METHOD FOR THE PRODUCTION OF ETHYLENEAMINES

Abstract

The 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 is first prepared and the catalyst precursor prepared in step a) is contacted simultaneously or successively with a soluble Ru compound and a soluble Co compound in a step b).

Claims

1.-16. (canceled)

17. A process for preparing alkanolamines and ethyleneamines in the liquid phase, which comprises 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 is first prepared and the catalyst precursor prepared in step a) is contacted simultaneously or successively with a soluble Ru compound and a soluble Co compound in a step b).

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

19. The process according to claim 18, wherein the catalyst precursor is prepared by coprecipitation in step a) and, before being contacted with Ru and Co in step b), comprises in the range from 1% to 95% by weight of catalytically active components of Sn, Cu and/or Ni, 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 18, wherein the catalyst precursor is prepared by precipitative application in step a) and, before being contacted with Ru and Co in step b), 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 of Sn, Cu and/or Ni, 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 18, wherein the catalyst precursor is prepared by impregnation in step a) and, before being contacted with Ru and Co in step b), 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 of Sn, Cu and/or Ni, calculated as CuO, NiO and SnO respectively and based in each case on the total mass of the catalyst precursor.

22. The process according to claim 17, wherein the catalyst precursor prepared in step a) comprises 10% to 75% by weight of catalytically active components of zirconium, calculated as ZrO.sub.2; 1% to 30% by weight of catalytically active components of copper, calculated as CuO, 10% to 70% by weight of catalytically active components of nickel, calculated as NiO, 0.1% to 10% by weight of catalytically active components of one or more metals selected from Sb, Pb, Bi and In, each calculated as Sb.sub.2O.sub.3, PbO, Bi.sub.2O.sub.3 and In.sub.2O.sub.3 respectively, based on the total mass of the catalyst precursor.

23. The process according to claim 17, wherein the catalyst precursor prepared in step a) comprises 10% to 75% by weight of catalytically active components of zirconium, calculated as ZrO.sub.2, 1% to 30% by weight of catalytically active components of copper, calculated as CuO, 10% to 70% by weight of catalytically active components of nickel, calculated as NiO, 10% to 50% by weight of catalytically active components of cobalt, calculated as CoO, and 0.1% to 10% by weight of catalytically active components of one or more metals selected from Pb, Bi, Sn, Sb and In, each calculated as PbO, Bi.sub.2O.sub.3, SnO, Sb.sub.2O.sub.3 and In.sub.2O.sub.3 respectively, based on the total mass of the catalyst precursor.

24. The process according to claim 17, wherein the catalyst precursor prepared in step a) comprises 20% to 70% by weight of catalytically active components of zirconium, calculated as ZrO.sub.2, 15% to 60% by weight of catalytically active components of nickel, calculated as NiO, 0.5% to 14% by weight of catalytically active components of iron, calculated as Fe.sub.2O.sub.3, and 0.2% to 5.5% by weight of catalytically active components of tin, lead, bismuth, molybdenum, antimony and/or phosphorus, each calculated as SnO, PbO, Bi.sub.2O.sub.3, MoO.sub.3, Sb.sub.2O.sub.3 and H.sub.3PO.sub.4 respectively, based on the total mass of the catalyst precursor.

25. The process according to claim 17, wherein the catalyst precursor prepared in step a) comprises 20% to 85% by weight of catalytically active components of zirconium, calculated as ZrO.sub.2, 0.2% to 25% by weight of catalytically active components of copper, calculated as CuO, 0.2% to 45% by weight of catalytically active components of nickel, calculated as NiO, 0.2% to 40% by weight of catalytically active components of cobalt, calculated as CoO, 0.1% to 5% by weight of catalytically active components of iron, calculated as Fe.sub.2O.sub.3, and 0.1% to 5.0% by weight of catalytically active components of lead, tin, bismuth and/or antimony, each calculated as PbO, SnO, Bi.sub.2O.sub.3 and Sb.sub.2O.sub.3 respectively, based on the total mass of the catalyst precursor.

26. The process according to claim 17, wherein the catalyst precursor prepared in step a) comprises 46% to 65% by weight of catalytically active components of zirconium, calculated as ZrO.sub.2, 5.5% to 18% by weight of catalytically active components of copper, calculated as CuO, 20% to 45% by weight of catalytically active components of nickel, calculated as NiO, 1.0% to 5.0% by weight of catalytically active components of cobalt, calculated as CoO, and 0.2% to 5.0% by weight of catalytically active components of vanadium, niobium, sulfur, phosphorus, gallium, boron, tungsten, lead and/or antimony, each calculated as V.sub.2O.sub.5, Nb.sub.2O.sub.5, H.sub.2SO.sub.4, H.sub.3PO.sub.4, Ga.sub.2O.sub.3, B.sub.2O.sub.3, WO.sub.3, PbO and Sb.sub.2O.sub.3 respectively, based on the total mass of the catalyst precursor.

27. The process according to claim 17, wherein the catalyst precursor prepared in step a) comprises 0.2% to 5.0% by weight of catalytically active components of tin, calculated as SnO, 10% to 30% by weight of catalytically active components of cobalt, calculated as CoO, 15% to 80% by weight of catalytically active components of aluminum, calculated as Al.sub.2O.sub.3, 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 0.2% to 5.0% by weight of catalytically active components of yttrium, lanthanum, cerium and/or hafnium, each calculated as Y.sub.2O.sub.3, La.sub.2O.sub.3, Ce.sub.2O.sub.3 and Hf.sub.2O.sub.3 respectively, based on the total mass of the catalyst precursor.

28. 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, 15% to 80% by weight of catalytically active components of aluminum, calculated as Al.sub.2O.sub.3, 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, based on the total mass of the catalyst precursor.

29. The process according to claim 28, wherein the catalyst precursor is prepared in the presence of tin nitrate and a complexing agent.

30. The process according to claim 17, wherein the catalyst precursor in step b) is simultaneously contacted with the soluble Ru compound and the soluble Co compound.

31. The process according to claim 17, wherein the concentration of the soluble Ru compound with which the catalyst precursor prepared in step a) is contacted in step b) is in the range from 0.1% to 50% by weight and the concentration of the soluble Co compound with which the catalyst precursor is contacted in step b) is in the range from 0.1% to 20% by weight.

32. The process according to claim 17, wherein the reaction of ethylene glycol and/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

Comparative Example 1

[0300] The catalyst precursor was prepared according to example B3 of WO 2013/072289. Prior to the reduction of the tablets thus prepared, they were comminuted to 1-2 mm spa.

[0301] The catalyst precursor thus obtained was reduced by the following method (see table 1)

TABLE-US-00001 TABLE 1 Duration Temperature Nitrogen Hydrogen Air (min) ( C.) (L (STP)/h) (L (STP)/h) (L (STP)/h) Remarks 1 30 min RT 100 Purge operation at RT 2 44 min 220 95 5 Heating to 220 C. 3 120 min 220 95 5 Hold time at 220 C. 4 30 min 280 95 5 Heating to 280 C. 5 15 min 280 95 5 Increase in the amount of hydrogen 6 15 min 280 90 10 Increase in the amount of hydrogen 7 15 min 280 80 20 Increase in the amount of hydrogen 8 15 min 280 70 30 Increase in the amount of hydrogen 9 15 min 280 60 40 Increase in the amount of hydrogen 10 15 min 280 50 50 Cooling operation to RT 11 120 min 280 50 50 Hold time at 280 C.

[0302] The reduction was followed by passivation of the catalyst precursor. For this purpose, a stream of 50 L (STP)/h of N2 and 0 L (STP)/h of air was passed over the reduced catalyst precursor.

[0303] The amount of air was increased gradually, while the amount of N2 was reduced slowly, until 20 L (STP)/h of N2 and 20 L (STP)/h of air were attained. The increase in the amount of air was conducted in such a way that the catalyst temperature did not exceed 35 C.

Comparative Example 2

[0304] 8.73 g of cobalt nitrate hexahydrate (20.25% by weight of Co) and 1.85 g of nickel nitrate hexahydrate (19% by weight of Ni) were initially charged.

[0305] 56.85 g of Ru nitrosylnitrate solution (16% by weight of Ru) were added to the mixture. The solution thus obtained was made up to a total of 74 mL with demineralized water.

[0306] The metal salt solution thus obtained was transferred to a spray vessel.

[0307] 150 g of Al.sub.2O.sub.3 support (1-2 mm spall) were calcined under an air atmosphere at 900 C. Thereafter, the maximum water absorption was determined. This was 0.55 mL/g.

[0308] The catalyst support was impregnated with the metal salt solution prepared beforehand to 90% of the water absorption in a rotary pan, by spraying the spall on the rotary pan with the corresponding amount of the metal salt solution.

[0309] The spall impregnated with the metal salt solution was then dried at 120 C. in an air circulation drying cabinet for 16 h.

[0310] After the drying, the catalyst precursor was reductively calcined under the conditions specified in table 2.

TABLE-US-00002 TABLE 2 Duration Temperature Heating rate Nitrogen Hydrogen Air (min) ( C.) ( C./min) (L (STP)/h) (L (STP)/h) (L (STP)/h) Remarks 1 30 min RT none 100 Purge operation at RT 2 150 min 150 1 95 5 Heating to 150 C. 3 120 min 150 none 95 5 Hold time at 150 C. 4 50 min 1 95 5 Heating to 150 C. 5 15 min 200 none 95 5 Increase in the amount of hydrogen 6 15 min 200 none 90 10 Increase in the amount of hydrogen 7 15 min 200 none 80 20 Increase in the amount of hydrogen 8 15 min 200 none 70 30 Increase in the amount of hydrogen 9 15 min 200 none 60 40 Increase in the amount of hydrogen 10 15 min 200 none 50 50 Cooling operation to RT 11 120 min 200 none 50 50 Hold time at 200 C.

[0311] After the reductive calcination, the catalyst was passivated by passing a gas stream of 50 L (STP)/h of N2 and 0 L (STP)/h of air over the catalyst at room temperature. The amount of air was increased gradually, while the amount of N2 was reduced slowly, until 20 L (STP)/h of N2 and 20 L (STP)/h of air were attained. The increase in the amount of air was conducted in such a way that the catalyst temperature did not exceed 35 C.

Comparative Example 3

[0312] 8.73 g of cobalt nitrate hexahydrate (20.25% by weight of Co) and 1.45 g of copper nitrate hydrate (26.3% by weight of Cu) were initially charged.

[0313] 56.85 g of Ru nitrosylnitrate solution (16% by weight of Ru) were added to the mixture. The solution thus obtained was made up to a total of 74 mL with demineralized water.

[0314] The metal salt solution thus obtained was transferred to a spray vessel.

[0315] 150 g of Al.sub.2O.sub.3 support (1-2 mm spall) were calcined under an air atmosphere at 900 C. Thereafter, the maximum water absorption was determined. This was 0.55 mL/g.

[0316] The catalyst support was impregnated with the metal salt solution prepared beforehand to 90% of the water absorption in a rotary pan, by spraying the spall on the rotary pan with the metal salt solution.

[0317] The spell impregnated with the metal salt solution was then dried at 120 C. in an air circulation drying cabinet for 16 h.

[0318] After the drying, the catalyst precursor was reductively calcined and passivated as in comparative example 2.

Example 1

[0319] A catalyst precursor was prepared according to example B3 of WO 2013072289.

[0320] The tablets thus obtained (3*3 mm) were comminuted to 1-2 mm spall. The maximum water absorption capacity of the spall was 0.30 mL/g.

[0321] A metal salt solution was prepared. For this purpose, 20.25 g of cobalt nitrate hexahydrate (20.25% by weight of Co) were dissolved in hot water, and 37.91 g of Ru nitrosylnitrate solution were added. The solution thus obtained was made up to 71 mL with demineralized water and transferred to a spray vessel.

[0322] The spell was sprayed in an impregnation apparatus with an amount that corresponds to 95% of the maximum water absorption of the spall. In order to ensure homogeneous uptake of the impregnation solution, the spell was rotated for a further 30 min.

[0323] Thereafter, the catalyst spall was dried in an air circulation drying cabinet at 120 C. for 16 h.

[0324] The catalyst precursor thus obtained was reductively calcined and passivated as described in comparative example 2.

Catalyst Testing:

[0325] The catalysts were tested in a continuously operated parallel plant on the pilot plant scale. The reaction part of the plant consists of eight individual reactors, of which four each are encompassed within one reactor block (heating block). Each individual reactor is a stainless steel tube of length 1.5 m with an internal diameter of 8 mm. The tubes are installed in an electrically heated reactor block consisting of an AlMg alloy.

[0326] The catalyst was introduced into the reactor in the form of spell (1.5 mm-2 mm) and borne on an inert bed of length about 33 cm consisting of glass beads of size 3 mm.

[0327] Above the catalyst bed there is a further, adjoining inert bed of length 15 cm consisting of glass beads of size 3 mm.

[0328] The catalyst and the inert bed were fixed in the reactor by a fabric wire of length 1 cm.

[0329] Each reactor was operated in straight pass and the flow was from the bottom.

[0330] The liquid reactant was supplied from a reservoir with the aid of an HPLC pump. Hydrogen, nitrogen and ammonia were supplied through separate pipelines.

[0331] Samples of the liquid reactor outputs were taken from a separator beyond the reactor exit. The reaction outputs were analyzed by gas chromatography.

[0332] The catalyst was activated prior to the reaction at 200 C. and 170 bar over a period of 18 h in a 50:50 mixture of hydrogen and nitrogen.

[0333] All catalysts were tested under the following conditions: [0334] Temperature: 165 C. [0335] Pressure: 170 bar [0336] H2: 5 L (STP)/h [0337] N2: 10 L (STP)/h [0338] Molar NH3:MEG ratio=10:1 [0339] Catalyst hourly space velocity: 0.3 kg/L/h-0.5 kg/L/h [0340] Catalyst volume: 50 mL

[0341] The exact conditions are summarized in table 3 below.

TABLE-US-00003 TABLE 3 NMEDA + (EDA + NEEDA + Tot. sel. (5 main DETA)/ Cat. HSV/ Conversion/ EDA/ DETA/ AEEA/ PIP/ MEA/ EtNH2/ products)/ (PIP + Catalyst kg/L/h area % area % area % area % area % area % area % area % AEEA) Comparative ex. 1 0.3 27.0 11.6 0.9 0.9 1.6 11.4 0.0 97.9 5.0 Comparative ex. 2 0.3 18.5 10.3 0.4 0.2 0.4 6.7 0.3 97.1 17.9 Comparative ex. 3 0.3 12.4 7.0 0.1 0.1 0.2 4.9 0.1 98.3 30.6 Example 1 0.3 36.4 14.0 2.7 2.0 4.7 11.3 0.1 95.1 2.5

[0342] Comparative example 1 shows a catalyst comprising the active metals Ni, Co, Cu and sn.

[0343] Example 1 differs from comparative example 1 in that the catalyst from comparative example 1 has been further impregnated with Co and Ru. It is clear that the further impregnation distinctly increased the activity.

[0344] In comparative examples 2 and 3, catalysts that comprise the combination of Ru, Co and Ni or Ru, Co and Cu were prepared directly by impregnating soluble compounds of Ru, Co and Ni or Cu on a catalyst support of aluminum oxide.

[0345] In example 1, an Ni-containing catalyst precursor that had been prepared by precipitative application of Ni, Cu, Sn and Co to a support material of aluminum oxide was further impregnated with Ru and Co.

[0346] The comparative examples that were obtained directly by impregnation of support materials with the appropriate active metals do show a high selectivity and low formation of unwanted by-products, such as NMEDA, but show significantly lower activity.

[0347] Only with catalyst precursors that were further impregnated with Ru and Co is it possible to achieve a balanced profile of properties in relation to activity, selectivity and the formation of unwanted by-products.