WO2003018532A1

WO2003018532A1 - Supported catalyst for nitrile hydrogenation

Info

Publication number: WO2003018532A1
Application number: PCT/EP2002/009823
Authority: WO
Inventors: André Harmen SIJPKES; Peter John Van Den Brink; René de Ruiter
Original assignee: Avantium International B.V.
Priority date: 2001-08-28
Filing date: 2002-08-28
Publication date: 2003-03-06
Also published as: WO2003018532B1

Abstract

The present invention relates to a supported catalyst, comprising a) a support b) a metal A, being chosen from nickel and copper or a combination thereof in metallic or oxidic state c) a metal B, being chosen from lithium and calcium or a combination thereof in metallic or oxidic state with the proviso that when metal A comprises nickel, metal B is lithium. Also, the present invention relates to processes for the preparation of the supported catalyst and to the use of the supported catalyst as a hydrogenation catalyst.

Description

SUPPORTED CATALYST FOR NITRILE HYDROGENATION

The present invention relates to a supported catalyst, a method for the preparation thereof and to the use of the said catalyst in the hydrogenation of nitriles.

In the hydrogenation of nitriles many different, optionally supported, catalysts are used, wherein generally a mixture of primary, secondary and tertiary amines is obtained, depending on the catalyst and reaction conditions used. Much research has been done on the control of the hydrogenation to one type of amine, as the isolation of the respective amines requires additional equipment and costs .

A problem that is encountered with known hydrogenation catalysts is that a high conversion of the nitriles in combination with a high selectivity of the hydrogenation reaction is difficult to obtain.

A further problem of known hydrogenation catalysts, such as Raney-nickel, is that they are often difficult to handle, which renders their use less attractive. Moreover, environmental objections are often associated with preparing and using of the known catalysts.

EP 0 566 197 describes a method for the selective preparation of primary amines using a supported nickel and/or cobalt catalyst, comprising an earth alkaline cocatalyst, preferably a potassium compound.

GB 1 590 309 teaches a cobalt catalyst on an earth alkaline metal oxide carrier for the hydrogenation of adiponitrile.

US 3 728 284 discloses on unsupported and unsintered nitrile hydrogenation catalyst comprising a mixture of sodium silicate and a cobalt oxide.

US 4 337 177 describes a supported ruthenium catalyst for the hydrogenation of unsaturated dinitriles.

EP 1 050 339 discloses a hydrogenation catalyst comprising palladium, in particular suitable for the hydrogenation of phenolic compounds . EP 0 985 655 teaches a supported palladium catalyst for the preparation of vinyl acetate, comprising a promoter such as gold, copper, cadmium and gold compounds as well as a salt of metal from Group I, II, lanthanides and transition metals. EP 0 685 451 relates to a supported vinyl acetate catalyst comprising a palladium compound.

US 5 856 262 describes a supported palladium catalyst for selective catalytic hydrogenation of acetylene.

It is an object of the present invention to provide novel catalysts for the hydrogenation of nitriles showing high conversion rates in combination with high selectivity.

The above object is achieved by providing a supported catalyst comprising: a) a support b) a metal A, being chosen from nickel and copper or a combination thereof in metallic or oxidic state c) a metal B, being chosen from lithium and calcium or a combination thereof in metallic or oxidic state with the proviso that when metal A comprises nickel, metal B is lithium. The supported catalyst according to the invention is preferably substantially free of palladium, i.e. comprising, on weight basis less than 10% of the weight content of metal A, preferably less than 5%, more preferably less than 1% even more preferably less than 0.5% and most preferably less than 0.1%. Further the supported catalyst is preferably substantially free of cobalt, i.e. comprising, on weight basis less than 10% of the weight content of metal A, preferably less than 5%, more preferably less than 1% even more preferably less than 0.5% and most preferably less than 0.1%. Preferably the same is true for ruthenium and other Group VIII metals. The supported catalyst according to the present invention shows surprisingly a high conversion rate and selectivity.

In particular it has been found that the supported catalyst according to the present invention exhibits, when used in the hydrogenation of nitriles, a surprisingly high conversion rate in combination with a high selectivity to the primary amine.

A further advantage of the catalyst of the present invention is that it can be used in a fixed bed reactor, but also in a batch process, both in gaseous and liquid phase. In addition, no additional additives are required, such as ammonia.

Also, in many known processes for preparation of catalysts batch reactors are used where the catalyst, which is usually in the form of a fine powder, needs to be separated from the product (s) .

Therefore additional process steps are necessary, for example product recycle steps to obtain sufficient conversion to the desired product, additional purification steps, such as distillation, the addition of other chemicals to enhance selectivity, such as the addition of NaOH or ammonia, all of which require additional processing hardware. In contrast herewith, the catalyst according to the present invention can be produced in a single pass process, i.e. the product does not require a recycle, as will be outlined further below.

The supported catalyst is preferably calcined, as will be outlined further below.

In the supported catalyst according to the present invention any suitable support may be used. It has been found that very good results are obtained, when the catalyst is supported on a porous support. Materials useful as support materials for the supported catalysts of the present invention include, for example, metal oxides, silicates, spinels, carbides, carbonates or mixtures thereof. Preferred supporting materials are aluminium oxides, zirconium oxides, silicon dioxides, silicon dioxide/aluminium oxide mixtures, amorphous silicas, kieselguhrs, barium, strontium or calcium carbonates, mixtures thereof optionally containing, in addition, silicon dioxides or aluminium oxides, titanium oxides, zirconium oxides, magnesium oxides, magnesium silicates, zirconium silicates, magnesium/aluminium spinels, silicon carbides, tungsten carbides, mixtures of silicon carbides with silicon dioxides, carbon, or any desired mixtures of the above-mentioned materials. Alumina and zirconia are particularly preferred. The supporting materials can be used in a very wide variety of forms, for example as spheres, granules, extrudates, tablets, saddle-shaped bodies, tubular sections, fragments and/or honeycomb ceramics. Suitably, the support may have a pore volume from 0.15 to 3.5 ml per gram of support, a surface area of 5 to 800 m² per gram of support and an apparent bulk density of 0.3 to 1.5 g/ml . Nominal size of the support particles is preferably between 1 urn - 5 mm. In particular for liquid phase applications, the particle size is preferably between 1 - 100 μm, more preferably between 4 - 25 μrα . For gas phase applications the particle size is preferably between 0,1 - 5,0 mm, more preferably between 1 - 3 mm for industrial applications . Preferably the porous support comprises metal oxides selected from the group consisting of silicon, aluminum, magnesium, calcium, titanium or zirconium. Most preferably, the support comprises zirconia or alumina; gamma-alumina is a preferred alumina.

Preferably, the composition comprises, based on the dry weight of the catalyst, at least 3 % by weight metal A.

According to a preferred embodiment of the present invention the catalyst comprises, based on the dry weight of the catalyst, at least 1%, preferably at least 4% by weight, of metal B.

It has been found that herewith the catalyst exhibits a particularly high selectivity and conversion. When less than 4% by weight is used, a high conversion rate may be obtained, but a high selectivity is often difficult to obtain. More than 20% by weight is not easily obtained using single step impregnation processes; therefore the catalyst according to the invention preferably comprises based on the dry weight of the catalyst, 4-20% by weight of metal B.

The catalyst preferably comprises 0.1-50 rnmol metal per gram dry support.

According to a particularly preferred embodiment of the present invention, and as is shown in the examples hereinafter, the catalyst comprises at least 4% by weight of lithium or calcium based on the weight of the supported catalyst.

Especially advantageous results are obtained when the catalyst comprises nickel or copper and lithium. Also, as is shown in the Examples, advantageous results are obtained when the catalyst comprises copper and calcium, preferably about 10% by weight of calcium based on the weight of the supported catalyst.

Especially advantageous results are obtained when the composition comprises nickel or copper and lithium. Also, as is shown in the Examples, advantageous results are obtained when the composition comprises copper and calcium, preferably about 10% by weight of calcium based on the weight of the supported catalyst. It has been found that good hydrogenation results are obtained when the catalyst comprises copper and lithium at concentration ranging from 0.1 to 50 mmol metal per gram of zirconia. In particular suitable hydrogenation results are obtained when the catalyst comprises copper at a concentration of 1-3 mmol, preferably about 2 mmol per gram of zirconia, and lithium at a concentration of 3-4 mmol per gram of zirconia.

It has also been found that good hydrogenation results are obtained when the catalyst comprises copper and/or nickel and lithium at concentrations ranging from 0.1 to 50 mmol metal per gram alumina. In particular suitable hydrogenation results are obtained when the catalyst comprises copper at a concentration of 0.8-0.9 mmol, preferably about 0.85 mmol copper per gram of alumina, and lithium at a concentration of 8-9, preferably about 8.1 mmol lithium per gram of alumina; or nickel at a concentration of 0.85-0.95 mmol, in particular about 0.9 mmol nickel per gram alumina, and lithium at a concentration of 8-9, preferably about 8.1 mmol lithium per gram of alumina. It has also been found that good hydrogenation results are obtained when the catalyst comprises copper and calcium at concentrations ranging from 0.1 to 50 mmol metal per gram alumina. In particular suitable hydrogenation results are obtained when the catalyst comprises copper at a concentration of 0.8-0.9 mmol; preferably about 0.85 mmol copper per gram of alumina, and calcium at a concentration of 2-3 mmol, preferably about 2.5 mmol calcium per gram alumina.

In a further aspect the present invention relates to a process for the preparation of a supported catalyst comprising the steps: a) treating the support with a solution comprising a dissolved salt of a metal B, being chosen from lithium and calcium or a combination thereof in metallic or oxidic state, b) treating a support with a solution comprising a dissolved salt of a metal A, being chosen from nickel and copper or a combination thereof in metallic or oxidic state, with the proviso that when metal A comprises nickel, metal B is lithium, c) calcining the treated support.

Herewith a surprisingly simple and elegant process for obtaining supported catalyst is provided. It has also been found that the catalysts obtained in the processes according to the present invention exhibit surprisingly high conversion rates, when used in the hydrogenation of nitriles, in combination with a high selectivity to the primary amine .

Steps a) and b) can be performed subsequently; the sequence of steps a) and b) can also be reversed, i.e. that first the support is treated with a solution of metal A. Although it is preferred to perform step a) before step b) in case the steps a) and b) are performed sequentially. Optionally, between steps a) and b) a drying and/or calcination step can be performed. Such a two-step impregnation is also called "sequential impregnation". However, preferably steps steps a) and b) are combined in that the support is treated with a solution comprising dissolved salts of both metals A and B. This one-step impregnation is also referred to as "co- impregnation". Such co-impregnation can e.g. be performed as follows: a salt of metal A, such as nickel or copper nitrate and a salt of metal B, such as lithium nitrate. Using a zirconia support, a solution can be prepared comprising of lithium nitrate and copper nitrate. The support can be treated with the solution, such that the composition obtains 1.9% by weight of lithium and 2% by weight of copper based on the weight of the supported catalyst. Using alumina as support, a solution can e.g. be prepared comprising of lithium nitrate and copper nitrate. The support can be treated with the solution, such that the composition obtains 5% by weight of lithium and 5% by weight of copper based on the weight of the supported catalyst. Such catalysts have the same composition as given in example 1, and show similar activity and selectivity as the catalyst of example 1. The above co-impregnations are further illustrated in example 2 below.

Preferably the impregnated support is dried before the calcination step. Drying can be performed in a manner which is in itself known. For example, the support may be dried discontinuously or continuously in a drying cabinet or in a stream of warm air at temperatures of about 50° to 200°C, and preferably at 80° to 150°C. Temperatures of 125° to 145°C, in particular about 140°C (i.e. ± 2°C) and pressures of 1 atm are preferred. All pressures indicated herein are absolute pressures. The impregnated support material is preferably dried in this way to a residual moisture content of less than 10%, preferably less than 5%, particularly preferentially less than 2% and very particularly preferentially less than 1% of the absorbency of the support.

After the impregnated support is dried, it is calcined preferably by exposure to an environment having a temperature greater than 200°C and below the melting point of the support, preferably between 350°-600°C, more preferably between 500°-580°C and most preferably at about 550°C (i.e. ± 10°C) , for a period of time sufficient to achieve at least partial thermal decomposition of the metal salt(s). Typically, the calcination step is conducted in air for a period of 0.5 to 12 hours, preferably 2 to 6 hours. The calcination step may be performed as a step separate from the drying step or as a continuation of the drying step by raising the drying temperature suitably and maintaining the impregnated support in this environment for a period of time sufficient to achieve at least partial but preferably complete calcination.

Preferably, the impregnated support is dried at a temperature of between 80 and 150 °C for at least 0.5 h, and calcined at a temperature of between 350 to 600°C for at least 0.5 h, while the heating rate is between 30 and 300°C/h. More preferably the treated support is dried at a temperature of about 120°-140°C during 2 h, and calcined at about 550°C during 2 h, with a heating rate of about 120°C/h.

As is shown in the examples hereinafter, the solution used in step (a) preferably contains a nickel or copper nitrate or a mixture thereof. Also it is preferred that the solution in step b) preferably contains a lithium nitrate.

It has been found that good results are obtained when the support comprises a porous support; examples of suitable supports are given above. The support preferably comprises silica, alumina, zirconia, titania, magnesium oxide, calcium carbonate and carbon, or a combination of at least two thereof, most preferably alumina; gamma-alumina is the most preferred alumina.

Preferably the catalyst obtained by the method according to the invention comprises based on the dry weight of the catalyst, at least 1 w/w%, preferably at least 4 w/w%, and most preferably 4-20 w/w% of metal B. The said catalyst preferably comprises at least 3% by weight of metal A. Also, the present invention relates to a catalyst obtainable according to the process according to the present invention.

Finally, the present invention relates to the use of the catalyst according to the present invention, in particular as a hydrogenation catalyst.

Preferably the catalysts according to the present invention are used in the hydrogenation of nitriles, in particular in the selective hydrogenation of nitriles for the production of amines in particular primary amines . The person skilled in the art will understand that 'nitriles' comprises its normal meaning, i.e. containing a cyano group. Therefore, 'nitriles' comprises acetonitrile, adiponitrile, etc. Further, the person skilled in the art will understand that many modifications may be made without departing from the spirit of the invention. For instance, in the hydrogenation of nitriles suitable additional compounds such as a cocatalyst may be used, if desired or appropriate.

Hereinafter the present invention will be illustrated in more detail by a series of non-limiting examples.

Example 1A

Preparation of a copper lithium zirconia catalyst (10.4Cu2. OLiZIR) A portion of 10.0 g zirconia (XA16052, Norpro, USA), comprising particles with an average particle size between 0.2 and 0.4 mm, and with a pore volume of 0.31 ml/g, was impregnated with 3.1 ml of a solution of 2.6 g of lithium nitrate dissolved in water. After homogenizing, the product was dried at 140 °C for 2 h and subsequently calcined at 550 °C for 2 h while heating at a rate of 120 °C/h. A portion of 1 g of the lithium-zirconia was impregnated with 0.27 ml of a solution of 0.48 g of copper (II) nitrate trihydrate in water. After homogenizing, the product was dried at 120 °C for 2 h and subsequently calcined at 550 °C for 2 h while heating at a rate of 120 °C/h. A supported catalyst was obtained, comprising 10.4% Cu, 2.0% Li, based on the weight of the supported catalyst. The concentrations of copper and lithium are preferably from 0.1 to 50 mmol per gram zirconia. The concentration of copper is more preferably 1.5 to 2.5, most preferably about 2.0 mmol copper per gram zirconia, and the concentration lithium is more preferably 3 to 4, most preferably about 3.6 mmol lithium per gram of zirconia.

Example IB Preparation of a copper lithium alumina catalyst (5Cu5LiALU) A portion of 10 g gamma-alumina (SA6*78, NorPro, USA), comprising particles with an average particle size between 0.2 and 0.6 mm, and with a pore volume of 0.7 ml/g, was impregnated with 7.0 ml of a solution of 6.3 g of lithium nitrate dissolved in water. After homogenizing, the product was dried at 140°C for 2 h and subsequently calcined at 550°C for 2 h while heating at a rate of 120°C/h. A portion of 1 g of the lithium-alumina was impregnated with 0.55 ml of a solution of 0.2 g of copper (II) nitrate trihydrate in water. After homogenizing, the product was dried at 120 °C for 2 h and subsequently calcined at 550 °C for 2 h while heating at a rate of 60°C/h. A supported catalyst was obtained, comprising 4.5% Cu, 4.6% Li, based on the weight of the supported catalyst.

Example 2A Preparation of a copper lithium zirconia catalyst (2. OCul .9LiZIR) A portion of 1.0 g zirconia (XA16052, NorPro, USA), comprising particles with an average particle size between 0.2 and 0.4 mm, and with a pore volume of 0.31 ml/g, was impregnated with 0.31 ml of a solution of 0.20 g of lithium nitrate and 0.082 g of copper (II) nitrate trihydrate in water. After homogenizing, the product was dried at 120 °C for 2 h and subsequently calcined at 550 °C for 2 h while heating at a rate of 120 °C/h. A supported catalyst was obtained, comprising 2.0% Cu, 1.9% Li, based on the weight of the supported catalyst.

The concentrations of copper and lithium are preferably 0.1 to 50 mmol per gram zirconia. The concentration of copper is more preferably 0.2 to 0.4, most preferably about 0.34 mmol copper per gram zirconia. The concentration of lithium is more preferably of 2 to 4, most preferably about 2.9 mmol lithium per gram of zirconia.

Example 2B

Preparation of a nickel lithium alumina catalyst (5Ni5LiALU) A portion of 10 g gamma-alumina (SA6*78, NorPro, USA), comprising particles with an average particle size between 0.2 and 0.6 mm, and with a pore volume of 0.7 ml/g, was impregnated with 7.0 ml of a solution of 6.3 g of lithium nitrate dissolved in water. After homogenizing, the product was dried at 140°C for 2 h and subsequently calcined at 550 °C for 2 h while heating at a rate of 120°C/h. A portion of 1 g of the lithium-alumina was impregnated with 0.55 ml of a solution of 0.26 g of nickel (II) nitrate hexahydrate in water. After homogenizing, the product was dried at 120°C for 2 h and subsequently calcined at 550°C for 2 h while heating at a rate of 60°C/h. A supported catalyst was obtained, comprising 4.4% Ni, 4.6% Li, based on the weight of the supported catalyst.

Comparative Example 1 Preparation of a copper cerium alumina catalyst (5Cul0CeALU) A portion of 10 g gamma-alumina (SA6*78, NorPro, USA), comprising particles with an average particle size between 0.2 and 0.6 mm, and with a pore volume of 0.7 ml/g, was impregnated with 7.0 ml of a solution of 3.5 g of cerium nitrate dissolved in water. After homogenizing, the product was dried at 140°C for 2 h and subsequently calcined at 550°C for 2 h while heating at a rate of 120°C/h. A portion of 1 g of the cerium-alumina was impregnated with 0.60 ml of a solution of 0.2 g of copper (II) nitrate trihydrate in water. After homogenizing, the product was dried at 120°C for 2 h and subsequently calcined at 550 °C for 2 h while heating at a rate of 60°C/h. A supported catalyst was obtained, comprising 4.4% Cu, 8.4% Ce, based on the weight of the supported catalyst.

Example 3 Preparation of a copper calcium alumina catalyst (5Cul0CaALU)

A portion of 10 g alumina (SA6*78, NorPro, USA) , comprising particles with an average particle size between 0.2 and 0.6 mm, and with a pore volume of 0.7 ml/g, was impregnated with 10.0 ml of a solution of 6.85 g of calcium nitrate tetrahydrate dissolved in water. After homogenizing, the product was dried at 140°C for 2 h and subsequently calcined at 550°C for 2 h while heating at a rate of 120°C/h. A portion of 1 g of the calcium-alumina was impregnated with 0.56 ml of a solution of 0.2 g of copper (II) nitrate trihydrate in water. After homogenizing, the product was dried at 120°C for 2 h and subsequently calcined at 550°C for 2 h while heating at a rate of 60°C/h. A supported catalyst was obtained, comprising 4.4% Cu, 8.3% Ca, based on the weight of the supported catalyst.

Example 4

Preparation of a copper lithium alumina catalyst (5CuxLiALU) .

A portion of 2.0 g of alumina (Pural BT, Condea, Germany), having an average particle size between 5 and 10 micron, and with a pore volume of 0.30 ml/g, was added to 10 ml water. To the slurry was added 0.46 g copper (II) nitrate trihydrate which dissolved readily. To the slurry was added 7.3 iti 10% LiOH to precipitate the Cu. The precipitated Cu on alumina slurry was washed three times with 10 ml 10% LiOH solution. The precipitated Cu on alumina was separated from the liquid by centrifugation. Finally, the wet residu was dried at 120 °C for 16 h and calcined at 550 °C for 2 h in a muffle oven.

Example 5

Liquid phase - batch reaction. A batch reactor (HEL, UK) was loaded with 2.05 g acetonitrile (50.0 mmol) dissolved in 15.0 mL isopropanol. Next, 100 mg of a catalyst (5Cul0CaALU, Example 3, ground and sieved to <50 micron particle size) was added to the solution. The reaction was run at a temperature of 170 °C, and a pressure of 50 bar H2 for 2 h. After cooling to room temperature a sample was withdrawn and analyzed by GC (Interscience, The Netherlands) . The following compounds were specifically targeted for analysis: acetonitrile, mono-, di-, and triethylamine (MEA, DEA, TEA, respectively) . The acetonitrile conversion was 91%, and the selectivity of the reaction was 100% MEA, i.e. no DEA and TEA were found, which was also found for the gas phase reaction (See Table 1, Ex. 3) .

Example 6 Comparative test The catalysts obtained in Examples 1-3 and Comparative Example 1 were tested on a parallel-reactor nanoflow equipment (Nanoflow 1A, Avantium Technologies B.V., Amsterdam, The Netherlands). An amount of 25 to 200 mg of catalyst was loaded in a reactor having an inner diameter of 4 mm. The temperature during the hydrogenation reaction was controlled by PID (Proportional Integral Differential) . Experiments were performed at eight temperatures, from 80 to 240°C. After reaching a temperature level the hydrogenation reaction was allowed to equilibrate for 30 to 60 minutes. The pressure during the reaction was maintained at 1 bar. A flow of acetonitrile (the partial pressure of acetonitrile was maintained at about 10 mbar) was cofed with gasflow of the hydrogen flow which was maintained at a GHSV (Gas

were specifically targeted for analysis: acetonitrile (AN), mono-, di-, and triethylamine (MEA, DEA, TEA, respectively) , ammonia (NH₃) , methane (M) , and ethane (E) , the latter three product occurring at high temperatures. Samples were taken at 80 minutes intervals over a period of 15 h. The test results are listed in Table 1.

Table 1 Test results

Table 1 (continued) Test results

¹ Compounds other than MEA, DEA, and TEA, being methane, ethane, and ammonia, are denoted by "Rest". This number was calculated by subtracting the amounts of MEA, DEA, and TEA from the amount of AN. As can be seen from Table 1, the catalysts according to the present invention show a high conversion rate of (aceto) nitrile in combination with a high selectivity of the hydrogenation of acetonitrile into monoethylamine (MEA) , when using the catalyst according to Example 1, 2 and 3 at 100-240°C. At temperatures higher than 220°C, the conversion of e.g. acetonitrile is sometimes accompanied by the formation of unwanted products such as methane, ethane, and ammonia. In addition, the formation of diethyla ine and triethylamine becomes more favoured at higher temperatures, so that the selectivity to the primary amine decreases. The preferred temperature range where the catalysts are used for the hydrogenation of (aceto) nitrile is 100 - 260°C, more preferably 160 - 240°C, even more preferably 180 - 220°C. Also, it has been found that the catalysts according to the present invention provide for a high conversion rate in combination with a high selectivity when used for the hydrogenation of other nitriles such as adiponitrile, valeronitrile, succinonitrile, fatty nitriles (preferably C₆ to C₂₂) etc.

Claims

C L A I M S

1. Supported catalyst, comprising a) a support b) a metal A, being chosen from nickel and copper or a combination thereof in metallic or oxidic state c) a metal B, being chosen from lithium and calcium or a combination thereof in metallic or oxidic state with the proviso that when metal A comprises nickel, metal B is lithium.

2. Supported catalyst according to claim 1, the support comprising silica, alumina, zirconia, titania, magnesiumoxide, calcium carbonate and carbon, or a combination of at least two thereof.

3. Supported catalyst to claim 2, the porous support comprising zirconia, alumina or a combination thereof.

4. Supported catalyst according to any of the preceding claims, wherein the catalyst comprises, based on the dry weight of the catalyst, at least 1%, preferably at least 4% by weight, of metal B.

5. Supported catalyst according to claim 4, wherein the catalyst comprises, based on the dry weight of the catalyst, 4-20% by weight of metal B.

6. Supported catalyst according to any of the preceding claims, wherein the catalyst comprises 0.1-50 mmol metal per gram dry support .

7. Catalyst according to one or more of the preceding claims, wherein metal B is lithium.

8. Catalyst according to one or more of the preceding claims, wherein the catalyst comprises copper and calcium.

9. Method for the preparation of a supported catalyst, comprising the steps of a) treating a support with a solution comprising a dissolved salt of a metal B, being chosen from lithium and calcium or a combination thereof in metallic or oxidic state, b) treating the support with a solution comprising a dissolved salt of a metal A, being chosen from nickel and copper or a combination thereof in metallic or oxidic state, with the proviso that when metal A comprises nickel, metal B is lithium, c) calcining the treated support.

10. Method according to claim 9, wherein steps a) and b) are combined in that the support is treated with a solution comprising dissolved salts of both metals A and B.

11. Method according to claim 9, wherein between steps a) and b) the support is calcined.

12. Method according to claim 11, wherein the calcination is performed between 350-600 °C, preferably between 500-580 °C, most preferably at about 550°C.

13. Method according to any of the claims 9-12, wherein the support is dried before the calcination step.

14. Method according to claim 13, wherein drying is performed between 80-150°C, preferably between 125-145°C, most preferably at about 140°C.

15. Method according to any of the claims 9-14, wherein the dissolved salt of at least one of the metals A and B, is a nitrate salt, preferably both being nitrate salts.

16. Method according to any of the claims 9-15, wherein the support comprises silica, alumina, zirconia, titania, magnesiumoxide, calcium carbonate and carbon, or a combination of at least two thereof.

17. Method according to any of the claims 9-16, wherein the obtained catalyst comprises, based on the dry weight of the catalyst, at least 1 w/w%, preferably at least 4 w/w%, and most preferably 4-20 w/w% of metal B.

18. Use of a catalyst according to any of the claims 1-9 for the hydrogenation of nitriles into amines.

19. Use of a catalyst obtainable by the method according to any of the claims 9-17, for the hydrogenation of nitriles into amines.