) The reaction was operated continuously over 960 hours without significant deactivation of the catalyst.

(14) TABLE-US-00003 Biscyanoethyl- Propylamine DEG TTD diethylene glycol Others  0 h 0.3 0.8 80.2 0.3 18.4 960 h 0.5 1.1 76.8 0.2 21.4

EXAMPLE 4

(15) Comparison of the Al.sub.2O.sub.3 and ZrO.sub.2 Supports in Semibatchwise Mode

(16) Hydrogenation of N,N-dimethylaminopropionitrile (DMAPN) to N,N-dimethylaminopropylamine (DMAPA)

(17) A 270 ml autoclave with baffles and a disk stirrer was charged with 5.0 g of the appropriate catalyst and 30 g of ammonia were injected. The autoclave is heated to 100° C. and hydrogen is injected up to a total pressure of 140 bar. The appropriate nitrile (6.0 g in 54 g of THF) was metered in over the course of 3 hours. The reaction mixture was stirred under the reaction conditions for a further 60 minutes. The composition of the hydrogenation discharges obtained after letdown, determined by gas chromatography, are compiled in tables 2 and 3.

(18) TABLE-US-00004 DMAPA DMAPN [GC area %] [GC area %] 2% Ru@Al.sub.2O.sub.3 73.6 24.9 Comparative example 2% Ru@ZrO.sub.2 95.7 0.4 Inventive example
Hydrogenation of N,N-biscyanoethylmethylamine to N,N-bisaminopropylmethylamine
Analogous to the Hydrogenation of Dimethylaminopropionitrile

(19) TABLE-US-00005 BAPMA BCEMA Mononitrile [GC area %] [GC area %] [GC area %] 2% Ru@Al.sub.2O.sub.3 42.6 31.7 22.2 Comparative example 2% Ru@ZrO.sub.2 73.4 12.7 9.4 Inventive example

EXAMPLE 5

(20) Comparison of the Supports Carbon and ZrO.sub.2 in Semibatchwise Mode

(21) Inventive Example: Hydrogenation of N,N-dimethylaminoacetonitrile (DMAAN) to N,N-dimethylaminoethylamine (DMAEA) Over Ruthenium on ZrO.sub.2

(22) A 270 ml autoclave with baffles and a disk stirrer was charged with 5.0 g of the catalyst (2% Ru on ZrO.sub.2, 3 mm strands) and 40 ml of ammonia were injected. The autoclave is heated to 100° C. and hydrogen is injected up to a total pressure of 140 bar. DMAAN (6 g in 54 g of THF) was metered in over the course of 1.5 hours. The reaction mixture was stirred under the reaction conditions for a further 60 minutes. The composition of the hydrogenation discharges obtained after letdown, determined by gas chromatography, are compiled in table 5.

(23) Comparative Example: Hydrogenation of N,N-dimethylaminoacetonitrile (DMAAN) to N,N-dimethylaminoethylamine (DMAEA) Over Ruthenium on Carbon

(24) A 270 ml autoclave with baffles and a disk stirrer was charged with 5.0 g of the catalyst (5% Ru on carbon) and 30 g of ammonia were injected. The autoclave is heated to 100° C. and hydrogen is injected up to a total pressure of 140 bar. DMAAN (6 g in 54 g of THF) was metered in over the course of 1.5 hours. The reaction mixture was stirred under the reaction conditions for a further 60 minutes. The composition of the hydrogenation discharges obtained after letdown, determined by gas chromatography, are compiled in table 5.

(25) TABLE-US-00006 DMAEA DMAAN [GC area %] [GC area %] 2% Ru@ZrO.sub.2 94 0 Inventive example 5% Ru@C 1 90 Comparative example