METHOD FOR THE PRODUCTION OF ETHYLENEAMINES

Abstract

The present invention relates to a process for preparing alkanolamines and ethyleneamines in the liquid phase, by reacting ethylene glycol and/or monoethanolamine with ammonia in the presence of an amination catalyst which is obtained by reducing a catalyst precursor, wherein the preparation of the catalyst precursor comprises a step a) in which a catalyst precursor comprising one or more catalytically active components of Sn, Cu and Ni, and a step b) in which the catalyst precursor prepared in step a) is contacted with a soluble Re compound.

Claims

1.-15. (canceled)

16. A process for preparing alkanolamines and ethyleneamines in the liquid phase, by reacting ethylene glycol, monoethanolamine, or a combination thereof with ammonia in the presence of an amination catalyst which is obtained by reducing a catalyst precursor, wherein the preparation of the catalyst precursor comprises a step a) in which a catalyst precursor comprising one or more catalytically active components of Sn, Cu and Ni is prepared, and a step b) in which the catalyst precursor prepared in step a) is contacted with a soluble Re compound.

17. The process according to claim 16, wherein the catalyst precursor prepared in step a) additionally comprises catalytically active components of Co.

18. The process according to claim 16, wherein the catalyst precursor in step a) is prepared by coprecipitation and comprises in the range from 1% to 95% by weight of catalytically active components selected from the group consisting of Sn, Cu Ni, and mixtures thereof, calculated as CuO, NiO and SnO respectively and based in each case on the total mass of the catalyst precursor.

19. The process according to claim 16, wherein the catalyst precursor is prepared by precipitative application in step a) and, comprises in the range from 5% to 95% by weight of support material and in the range from 5% to 90% by weight of catalytically active components selected from the group consisting of Sn, Cu Ni, and mixtures thereof, calculated as CuO, NiO and SnO respectively and based in each case on the total mass of the catalyst precursor.

20. The process according to claim 16, wherein the catalyst precursor is prepared by impregnation in step a) and, comprises in the range from 50% to 99% by weight of support material and in the range from 1% to 50% by weight of catalytically active components selected from the group consisting of Sn, Cu Ni, and mixtures thereof, calculated as CuO, NiO and SnO respectively and based in each case on the total mass of the catalyst precursor.

21. The process according to claim 17, wherein the catalyst precursor prepared in step a) comprises, 0.2% to 5% by weight of catalytically active components of tin, calculated as SnO, 1% to 20% by weight of catalytically active components of copper, calculated as CuO, 5% to 35% by weight of catalytically active components of nickel, calculated as NiO, and 5% to 35% by weight of catalytically active components of cobalt, calculated as CoO, and 15% to 80% by weight of catalytically active components of aluminum, calculated as Al.sub.2O.sub.3 as support material, based on the total mass of the catalyst precursor.

22. The process according to claim 21, wherein the catalyst precursor is prepared in the presence of tin nitrate and a complexing agent.

23. The process according to claim 16, wherein the catalyst precursor in step b) is contacted with a soluble Re compound by post-impregnating the catalyst precursor with an impregnating solution comprising a soluble Re compound and the Re concentration in the impregnating solution being in the range of 0.1 to 50% by weight.

24. The process according to claim 16, wherein the catalyst precursor in step b) is contacted with a soluble compound of an active metal or an added catalyst element other than Re.

25. The process according to claim 16, wherein the catalyst precursor in step b) is contacted with a soluble Ru compound and/or a soluble Co compound by post-impregnating the catalyst precursor with an impregnating solution comprising a soluble Ru compound and/or a soluble Co compound and the Ru concentration in the impregnating solution being in the range of 0.1 to 50% by weight or the Co concentration in the impregnating solution being in the range of 0.1 to 20% by weight.

26. The process according to claim 16, wherein the catalyst precursor is dried after step b) before reducing the catalyst precursor to obtain the amination catalyst.

27. The process according to claim 26, wherein the catalyst precursor comprises 0.1% to 20% by weight of catalytically active components of Re, calculated as ReO.sub.3 and based on the total mass of the catalyst precursor after the last drying step.

28. The process according to claim 26, wherein the catalyst precursor comprises 0.1% to 50% by weight of catalytically active components of Co, calculated as CoO and based on the total mass of the catalyst precursor after the last drying step or wherein the catalyst precursor comprised 0.1% to 50% by weight of catalytically active components of Ru, calculated as RuO.sub.2 and based on the total mass of the catalyst precursor after the last drying step

29. The process according to claim 16, wherein the catalyst precursors prepared in step a) are further processed by performing one or more of the following processing steps before submitting the catalyst precursor to step b): aa) liquid separation, ab) washing, ac) drying, ad) calcination, ae) shaping.

30. The process according to claim 16, wherein the reaction of ethylene glycol or monoethanolamine with ammonia is effected in the liquid phase at a pressure of 5 to 30 MPa and a temperature in the range from 80 to 350° C.

Description

EXAMPLE 1: PREPARATION OF THE CATALYST PRECURSOR (STEP A))

[0335] A catalyst precursor was obtained according to example B3 of WO 2013/072289. The tablets (3×3 mm) obtained in this way were comminuted to spall of 1 to 2 mm in size. The solvent capacity SC of the spall for water was determined to be 0.29 ml/g.

Examples 2 to 13: Preparation of the Catalysts (Step b)) by Post-Impregnation of the Catalyst Precursor Prepared in Example 1

[0336] Aqueous metal salt solutions (impregnation solutions) were prepared according to Table 1 and used for the post-impregnation of the catalyst precursor obtained in Example 1. The metal content of the aqueous metal salt solutions was as follows:

Perrhenic acid: 50 g Re per 100 g

Ru-nitrosylnitrate: 20 g Ru per 100 g

[0337] Co-nitrate hexahydrate: 20 g Co per 100 g.

[0338] The impregnation solutions were obtained by mixing the amounts of each aqueous metal salt solution as depicted in Columns 2 to 4 of Table 1 and adding additional water to obtain impregnation solutions having the total volume set out in Column 5 of Table 1.

[0339] Post-impregnation was carried out in an impregnation apparatus by the incipient wetness method, wherein the respective impregnation solutions were added in an amount corresponding to x % (see Column 9 of Table 1) of the solvent capacity SC determined in Example 1. The post-impregnated spall was revolved for 30 minutes in the impregnation apparatus to achieve a homogeneous uptake of the metal salt solutions by the spall. In case of a one-step post-impregnation, the post-impregnated spall was subsequently dried for 16 hours at 120° C. in a drying chamber. In case of a two-step post-impregnation, the post-impregnated spall obtained during the first post-impregnation step was dried in the impregnation apparatus under a water-jet vacuum at 120° C. for 4 hours before the second post-impregnation step was performed. The second post-impregnation step was also carried out by the incipient wetness method by adding an amount of metal salt solution corresponding to x % of the solvent capacity determined in Example 1 (see Column 9 of Table 1). The drying step after the second post-impregnation step was carried out for 4 hours under a water jet vacuum at 120° C.

[0340] The theoretical metal content of the catalyst precursors after the last drying step is depicted in Columns 6 to 8 of Table 1.

TABLE-US-00001 TABLE 1 Total Theor Theor Theor Volume of Re- Ru- Co- Ruthenium- Mixed Metal content. content. content. nitrosyl- Cobalt- Salt Solution (% by (% by (% by nitrat- nitrate- after weight weight weight Perrrhenic solution. hexahydrate Addition per per per Impreg- Example. acid (g) (g) (g) of Water 100 g) 100 g) 100 g) nation.sup.1)  2 2.6 18.4 7.0 39 0.9 2.0 0.9 1* 90% SC  3 13.8 18.7 7.1 39 5.0 2.0 1.0 1* 90% SC  4 6.7 9.2 7.1 70 2.4 1.0 1.0 2* 90%/ 70% SC  5 6.9 18.7 7.1 70 2.5 2.0 1.0 2* 90%/ 70% SC  6 29.1 24.9 7.7 70 10.5 2.7 1.0 2* 90%/ 70% SC  7 3.3 5.6 3.5 70 1.2 0.6 0.5 2* 90%/ 70% SC  8 8.5 23.3 5.8 70 3.1 2.5 0.8 2* 90%/ 70% SC  9 4.3 14.5 4.6 70 1.6 1.6 0.6 2* 80% SC 10 3.1 10.5 3.0 70 1.1 1.1 0.4 2* 80% SC 11 11.6 0.0 0.0 39 4.2 0.0 0.0 1* 90% SC 12 0.0 18.2 7.0 39 0.0 2.0 0.9 1* (Com- 90% parative SC Example) 13 0 0 0 0 (Com- parative Example) .sup.1)One step post-impregnation is designated as “1*”. Two-step post-impregnation is designated as “2*”.

[0341] The catalyst precursor obtained in this manner was reduced by reductive calcination according to Comparative Example 4 in WO 2018/224316 and subsequently passivated as in WO 2018/224316, Comparative Example 1.

Testing of the Catalysts:

[0342] The testing of the catalysts was carried out as described in WO 2018/224316, page 37, except that the testing was conducted at a temperature of 170° C. and a catalyst hourly space velocity in the range of 0.3 to 0.6 kg/l/h (see Column 3 of Table 2).

[0343] The results of the testing are summarized in Table 2.

[0344] For a better comparison, the testing results (selectivity S of the respective products) at different hourly space velocities were evaluated in a manner that load depending measurement values in the range of 25 to 35% conversion and in a range of 35 to 45% conversion were linearly interpolated to a conversion of 35%.

TABLE-US-00002 TABLE 2 MEG- Catalyst Con- hourly Precursor ver- space S S S S S from sion velocity EDA MEOA PIP DETA AEEA Example Nr. % g/ml/h SQ % % % % % 12 35 0.38 4.4 49.0 29.3 9.2 5.9 3.6 (Comparative Example) 2 35 0.37 4.8 51.6 27.1 9.2 5.9 3.2 3 35 0.46 5.6 51.1 31.7 7.5 4.4 2.8 4 35 0.39 4.7 49.1 30.3 8.5 5.6 3.2 5 35 0.43 5.0 52.1 27.5 8.3 5.6 3.0 6 35 0.50 5.6 50.9 30.7 7.1 5.7 3.1 7 35 0.39 4.6 48.7 30.5 8.6 5.4 3.2 8 35 0.42 5.1 49.9 30.6 8.0 5.6 3.1 9 35 0.40 4.9 50.2 30.1 8.2 5.5 3.1 10 35 0.44 5.0 50.7 29.5 8.3 5.1 3.1 13 35 0.17 3.8 45.9 34.9 7.4 4.4 5.0 (Comparative Example) 11 35 0.44 4.7 47.8 32.7 8.1 5.2 3.4

[0345] It is evident that the post-impregnation of catalyst precursors with Co and Ru (Comparative Example 12) compared to non-impregnated catalyst precursors (Comparative Example 13) already leads to an increase of the selectivity quotient SQ (SQ=(S(DETA)+S(EDA))/(S(PIP)+S(AEEA)) from 3.8 to 4.4.

[0346] An increase of SQ corresponds to an increase of the sum of the selectivity of the desired products EDA and DETA and a decrease of the sum of the selectivity of the undesired products PIP and AEEA.

[0347] If the post-impregnation is carried out with Re (Example 11) instead of Co and Ru (Comparative Example 12), it becomes evident that the post-impregnation with Re without a post-impregnation of Co and Ru results in a further increase of SQ from 4.4 to 4.7.

[0348] If post-impregnation is carried out with Re in combination with Ru and Co (Examples 2 to 10), further increases of SQ to values of up to 5.6 are achieved.