Hydrogenation catalyst and precursor thereof and use thereof in the hydrogenation of petrochemical resins

Abstract

The present invention relates to a supported nickel catalyst precursor comprising Ni, Si, Al and O, wherein the catalyst precursor shows a specific total intrusion volume determined by Hg intrusion. In addition, the present invention relates to a method for preparing the catalyst precursor. In addition, the present invention relates to a supported nickel catalyst prepared from the catalyst precursor. In addition to this, the present invention also relates to its use in the hydrogenation reaction of aromatic compounds.

Description

Technical Field

[0001] The present invention relates to a supported nickel catalyst and its precursor comprising Ni, Si, Al and O, wherein the catalyst precursor shows a specific total intrusion volume determined by Hg intrusion. In addition, the present invention relates to a method for preparing the catalyst and its precursor and its use in the hydrogenation reaction of aromatic compounds.

[0002] introduce

[0003] Petrochemical resins have their applications in the field of adhesives, especially nonwovens, coatings and construction. Petrochemical resins are produced by polymerization of the C9 fraction after distillation of the raw materials obtained from naphtha cracking. However, the resulting aromatic polymers are relatively unstable to thermal and oxidative conditions, which will lead to degradation and thus reduce their adhesive properties. In order to overcome the instability of C9 resins, hydrogenation is usually carried out. As a result, the double bonds that are the cause of thermal and oxidative instability are removed.

[0004] As for the catalysts usually used for hydrogenation, they usually contain nickel as the catalytically active component. In order to obtain a highly dispersed catalyst, the active metal catalyst is usually supported on an oxide support, for example on a combined SiO2-Al2O3 support.

[0005] WO 01 / 36093 A1 relates to a catalyst for the hydrogenation of hydrocarbon resins, comprising an iron-containing nickel catalyst supported on silica and alumina. WO 2004 / 035204 A1 relates to a catalyst for hydrogenation reactions, wherein the catalyst comprises nickel, silica, alumina and magnesium. US 9,045,410 B2 relates to a catalyst comprising nickel and a solid silica support, wherein the catalyst is used for the hydrogenation of unsaturated fatty materials.

[0006] WO 2015 / 008247 A2 relates to a process and a catalyst for the hydrogenation of resins, wherein the catalyst comprises cobalt-promoted nickel supported on silica-alumina. WO 2014 / 128204 A1 relates to a process for preparing a catalyst, wherein the process comprises, inter alia, precipitating the catalyst from a solution comprising a nickel salt and a copper salt; mixing the catalyst with an organic fatty acid comprising a carboxylic acid group; and subjecting the obtained mixture to an elevated temperature to decompose the organic fatty acid, obtaining a heat-treated material.

[0007] Despite the progress made in providing efficient hydrogenation catalysts, particularly in the hydrogenation of petrochemical resins, there continues to be a need for better performing catalysts, particularly with respect to their activity in hydrogenation reactions. DETAILED DESCRIPTION

[0008] The object of the present invention is to provide an improved hydrogenation catalyst, in particular with respect to its catalytic activity, and to provide a method for producing such an improved hydrogenation catalyst. Thus, it has surprisingly been found that the process of the present invention allows the production of hydrogenation catalysts with significantly increased activity, in particular in the hydrogenation of petrochemical resins. In particular, it has been unexpectedly found that the process of the present invention allows the production of hydrogenation catalysts showing a specific porosity, resulting in a significantly increased hydrogenation activity. More specifically, it has been surprisingly found that the process of the present invention leads to a greatly increased mesopores of the resulting material compared to catalyst materials known in the art, resulting in an unexpected increase in the activity of the catalyst of the present invention.

[0009] Thus, preferably, the present invention relates to a supported nickel catalyst precursor obtainable and / or obtained by the process according to any one of the embodiments disclosed herein, comprising Ni, Si, Al and O, and / or wherein the catalyst precursor exhibits a total intrusion volume of 2.5 to 6.5 cm 3 / g (ml / g), preferably 3 to 5.5cm 3 / g (ml / g), more preferably 3.5 to 5cm 3 / g (ml / g), more preferably 3.7 to 4.7 cm 3 / g (ml / g), more preferably 3.8 to 4.5 cm 3 / g (ml / g), more preferably 3.9 to 4.3 cm 3 / g (ml / g), more preferably 4 to 4.2cm 3 Preferably, the total invasion volume is determined according to Reference Example 1.

[0010] Preferably, the total pore volume of the catalyst precursor is in the range of 0.5 to 2 cm 3 / g, more preferably 0.6 to 1.8 cm 3 / g, more preferably 0.65 to 1.5 cm 3 / g, more preferably 0.7 to 1.3 cm 3 / g, more preferably 0.75 to 1.1 cm 3 / g, more preferably 0.8 to 1 cm 3 / g, more preferably 0.85 to 0.95 cm 3 / g, more preferably 0.9 to 0.92 cm 3 Preferably, the total pore volume is determined according to Reference Example 2.

[0011] Preferably, the cumulative pore volume of the catalyst precursor with pore diameters of 2 to 5 nm is in the range of 0.1 to 0.5 cm 3 / g, more preferably 0.13 to 0.4 cm 3 / g, more preferably 0.15 to 0.35 cm 3 / g, more preferably 0.18 to 0.32 cm3 / g, more preferably 0.2 to 0.29 cm3 / g, more preferably 0.22 to 0.27 cm3 / g, more preferably 0.24 to 0.25 cm3 / g. Preferably, the cumulative pore volume is determined according to Reference Example 2.

[0012] Preferably, the cumulative pore volume of the catalyst precursor with pore diameters of 2 to 60 nm is in the range of 0.3 to 1.5 cm 3 / g, more preferably 0.5 to 1.2 cm 3 / g, more preferably 0.55 to 1 cm 3 / g, more preferably 0.6 to 0.9 cm 3 / g, more preferably 0.65 to 0.85 cm 3 / g, more preferably 0.7 to 0.8 cm 3 / g, more preferably 0.73 to 0.77 cm 3 Preferably, the cumulative pore volume is determined according to Reference Example 2.

[0013] Preferably, the cumulative pore volume of the catalyst precursor with a pore size of 20 to 80 nm is in the range of 0.15 to 0.7 cm 3 / g, more preferably 0.18 to 0.55 cm 3 / g, more preferably 0.2 to 0.45 cm 3 / g, more preferably 0.23 to 0.4 cm 3 / g, more preferably 0.25 to 0.38 cm 3 / g, more preferably 0.28 to 0.35 cm 3 / g, more preferably 0.31 to 0.33 cm 3 Preferably, the cumulative pore volume is determined according to Reference Example 2.

[0014] Preferably, the BET surface area of ​​the catalyst precursor is in the range of 200 to 350 m 2 / g, more preferably 230 to 320m 2 / g, more preferably 250 to 300m 2 / g, more preferably 260 to 285m 2 / g, more preferably 265 to 280m 2 Preferably, the BET surface area is determined according to ISO 9277:2010.

[0015] In addition, the present invention relates to a method for preparing a supported nickel catalyst precursor, comprising

[0016] (1) preparing a first aqueous solution (S1) containing one or more bases;

[0017] (2) preparing a second aqueous solution (S2) comprising one or more nickel-containing compounds and one or more aluminum-containing compounds;

[0018] (3) preparing a third aqueous solution (S3) containing one or more silicon-containing compounds;

[0019] (4) optionally preparing a fourth aqueous solution (S4) comprising one or more aluminum-containing compounds;

[0020] (5) feeding solutions S2 and S3 and optionally solution S4 into solution S1 to precipitate a supported nickel catalyst precursor, wherein the pH of the resulting mixture is in the range of 6.5 to 8.5;

[0021] (6) Separating the supported nickel catalyst precursor from the mixture obtained in (5).

[0022] Preferably, the pH of the mixture obtained in (5) is in the range of 6.9 to 8.1, more preferably 7.1 to 7.9, more preferably 7.3 to 7.8, more preferably 7.4 to 7.7.

[0023] Preferably, the one or more bases in (1) are selected from the group consisting of inorganic bases and organic bases, preferably the group of inorganic bases, wherein preferably the one or more bases are selected from the group consisting of hydroxides, carbonates, aluminates and mixtures of two or more thereof, more preferably selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, more preferably selected from the group consisting of alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb, Cs and mixtures of two or more thereof, more preferably selected from the group consisting of Li, Na, K and mixtures of two or more thereof, wherein more preferably the alkali metal is Na and / or K, preferably Na, and wherein, more preferably, the one or more bases comprise sodium carbonate and / or sodium aluminate, preferably sodium carbonate, wherein more preferably, the one or more bases are sodium carbonate and / or sodium aluminate, preferably sodium carbonate.

[0024] Preferably, the one or more bases comprise one or more polybasic salts, preferably, one or more polybasic salts selected from the group consisting of: dibasic salts, ternary salts and quaternary salts, including mixtures of two or more thereof, more preferably selected from the group consisting of: dibasic and ternary salts, including mixtures of two or more thereof, wherein more preferably, the one or more bases comprise one or more dibasic salts and / or one or more ternary salts, and more preferably are one or more dibasic salts, wherein more preferably, the one or more bases consist of one or more dibasic salts and / or one or more ternary salts, more preferably consist of one or more dibasic salts.

[0025] In case the one or more bases comprise one or more polybasic salts, preferably, the one or more cations of the one or more polybasic salts are selected from the group consisting of alkali metals and alkaline earth metals, including mixtures and / or combinations of two or more thereof, more preferably selected from the group consisting of alkali metals, including mixtures and / or combinations of two or more thereof, more preferably selected from the group consisting of Li, Na, K, Rb and Cs, including mixtures and / or combinations of two or more thereof, more preferably selected from the group consisting of Li, Na and K, including mixtures and / or combinations of two or more thereof, wherein, more preferably, the one or more cations of the one or more polybasic salts are Na and / or K, preferably Na.

[0026] Preferably, the one or more nickel-containing compounds in (2) are one or more nickel salts, more preferably one or more Ni(II) salts, wherein the anions of the one or more nickel salts are preferably selected from the group consisting of: halides, carbonates, bicarbonates, sulfates, bisulfates, hydroxides, nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, acetates and combinations of two or more thereof, more preferably selected from the group consisting of: chlorides, bromides, fluorides, bicarbonates, hydrogen sulfates, nitrates, dihydrogen phosphates, acetates and combinations of two or more thereof, more preferably selected from the group consisting of: chlorides, fluorides, nitrates, acetates and combinations of two or more thereof, wherein, more preferably, the anions of the one or more nickel salts are chlorides and / or nitrates, preferably chlorides, and wherein, more preferably, the one or more nickel-containing compounds comprise nickel(II) chloride, wherein more preferably, the one or more nickel-containing compounds are nickel(II) chloride.

[0027] Preferably, the one or more aluminum-containing compounds in (2) are one or more aluminum salts, wherein the anions of the one or more aluminum salts are preferably selected from the group consisting of halides, sulfates, hydroxides, nitrates and combinations of two or more thereof, more preferably selected from the group consisting of chlorides, fluorides, sulfates, hydroxides, nitrates and combinations of two or more thereof, wherein, more preferably, the anions of the one or more aluminum salts are chlorides and / or sulfates, preferably chlorides, and wherein, more preferably, the one or more aluminum-containing compounds comprise aluminum chloride, wherein, more preferably, the one or more aluminum-containing compounds are aluminum chloride.

[0028] Preferably, the one or more silicon-containing compounds in (3) are selected from the group consisting of silicates, more preferably selected from the group consisting of silicates, more preferably selected from the group consisting of alkali metal silicates and mixtures thereof, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs and mixtures of two or more thereof, more preferably selected from the group consisting of Li, Na, K and mixtures of two or more thereof, wherein more preferably the alkali metal is Na and / or K, preferably Na, and wherein, more preferably, the one or more silicon-containing compounds comprise sodium silicate, wherein more preferably, the one or more silicon-containing compounds are sodium silicate.

[0029] Preferably, the solution S3 prepared in (3) further comprises one or more bases, wherein the one or more bases are preferably selected from the group consisting of: inorganic bases and organic bases, preferably selected from the group consisting of: inorganic bases, wherein preferably, the one or more bases are selected from the group consisting of: hydroxides, carbonates, aluminates and mixtures of two or more thereof, more preferably selected from the group consisting of: alkali metal hydroxides, alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, more preferably selected from the group consisting of: alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, wherein more preferably, the one or more bases comprise one or more alkali metal carbonates, wherein the alkali metal is preferably selected from the group consisting of: Li, Na, K, Rb and Cs and mixtures of two or more thereof, more preferably selected from the group consisting of: Li, Na, K and mixtures of two or more thereof, wherein more preferably, the alkali metal is Na and / or K, preferably Na.

[0030] In the case where the solution S3 prepared in (3) further comprises one or more bases, preferably, the concentration of the one or more bases is in the range of 0.01 to 10 mol / l, more preferably 0.05 to 5 mol / l, more preferably 0.1 to 3 mol / l, more preferably 0.3 to 2.5 mol / l, more preferably 0.5 to 2.1 mol / l, more preferably 0.8 to 1.8 mol / l, more preferably 1 to 1.6 mol / l, more preferably 1.2 to 1.4 mol / l, more preferably 1.25 to 1.35 mol / l, more preferably 1.28 to 1.3 mol / l.

[0031] Preferably, the one or more aluminum-containing compounds in (4) are selected from the group consisting of aluminates, more preferably from the group consisting of aluminates, more preferably from the group consisting of alkali metal aluminates and mixtures thereof, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs and mixtures of two or more thereof, more preferably selected from the group consisting of Li, Na, K and mixtures of two or more thereof, wherein more preferably the alkali metal is Na and / or K, preferably Na, and wherein, more preferably, the one or more aluminum-containing compounds comprise sodium aluminate, wherein more preferably, the one or more aluminum-containing compounds are sodium aluminate.

[0032] Preferably, the concentration of the one or more bases in (1) ranges from 0.005 to 1 mol / l, more preferably from 0.01 to 0.7 mol / l, more preferably from 0.03 to 0.5 mol / l, more preferably from 0.05 to 0.3 mol / l, more preferably from 0.08 to 0.2 mol / l, more preferably from 0.1 to 0.15 mol / l, more preferably from 0.11 to 0.13 mol / l.

[0033] Preferably, the concentration of one or more nickel-containing compounds in (2) ranges from 0.05 to 5 mol / l, more preferably from 0.1 to 4 mol / l, more preferably from 0.3 to 3 mol / l, more preferably from 0.5 to 2.5 mol / l, more preferably from 0.8 to 2 mol / l, more preferably from 1 to 1.8 mol / l, more preferably from 1.2 to 1.5 mol / l, more preferably from 1.35 to 1.4 mol / l.

[0034] Preferably, the concentration of the one or more aluminum-containing compounds in (2) ranges from 0.001 to 0.5 mol / l, more preferably from 0.005 to 0.3 mol / l, more preferably from 0.01 to 0.2 mol / l, more preferably from 0.03 to 0.15 mol / l, more preferably from 0.04 to 0.1 mol / l, more preferably from 0.05 to 0.08 mol / l, more preferably from 0.055 to 0.075 mol / l, more preferably from 0.06 to 0.07 mol / l.

[0035] Preferably, the concentration of the one or more silicon-containing compounds in (3) ranges from 0.01 to 5 mol / l, more preferably from 0.05 to 3 mol / l, more preferably from 0.1 to 1.5 mol / l, more preferably from 0.2 to 1 mol / l, more preferably from 0.3 to 0.8 mol / l, more preferably from 0.35 to 0.6 mol / l, more preferably from 0.4 to 0.55 mol / l, more preferably from 0.45 to 0.5 mol / l.

[0036] Preferably, the concentration of the one or more aluminum-containing compounds in (4) ranges from 0.001 to 5 mol / l, more preferably from 0.05 to 3 mol / l, more preferably from 0.1 to 2 mol / l, more preferably from 0.3 to 1.5 mol / l, more preferably from 0.4 to 1 mol / l, more preferably from 0.5 to 0.8 mol / l, more preferably from 0.55 to 0.7 mol / l, more preferably from 0.6 to 0.65 mol / l.

[0037] In the case where the concentration of one or more aluminum-containing compounds in (4) is in the range of 0.001 to 5 mol / l, preferably, the concentration of one or more aluminum-containing compounds in (2) is in the range of 0.001 to 0.2 mol / l, more preferably 0.005 to 0.1 mol / l, more preferably 0.01 to 0.08 mol / l, more preferably 0.015 to 0.05 mol / l, more preferably 0.02 to 0.04 mol / l, more preferably 0.025 to 0.035 mol / l.

[0038] Preferably, the ratio S2:S3 of the total volume of solution S2 fed into solution S1 to the total volume of solution S3 is in the range of 0.05:1 to 1:0.05, more preferably 0.1:1 to 1:0.1, more preferably 0.3:1 to 1:0.3, more preferably 0.5:1 to 1:0.5, more preferably 0.7:1 to 1:0.7, more preferably 0.8:1 to 1:0.8, more preferably 0.9:1 to 1:0.9.

[0039] Preferably, the ratio S2:S3:S4 of the total volume of solution S2 fed into solution S1, the total volume of solution S3, and the total volume of optional solution S4, respectively, is in the following range: (0.05 to 20):(0.05 to 20):(0.0005 to 2), more preferably (0.1 to 10)):(0.1 to 10):(0.001 to 1), more preferably (0.3 to 3):(0.3 to 3):(0.005 to 0.07), more preferably (0.5 to 2):(0.5 to 2):(0.01 to 0.05), more preferably (0.7 to 1.5):(0.7 to 1.5):(0.015 to 0.045), more preferably (0.8 to 1.3):(0.8 to 1.3):(0.02 to 0.04), more preferably (0.9 to 1.1):(0.9 to 1.1):(0.025 to 0.035).

[0040] Preferably, the ratio S2:S1 of the total volume of solution S2 to the total volume of solution S1 fed thereto is in the range of 0.01 to 5, more preferably 0.05 to 2, more preferably 0.1 to 1, more preferably 0.3 to 0.7, more preferably 0.4 to 0.55, more preferably 0.45 to 0.5.

[0041] Preferably, the ratio S3:S1 of the total volume of solution S2 to the total volume of solution S1 fed thereto is in the range of 0.01 to 5, more preferably 0.05 to 2, more preferably 0.1 to 1, more preferably 0.3 to 0.7, more preferably 0.4 to 0.55, more preferably 0.45 to 0.5.

[0042] Preferably, the ratio S4:S1 of the total volume of the optional solution S4 to the total volume of the solution S1 fed thereto is comprised in the range of 0.0001 to 1, more preferably 0.0005 to 0.5, more preferably 0.001 to 0.1, more preferably 0.003 to 0.05, more preferably 0.005 to 0.03, more preferably 0.008 to 0.025, more preferably 0.01 to 0.02, more preferably 0.013 to 0.017.

[0043] Preferably, in (5), independently of each other, the duration of feeding of S2, S3 solutions and optional solution S4 is 1 min to 24 h, more preferably 0.05 to 12 h, more preferably 0.1 to 6 h, more preferably 0.25 to 3 h, more preferably 0.5 to 1.5 h, more preferably 0.75 to 1.25 h.

[0044] Preferably, solutions S2 and S3 and optionally solution S4 are fed to solution S1 in (4) subsequently or simultaneously, more preferably simultaneously.

[0045] Preferably, the feeding of solutions S2 and S3 into solution S1 in (4) is performed under stirring of solution S1, wherein the stirring of solution S1 is more preferably achieved by stirring.

[0046] Preferably, solutions S1, S2, S3 and optional solution S4 are heated before solutions S2 and S3 and optional solution S4 are fed into solution S1 in (5), wherein the temperature to which each solution is heated before being fed into (5) is 30 to 100°C, preferably 50 to 99°C, more preferably 60 to 98°C, more preferably 70 to 96°C, more preferably 75 to 94°C, more preferably 80 to 92°C, more preferably 85 to 90°C.

[0047] Preferably, during the feeding period of (5), the resulting mixture is heated and maintained at a temperature in the range of 30 to 100°C, preferably 50 to 99°C, more preferably 60 to 98°C, more preferably 70 to 96°C, more preferably 75 to 94°C, more preferably 80 to 92°C, more preferably 85 to 90°C.

[0048] The method may include further steps. Preferably, the method further includes

[0049] (7) washing the supported nickel catalyst precursor obtained in (6); and / or, preferably and

[0050] (8) Drying the supported nickel catalyst precursor obtained in (6) or (7).

[0051] As mentioned above, the method may include further method steps. Preferably, the method further comprises

[0052] (9) calcining the supported nickel catalyst precursor obtained in (6), (7) or (8) to obtain a supported nickel catalyst precursor comprising a mixed oxide of NiO, SiO2 and Al2O3.

[0053] In the case where the method further includes (9), preferably, the temperature range for calcining in (9) is 200 to 900°C, more preferably 230 to 700°C, more preferably 250 to 600°C, more preferably 280 to 550°C, more preferably 300 to 500°C, more preferably 330 to 450°C, more preferably 350 to 400°C, more preferably 370 to 380°C.

[0054] In addition, when the method further includes (9), the calcination in (9) is preferably performed in an atmosphere containing air, wherein the calcination in (9) is preferably performed in air.

[0055] In addition, the present invention relates to a supported nickel catalyst precursor obtainable and / or obtained by a method according to any one embodiment of the present disclosure, preferably according to a method (1), (2), (3), preferably (4), (5), (6), preferably (7), preferably (8), and preferably (9) as disclosed herein, more preferably, according to a method including the present disclosure, which includes method steps (1), (2), (3), preferably (4), (5), (6), (7), (8), and preferably (9) as disclosed herein, more preferably, according to a method including the present disclosure, which includes method steps (1), (2), (3), preferably (4), (5), (6), preferably (7), and preferably (8) as disclosed herein, more preferably, according to a method including the present disclosure, which includes method steps (1), (2), (3), preferably (4), (5), (6), (7), and (8) as disclosed herein.

[0056] In addition, the present invention also relates to a supported nickel catalyst precursor obtainable and / or obtained according to any one of the specific and preferred embodiments disclosed herein, which comprises a mixed oxide of NiO, SiO2 and Al2O3, which comprises a step of calcining the supported nickel catalyst precursor.

[0057] Furthermore, the present invention relates to a method for preparing a supported nickel catalyst, comprising

[0058] (i) providing a supported nickel catalyst precursor obtainable and / or obtained according to the method of any one of the embodiments disclosed herein;

[0059] (ii) reducing the supported nickel catalyst precursor provided in (i) in a hydrogen atmosphere to obtain a supported nickel catalyst.

[0060] Preferably, the temperature at which the reduction is carried out in (ii) ranges from 200 to 500°C, more preferably from 300 to 470°C, more preferably from 350 to 450°C, more preferably from 400 to 440°C, more preferably from 420 to 430°C.

[0061] Preferably, the duration of the reduction in (ii) ranges from 0.25 to 5 h, more preferably from 0.5 to 4 h, more preferably from 1 to 3.5 h, more preferably from 1.25 to 3 h, more preferably from 1.5 to 2.5 h, more preferably from 1.75 to 2.25 h.

[0062] The method for preparing a supported nickel catalyst may comprise further method steps. Preferably, the method for preparing a supported nickel catalyst further comprises

[0063] (iii) passivating the supported nickel catalyst obtained in (ii) in an atmosphere containing air, preferably in an atmosphere consisting of air.

[0064] Preferably, the temperature range for passivation in (iii) is 75 to 150°C, more preferably 80 to 130°C, more preferably 85 to 120°C, more preferably 90 to 110°C, more preferably 95 to 105°C.

[0065] Preferably, the time for passivation in (iii) is in the range of 0.25 to 4 h, more preferably 0.5 to 3 h, more preferably 0.75 to 2.5 h, more preferably 1 to 2 h, more preferably 1.25 to 1.75 h.

[0066] Furthermore, the present invention relates to a supported nickel catalyst obtainable and / or obtained according to the process of any one of the embodiments of the present disclosure.

[0067] Furthermore, the present invention relates to a method for hydrogenating aromatic compounds, comprising

[0068] (A) preparing a mixture of one or more aromatic compounds and a supported nickel catalyst according to any one of the embodiments disclosed herein and / or a supported nickel catalyst precursor according to any one of the embodiments disclosed herein; and

[0069] (B) contacting the mixture obtained in (A) with hydrogen at a temperature in the range of 100 to 400°C.

[0070] Preferably, the aromatic compound is selected from the group consisting of aromatic polymer compounds, more preferably selected from the group consisting of petrochemical resins, wherein more preferably, the one or more aromatic compounds comprise a polymerization product of a C9 fraction obtained from crude naphtha distillation.

[0071] In the case where the aromatic compound is selected from the group consisting of aromatic polymer compounds, preferably, the aromatic polymer compound is obtained by polymerization of one or more monomers, which monomers contain one or more selected from the group consisting of: vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene, methylindene, and a mixture of two or more thereof, wherein preferably, the one or more monomers include one or more vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene and one or more methylindene.

[0072] Preferably, the contacting temperature in (B) ranges from 150 to 350°C, more preferably from 200 to 320°C, more preferably from 230 to 300°C, more preferably from 250 to 290°C, more preferably from 260 to 280°C, more preferably from 265 to 275°C.

[0073] Preferably, the duration of the contact in (B) is from 0.1 to 10 h, more preferably from 0.5 to 5 h, more preferably from 1 to 3 h, more preferably from 1.5 to 2.5 h, more preferably from 1.8 to 2.2 h.

[0074] Preferably, the contacting pressure in (B) ranges from 5 to 200 bar, more preferably from 10 to 150 bar, more preferably from 30 to 120 bar, more preferably from 50 to 100 bar, more preferably from 70 to 90 bar, more preferably from 75 to 85 bar.

[0075] Preferably, the contacting in (B) is performed under agitation of the mixture, wherein the agitation of the mixture is preferably achieved by stirring.

[0076] Preferably, the mixture prepared in (A) comprises 0.01 to 5 wt.-% of catalyst, based on 100 wt.-% of one or more aromatic compounds, more preferably 0.05 to 3 wt.-%, more preferably 0.1 to 2.5 wt.-%, more preferably 0.3 to 2.1 wt.-%, more preferably 0.5 to 1.8 wt.-%, more preferably 0.7 to 1.5 wt.-%, more preferably 0.8 to 1.3 wt.-%, more preferably 0.9 to 1.1 wt.-%.

[0077] Preferably, the contacting in (B) is carried out under continuous and / or batch conditions, preferably under batch conditions.

[0078] In addition, the present invention relates to the use of a supported nickel catalyst precursor according to any one of the embodiments disclosed herein and / or a supported nickel catalyst according to any one of the embodiments disclosed herein in the hydrogenation of aromatic compounds, preferably aromatic polymer compounds, more preferably petrochemical resins, and more preferably aromatic compounds, wherein the aromatic compounds comprise polymerization products of the C9 fraction obtained from the distillation of crude naphtha.

[0079] Preferably, the aromatic polymer compound is obtained by polymerization of one or more monomers, wherein the monomers include one or more selected from vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene, methylindene, and a mixture of two or more of the above monomers, wherein preferably, the one or more monomers include one or more vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene and one or more methylindene.

[0080] The unit bar (abs) refers to 10 5 Pa absolute pressure, unit angstrom refers to 10 -10 The length of m.

[0081] The present invention is further illustrated by the following groups of embodiments and combinations of embodiments resulting from the indicated dependencies and back-references. In particular, it should be noted that in each case where the scope of an embodiment is mentioned, for example in the context of a term such as "a method of any one of embodiments 1 to 4", each embodiment within the scope is meant to be explicitly disclosed by a person skilled in the art, i.e., the wording of the term should be understood by a skilled person as being synonymous with "a method of any one of embodiments 1, 2, 3 and 4". In addition, it should be explicitly pointed out that the following group of embodiments is not a group of claims that determine the scope of protection, but rather an appropriate structural part of the description of general aspects and preferred aspects of the present invention.

[0082] 1. A supported nickel catalyst precursor comprising Ni, Si, Al and O, which is preferably obtainable and / or obtained according to the method of any one of embodiments 7 to 39, wherein the catalyst precursor exhibits a total intrusion volume in the range of 2.5 to 6.5 cm 3 / g (ml / g), preferably 3 to 5.5cm 3 / g (ml / g), more preferably 3.5 to 5cm 3 / g (ml / g), more preferably 3.7 to 4.7 cm 3 / g (ml / g), more preferably 3.8 to 4.5 cm 3 / g (ml / g), more preferably 3.9 to 4.3 cm 3 / g (ml / g), more preferably 4 to 4.2cm 3 / g(ml / g),

[0083] Herein, the total intrusion volume is preferably determined according to Reference Example 1.

[0084] 2. The catalyst precursor of embodiment 1, wherein the catalyst precursor exhibits a total pore volume in the range of 0.5 to 2 cm 3 / g, preferably 0.6 to 1.8 cm 3 / g, more preferably 0.65 to 1.5 cm 3 / g, more preferably 0.7 to 1.3 cm 3 / g, more preferably 0.75 to 1.1 cm 3 / g, more preferably 0.8 to 1 cm 3 / g, more preferably 0.85 to 0.95 cm 3 / g, more preferably 0.9 to 0.92 cm 3 / g,

[0085] Among them, the total pore volume is preferably determined according to Reference Example 2.

[0086] 3. The catalyst precursor according to embodiment 1 or 2, wherein the cumulative pore volume of the catalyst precursor with a pore size of 2 to 5 nm is in the range of 0.1 to 0.5 cm 3 / g, preferably 0.13 to 0.4 cm 3 / g, more preferably 0.15 to 0.35 cm 3 / g, more preferably 0.18 to 0.32 cm 3 / g, more preferably 0.2 to 0.29 cm 3 / g, more preferably 0.22 to 0.27 cm 3 / g, more preferably 0.24 to 0.25 cm 3 / g,

[0087] Among them, the cumulative pore volume is preferably determined according to Reference Example 2.

[0088] 4. The catalyst precursor according to any one of embodiments 1 to 3, wherein the cumulative pore volume of the catalyst precursor with a pore size of 2 to 60 nm is in the range of 0.3 to 1.5 cm 3 / g, preferably 0.5 to 1.2 cm 3 / g, more preferably 0.55 to 1 cm 3 / g, more preferably 0.6 to 0.9 cm 3 / g, more preferably 0.65 to 0.85 cm 3 / g, more preferably 0.7 to 0.8 cm 3 / g, more preferably 0.73 to 0.77 cm 3 / g,

[0089] Among them, the cumulative pore volume is preferably determined according to Reference Example 2.

[0090] 5. The catalyst precursor according to any one of embodiments 1 to 4, wherein the cumulative pore volume of the catalyst precursor with a pore size of 20 to 80 nm is in the range of 0.15 to 0.7 cm 3 / g, preferably 0.18 to 0.55 cm 3 / g, more preferably 0.2 to 0.45 cm 3 / g, more preferably 0.23 to 0.4 cm 3 / g, more preferably 0.25 to 0.38 cm 3 / g, more preferably 0.28 to 0.35 cm 3 / g, more preferably 0.31 to 0.33 cm 3 / g,

[0091] Among them, the cumulative pore volume is preferably determined according to Reference Example 2.

[0092] 6. The catalyst precursor according to any one of embodiments 1 to 5, wherein the BET surface area of ​​the catalyst precursor is in the range of 200 to 350 m 2 / g, preferably 230 to 320m 2 / g, more preferably 250 to 300m 2 / g, more preferably 260 to 285m 2 / g, more preferably 265 to 280m 2 / g, wherein the BET surface area is preferably determined according to ISO 9277:2010.

[0093] 7. A method for preparing a supported nickel catalyst precursor, preferably a supported nickel catalyst precursor according to any one of embodiments 1 to 6, comprising

[0094] (1) preparing a first aqueous solution (S1) containing one or more bases;

[0095] (2) preparing a second aqueous solution (S2) comprising one or more nickel-containing compounds and one or more aluminum-containing compounds;

[0096] (3) preparing a third aqueous solution (S3) containing one or more silicon-containing compounds;

[0097] (4) optionally preparing a fourth aqueous solution (S4) comprising one or more aluminum-containing compounds;

[0098] (5) feeding solutions S2 and S3 and optionally solution S4 into solution S1 to precipitate the supported nickel catalyst precursor, wherein

[0099] The pH of the resulting mixture is in the range of 6.5 to 8.5;

[0100] (6) Separating the supported nickel catalyst precursor from the mixture obtained in (5).

[0101] 8. The method according to embodiment 7, wherein the pH of the mixture obtained in (5) is in the range of 6.9 to 8.1, preferably 7.1 to 7.9, more preferably 7.3 to 7.8, and more preferably 7.4 to 7.7.

[0102] 9. The method according to embodiment 7 or 8, wherein the one or more bases in (1) are selected from the group consisting of inorganic bases and organic bases, preferably the group of inorganic bases, wherein preferably the one or more bases are selected from the group consisting of hydroxides, carbonates, aluminates and mixtures of two or more thereof,

[0103] More preferably selected from the group consisting of alkali metal hydroxides, alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof,

[0104] More preferably selected from the group consisting of alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof,

[0105] wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb, Cs and a mixture of two or more thereof,

[0106] More preferably selected from the group consisting of Li, Na, K and mixtures of two or more thereof,

[0107] More preferably, the alkali metal is Na and / or K, preferably Na,

[0108] And wherein, more preferably, the one or more bases include sodium carbonate and / or sodium aluminate, preferably sodium carbonate, wherein more preferably, the one or more bases are sodium carbonate and / or sodium aluminate, preferably sodium carbonate.

[0109] 10. A method according to any one of embodiments 7 to 9, wherein the one or more bases comprise one or more polybasic salts, preferably one or more polybasic salts selected from the group consisting of binary salts, ternary salts and quaternary salts, including mixtures of two or more thereof, more preferably selected from the group consisting of binary and ternary salts, including mixtures of two or more thereof, wherein more preferably, the one or more bases comprise one or more binary salts and / or one or more ternary salts, and more preferably are one or more binary salts, wherein more preferably, the one or more bases consist of one or more binary salts and / or one or more ternary salts, more preferably consist of one or more binary salts.

[0110] 11. The method according to embodiment 10, wherein the one or more cations of the one or more polybasic salts are selected from the group consisting of alkali metals and alkaline earth metals, including mixtures and / or combinations of two or more thereof, preferably selected from the group consisting of alkali metals, including mixtures and / or combinations of two or more thereof,

[0111] More preferably selected from the group consisting of Li, Na, K, Rb, and Cs, including mixtures and / or combinations of two or more thereof,

[0112] More preferably selected from the group consisting of Li, Na and K, including mixtures and / or combinations of two or more thereof,

[0113] Among them, more preferably, one or more cations of the one or more polybasic salts are Na and / or K, preferably Na.

[0114] 12. The method according to any one of embodiments 7 to 11, wherein the one or more nickel-containing compounds in (2) are one or more nickel salts, preferably one or more Ni(II) salts, wherein the anions of the one or more nickel salts are preferably selected from the group consisting of halides, carbonates, bicarbonates, sulfates, bisulfates, hydroxides, nitrates, phosphates, hydrogen phosphates, dihydrogen phosphates, acetates, and combinations of two or more thereof,

[0115] More preferably selected from the group consisting of chloride, bromide, fluoride, bicarbonate, bisulfate, nitrate, dihydrogen phosphate, acetate and combinations of two or more thereof,

[0116] More preferably selected from the group consisting of chloride, fluoride, nitrate, acetate and combinations of two or more thereof,

[0117] wherein, more preferably, the anion of the one or more nickel salts is chloride and / or nitrate, preferably chloride, and wherein, more preferably, the one or more nickel-containing compounds comprise nickel(II) chloride, wherein more preferably, the one or more nickel-containing compounds is nickel(II) chloride.

[0118] 13. The method according to any one of embodiments 7 to 12, wherein the one or more aluminum-containing compounds in (2) are one or more aluminum salts, wherein the anion of the one or more aluminum salts is preferably selected from the group consisting of halides, sulfates, hydroxides, nitrates, and combinations of two or more thereof,

[0119] More preferably selected from the group consisting of chlorides, fluorides, sulfates, hydroxides, nitrates and combinations of two or more thereof,

[0120] Among them, more preferably, the anion of one or more aluminum salts is chloride ion and / or sulfate, preferably chloride ion,

[0121] And wherein, more preferably, the one or more aluminum-containing compounds comprise aluminum chloride, wherein, more preferably, the one or more aluminum-containing compounds are aluminum chloride.

[0122] 14. The method according to any one of embodiments 7 to 13, wherein the one or more silicon-containing compounds in (3) are selected from the group consisting of silicates, preferably selected from the group consisting of silicates, more preferably selected from the group consisting of alkali metal silicates and mixtures thereof, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs and mixtures of two or more thereof, more preferably selected from the group consisting of Li, Na, K and mixtures of two or more thereof, wherein more preferably the alkali metal is Na and / or K, preferably Na,

[0123] And wherein, more preferably, the one or more silicon-containing compounds comprise sodium silicate, wherein more preferably, the one or more silicon-containing compounds are sodium silicate.

[0124] 15. A method according to any one of embodiments 7 to 14, wherein the solution S3 prepared in (3) further comprises one or more bases, wherein the one or more bases are preferably selected from the group consisting of: inorganic bases and organic bases, preferably selected from the group consisting of: inorganic bases, wherein preferably, the one or more bases are selected from the group consisting of: hydroxides, carbonates, aluminates and mixtures of two or more thereof, more preferably selected from the group consisting of: alkali metal hydroxides, alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, more preferably selected from the group consisting of: alkali metal carbonates, alkali metal aluminates and mixtures of two or more thereof, wherein more preferably, the one or more bases comprise one or more alkali metal carbonates, wherein the alkali metal is preferably selected from the group consisting of: Li, Na, K, Rb and Cs and mixtures of two or more thereof, more preferably selected from the group consisting of: Li, Na, K and mixtures of two or more thereof, wherein more preferably, the alkali metal is Na and / or K, preferably Na.

[0125] 16. A method according to embodiment 15, wherein the concentration of the one or more bases ranges from 0.01 to 10 mol / l, preferably 0.05 to 5 mol / l, more preferably 0.1 to 3 mol / l, more preferably 0.3 to 2.5 mol / l, more preferably 0.5 to 2.1 mol / l, more preferably 0.8 to 1.8 mol / l, more preferably 1 to 1.6 mol / l, more preferably 1.2 to 1.4 mol / l, more preferably 1.25 to 1.35 mol / l, more preferably 1.28 to 1.3 mol / l.

[0126] 17. The method according to any one of embodiments 7 to 16, wherein the one or more aluminum-containing compounds in (4) are selected from the group consisting of aluminates, more preferably from the group consisting of aluminates, more preferably from the group consisting of alkali metal aluminates and mixtures thereof, wherein the alkali metal is preferably selected from the group consisting of Li, Na, K, Rb and Cs and mixtures of two or more thereof, more preferably from the group consisting of Li, Na, K and mixtures of two or more thereof, wherein more preferably the alkali metal is Na and / or K, preferably Na,

[0127] And wherein, more preferably, the one or more aluminum-containing compounds comprise sodium aluminate, wherein more preferably, the one or more aluminum-containing compounds are sodium aluminate.

[0128] 18. A method according to any one of embodiments 7 to 17, wherein the concentration of the one or more bases in (1) ranges from 0.005 to 1 mol / l, preferably 0.01 to 0.7 mol / l, more preferably 0.03 to 0.5 mol / l, more preferably 0.05 to 0.3 mol / l, more preferably 0.08 to 0.2 mol / l, more preferably 0.1 to 0.15 mol / l, more preferably 0.11 to 0.13 mol / l.

[0129] 19. A method according to any one of embodiments 7 to 18, wherein the concentration of one or more nickel-containing compounds in (2) ranges from 0.05 to 5 mol / l, preferably 0.1 to 4 mol / l, more preferably 0.3 to 3 mol / l, more preferably 0.5 to 2.5 mol / l, more preferably 0.8 to 2 mol / l, more preferably 1 to 1.8 mol / l, more preferably 1.2 to 1.5 mol / l, more preferably 1.35 to 1.4 mol / l.

[0130] 20. A method according to any one of embodiments 7 to 19, wherein the concentration of the one or more aluminum-containing compounds in (2) ranges from 0.001 to 0.5 mol / l, preferably 0.005 to 0.3 mol / l, more preferably 0.01 to 0.2 mol / l, more preferably 0.03 to 0.15 mol / l, more preferably 0.04 to 0.1 mol / l, more preferably 0.05 to 0.08 mol / l, more preferably 0.055 to 0.075 mol / l, more preferably 0.06 to 0.07 mol / l.

[0131] 21. A method according to any one of embodiments 7 to 20, wherein the concentration of the one or more silicon-containing compounds in (3) ranges from 0.01 to 5 mol / l, preferably 0.05 to 3 mol / l, more preferably 0.1 to 1.5 mol / l, more preferably 0.2 to 1 mol / l, more preferably 0.3 to 0.8 mol / l, more preferably 0.35 to 0.6 mol / l, more preferably 0.4 to 0.55 mol / l, more preferably 0.45 to 0.5 mol / l.

[0132] 22. A method according to any one of embodiments 7 to 21, wherein the concentration of the one or more aluminum-containing compounds in (4) ranges from 0.001 to 5 mol / l, preferably 0.05 to 3 mol / l, more preferably 0.1 to 2 mol / l, more preferably 0.3 to 1.5 mol / l, more preferably 0.4 to 1 mol / l, more preferably 0.5 to 0.8 mol / l, more preferably 0.55 to 0.7 mol / l, more preferably 0.6 to 0.65 mol / l.

[0133] 23. A method according to embodiment 22, wherein the concentration of one or more aluminum-containing compounds in (2) ranges from 0.001 to 0.2 mol / l, preferably 0.005 to 0.1 mol / l, more preferably 0.01 to 0.08 mol / l, more preferably 0.015 to 0.05 mol / l, more preferably 0.02 to 0.04 mol / l, more preferably 0.025 to 0.035 mol / l.

[0134] 24. A method according to any one of embodiments 7 to 23, wherein the ratio S2:S3 of the total volume of solution S2 fed into solution S1 to the total volume of solution S3 is in the range of 0.05:1 to 1:0.05, preferably 0.1:1 to 1:0.1, more preferably 0.3:1 to 1:0.3, more preferably 0.5:1 to 1:0.5, more preferably 0.7:1 to 1:0.7, more preferably 0.8:1 to 1:0.8, more preferably 0.9:1 to 1:0.9.

[0135] 25. The method according to any one of embodiments 7 to 24, wherein the ratio S2:S3:S4 of the total volume of solution S2, the total volume of solution S3, and the total volume of optional solution S4, respectively fed into solution S1, is in the following range: (0.05 to 20): (0.05 to 20): (0.0005 to 2), preferably (0.1 to 10)): (0.1 to 10): (0.001 to 1), more preferably (0.3 to 3): (0. 3 to 3):(0.005 to 0.07), more preferably (0.5 to 2):(0.5 to 2):(0.01 to 0.05), more preferably (0.7 to 1.5):(0.7 to 1.5):(0.015 to 0.045), more preferably (0.8 to 1.3):(0.8 to 1.3):(0.02 to 0.04), more preferably (0.9 to 1.1):(0.9 to 1.1):(0.025 to 0.035).

[0136] 26. A method according to any one of embodiments 7 to 25, wherein the ratio S2:S1 of the total volume of solution S2 to the total volume of solution S1 fed thereto is in the range of 0.01 to 5, more preferably 0.05 to 2, more preferably 0.1 to 1, more preferably 0.3 to 0.7, more preferably 0.4 to 0.55, more preferably 0.45 to 0.5.

[0137] 27. A method according to any one of embodiments 7 to 26, wherein the ratio S3:S1 of the total volume of solution S2 to the total volume of solution S1 fed thereto is in the range of 0.01 to 5, more preferably 0.05 to 2, more preferably 0.1 to 1, more preferably 0.3 to 0.7, more preferably 0.4 to 0.55, more preferably 0.45 to 0.5.

[0138] 28. A method according to any one of embodiments 7 to 27, wherein the ratio S4:S1 of the total volume of the optional solution S4 to the total volume of the solution S1 fed thereto is in the range of 0.0001 to 1, preferably 0.0005 to 0.5, more preferably 0.001 to 0.1, more preferably 0.003 to 0.05, more preferably 0.005 to 0.03, more preferably 0.008 to 0.025, more preferably 0.01 to 0.02, more preferably 0.013 to 0.017.

[0139] 29. A method according to any one of embodiments 7 to 28, wherein, in (5), independently of each other, the duration of feeding S2, S3 solution and optional solution S4 is 1 min to 24 h, preferably 0.05 to 12 h, more preferably 0.1 to 6 h, more preferably 0.25 to 3 h, more preferably 0.5 to 1.5 h, more preferably 0.75 to 1.25 h.

[0140] 30. The method according to any one of embodiments 7 to 29, wherein in (4) solutions S2 and S3 and optionally solution S4 are fed to solution S1 subsequently or simultaneously, preferably simultaneously.

[0141] 31. The method according to any one of embodiments 7 to 30, wherein feeding solutions S2 and S3 into solution S1 in (4) is performed under stirring of solution S1, wherein the stirring of solution S1 is more preferably achieved by stirring.

[0142] 32. A method according to any one of embodiments 7 to 31, wherein solutions S1, S2, S3 and optional solution S4 are heated before solutions S2 and S3 and optional solution S4 are fed into solution S1 in (5), wherein the temperature to which each solution is heated before being added to (5) is 30 to 100°C, preferably 50 to 99°C, more preferably 60 to 98°C, more preferably 70 to 96°C, more preferably 75 to 94°C, more preferably 80 to 92°C, more preferably 85 to 90°C.

[0143] 33. A method according to any one of embodiments 7 to 32, wherein during the feeding in (5), the resulting mixture is heated and maintained at a temperature in the range of 30 to 100°C, preferably 50 to 99°C, more preferably 60 to 98°C, more preferably 70 to 96°C, more preferably 75 to 94°C, more preferably 80 to 92°C, more preferably 85 to 90°C.

[0144] 34. The method according to any one of embodiments 7 to 33, wherein the method further comprises

[0145] (7) washing the supported nickel catalyst precursor obtained in (6); and / or, preferably and

[0146] (8) Drying the supported nickel catalyst precursor obtained in (6) or (7).

[0147] 35. The method according to any one of embodiments 7 to 34, wherein the method further comprises

[0148] (9) calcining the supported nickel catalyst precursor obtained in (6), (7) or (8) to obtain a supported nickel catalyst precursor of a mixed oxide of NiO, SiO2 and Al2O3.

[0149] 36. A method according to embodiment 35, wherein the temperature range for calcining in (9) is 200 to 900°C, more preferably 230 to 700°C, more preferably 250 to 600°C, more preferably 280 to 550°C, more preferably 300 to 500°C, more preferably 330 to 450°C, more preferably 350 to 400°C, more preferably 370 to 380°C.

[0150] 37. The method according to embodiment 35 or 36, wherein the calcination in (9) is carried out in an atmosphere containing air, wherein the calcination in (9) is preferably carried out in air.

[0151] 38. A supported nickel catalyst precursor obtainable and / or obtained according to the method of any one of embodiments 7 to 37, preferably according to the method of any one of embodiments 7 to 34.

[0152] 39. A supported nickel catalyst precursor comprising a mixed oxide of NiO, SiO2 and Al2O3, which is obtainable and / or obtained according to the method of any one of embodiments 35 to 37.

[0153] 40. A method for preparing a supported nickel catalyst, comprising

[0154] (i) providing a supported nickel catalyst precursor according to embodiment 38 or 39;

[0155] (ii) reducing the supported nickel catalyst precursor provided in (i) in a hydrogen atmosphere to obtain a supported nickel catalyst.

[0156] 41. A method according to embodiment 40, wherein the temperature for reduction in (ii) ranges from 200 to 500°C, more preferably from 300 to 470°C, more preferably from 350 to 450°C, more preferably from 400 to 440°C, more preferably from 420 to 430°C.

[0157] 42. A method according to embodiment 40 or 41, wherein the duration of reduction in (ii) ranges from 0.25 to 5 h, preferably 0.5 to 4 h, more preferably 1 to 3.5 h, more preferably 1.25 to 3 h, more preferably 1.5 to 2.5 h, more preferably 1.75 to 2.25 h.

[0158] 43. The method according to any one of embodiments 40 to 42, wherein the method further comprises

[0159] (iii) passivating the supported nickel catalyst obtained in (ii) in an atmosphere containing air, preferably in an atmosphere consisting of air.

[0160] 44. The method according to embodiment 43, wherein the temperature range of passivation in (iii) is 75 to 150°C, preferably 80 to 130°C, more preferably 85 to 120°C, more preferably 90 to 110°C, more preferably 95 to 105°C.

[0161] 45. The method according to embodiment 44, wherein the time for passivation in (iii) is in the range of 0.25 to 4 h, preferably 0.5 to 3 h, more preferably 0.75 to 2.5 h, more preferably 1 to 2 h, more preferably 1.25 to 1.75 h.

[0162] 46. ​​A supported nickel catalyst obtainable and / or obtained according to the method of any one of embodiments 40 to 45.

[0163] 47. A method for hydrogenating aromatic compounds, comprising

[0164] (A) preparing a mixture of one or more aromatic compounds and the catalyst according to embodiment 46 and / or the catalyst precursor according to any one of embodiments 1 to 6, 38 and 39; and

[0165] (B) contacting the mixture obtained in (A) with hydrogen at a temperature in the range of 100 to 400°C.

[0166] 48. A method according to embodiment 47, wherein the aromatic compound is selected from the group consisting of aromatic polymer compounds, preferably selected from the group consisting of petrochemical resins, wherein more preferably, the one or more aromatic compounds comprise a polymerization product of a C9 fraction obtained from crude naphtha distillation.

[0167] 49. A method according to embodiment 48, wherein the aromatic polymer compound is obtained by polymerization of one or more monomers, the monomers comprising one or more selected from vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene, methylindene, and a mixture of two or more of the above monomers, wherein preferably, the one or more monomers comprise one or more vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene and one or more methylindene.

[0168] 50. A method according to any one of embodiments 47 to 49, wherein the contacting temperature in (B) ranges from 150 to 350°C, preferably 200 to 320°C, more preferably 230 to 300°C, more preferably from 250 to 290°C, more preferably 260 to 280°C, more preferably 265 to 275°C.

[0169] 51. The method according to any one of embodiments 47 to 50, wherein the duration of contacting in (B) is 0.1 to 10 h, preferably 0.5 to 5 h, more preferably 1 to 3 h, more preferably 1.5 to 2.5 h, more preferably 1.8 to 2.2 h.

[0170] 52. A method according to any one of embodiments 47 to 51, wherein the pressure of the contact in (B) ranges from 5 to 200 bar, preferably 10 to 150 bar, more preferably 30 to 120 bar, more preferably 50 to 100 bar, more preferably 70 to 90 bar, more preferably 75 to 85 bar.

[0171] 53. The method of any one of embodiments 47 to 52, wherein the contacting in (B) is performed with agitation of the mixture, wherein the agitation of the mixture is preferably achieved by stirring.

[0172] 54. A method according to any one of embodiments 47 to 53, wherein the mixture prepared in (A) contains 0.01 to 5 wt.-% of catalyst precursor, based on 100 wt.-% of one or more aromatic compounds, more preferably 0.05 to 3 wt.-%, more preferably 0.1 to 2.5 wt.-%, more preferably 0.3 to 2.1 wt.-%, more preferably 0.5 to 1.8 wt.-%, more preferably 0.7 to 1.5 wt.-%, more preferably 0.8 to 1.3 wt.-%, more preferably 0.9 to 1.1 wt.-%.

[0173] 55. The method according to any one of embodiments 47 to 54, wherein the contacting in (B) is carried out under continuous and / or batch conditions, preferably under batch conditions.

[0174] 56. Use of a supported nickel catalyst according to embodiment 46 and / or a supported nickel catalyst precursor according to any one of embodiments 1 to 6, 38 and 39 in the hydrogenation of aromatic compounds, preferably aromatic polymer compounds, more preferably petrochemical resins, and more preferably aromatic compounds, wherein the aromatic compounds include polymerization products of the C9 fraction obtained from crude naphtha distillation.

[0175] 57. The use according to embodiment 56, wherein the aromatic polymer compound is obtained by polymerization of one or more monomers, the monomers comprising one or more selected from vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene, methylindene, and a mixture of two or more of the above monomers, wherein preferably, the one or more monomers comprise one or more vinyltoluene, dicyclopentadiene, indene, methylstyrene, styrene and one or more methylindene.

[0176] Experimental Section

[0177] The present invention is further illustrated by the following examples and reference examples.

[0178] Reference Example 1: Determination of total pore volume by Hg intrusion

[0179] The total pore volume is determined by mercury intrusion porosimetry according to standard ASTM D 4284-12.

[0180] Reference Example 2: Determination of pore volume by N2 adsorption method

[0181] The total pore volume is preferably determined by nitrogen adsorption according to DIN 66134 or ASTM D4641-12 by the BJH method.

[0182] Reference Example 3: Determination of pH

[0183] The pH was measured using a pH 3310 pH meter from WTW. The pH electrode was calibrated at room temperature using standard solutions of pH = 7 and pH = 10 for calibration before each use. The pH value of the starting solution was measured at room temperature. In order to monitor the pH curve during the synthesis, the pH value was measured continuously under conditions corresponding to the coprecipitation conditions, and the pH value was recorded once every minute (T = 90 ° C). The temperature dependence of the pH value was also taken into account.

[0184] Reference Example 4: HAC determination

[0185] Hydrogen Adsorption Capacity (HAC) is a common measurement method to determine the level of nickel surface area available for catalysis. The catalysts of the present invention typically have a HAC in the range of 24 to 32 ml H2 / g of catalyst.

[0186] The HAC of the catalyst was measured using an Autochem 2920 from Micromeritics. For a typical step, 0.2 g of catalyst was used. The HAC was determined from the amount of hydrogen desorbed when the temperature was increased from -75°C to 700°C at a rate of 10°C / min under an argon atmosphere.

[0187] Reference Example 5: Preparation of hydrogenation catalyst precursor

[0188] The catalytically active phase of the hydrogenation catalyst is usually elemental Ni. In order to obtain a highly dispersed catalyst, the catalytically active phase is usually supported on an oxide support, such as a combined SiO2-Al2O3 support.

[0189] Coprecipitation is carried out in a stirred tank reactor with baffles to obtain mixing that minimizes concentration differences in the container, as changes in concentration may result in a homogeneous product. The container can be heated to the desired temperature. The stirred tank initially contains a water / carrier (precursor) solution, called the "heel". A Gilson pump is then used to simultaneously add two different liquid streams to the container at the desired flow rate. In one stream, the metal solution is pumped into the container, and in another stream, the carrier solution is pumped into the container.

[0190] For example, a Ni hydrogenation catalyst precursor (also referred to herein as NiO / SiO2-Al2O3) can be prepared by co-precipitating an insoluble Ni salt and / or hydroxide with NaSiO3·6H2O, NaAlO2 and soda (Na2CO3) from a NiCl2 solution, providing NaAlO2 and soda as tailings, an acidic stream (stream 1) comprising NiCl2 and an alkaline stream (stream 2) comprising NaSiO3·6H2O and soda.

[0191] Example 1: Preparation of supported nickel catalyst

[0192] The setup according to Reference Example 3 was applied, whereby the following conditions applied. A typical precipitation preparation was performed using the following parameters, conditions and features:

[0193] - The tailings were prepared by mixing 1600 ml of water with 46.5 g of NaAlO2 solution (NaAlO2 concentration = 51.6 g / kg).

[0194] for

[0195] - Heat the tailings to 90°C and stir at 450 rpm.

[0196] - Stream 1 was provided by preparing a metal precursor solution comprising 132.2 g of NiCl2, 5.4 g of AlCl3.6H2O and 750 ml of water.

[0197] - Stream 2 is provided by preparing a support precursor solution comprising 74 g of Na2SiO3.5H2O, 102.5 g of Na2CO3 and 750 ml of water.

[0198] These streams were added simultaneously to the tailings over a period of 1 hour at a temperature of 90° C. The final pH was 7.6, thus within the range of 7.0 to 8.5.

[0199] Thus, after precipitation (addition of solution), after about 1 hour, the slurry was transferred to a filtering and washing apparatus. The total volume of the slurry after precipitation was 3000 ml. After filtering, washing (with about 40 to 60 L of H2O) and drying (overnight at 100°C), the amount of solid material was about 120 g.

[0200] A sample of the resulting product - calcined in static air at 375°C (5°C / min, 1.5 hours) - had a 305 m 2 / g BET specific surface area, 0.72cm 3 Total pore volume / g, 0.28 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters of 2 to 5 nm, 0.61 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters ranging from 2 to 60 nm, 0.20 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters of 20 to 80 nm. In addition, the calcined sample of the obtained product has a pore size of 3.7 cm 3 / g (ml / g) total intrusion volume.

[0201] The dried solid material is activated with hydrogen at 425°C for two hours and, if necessary, subsequently passivated.

[0202] The supported nickel catalyst obtained had a hydrogen adsorption capacity of 26.2 ml H2 / g catalyst. The reaction rate constant of the catalyst for hydrogenation of hydrocarbon resin (RRH) was determined to be 1.362 h -1 The activity of the catalyst was 100%.

[0203] Example 2: Preparation of hydrogenation catalyst

[0204] The application is based on the setup of reference example 3, whereby the following conditions apply. 750 ml of an aqueous solution containing NiCl2 (132.2 g) and AlCl3 (11.6 g), and 750 ml of an aqueous solution containing sodium metasilicate (74.1 g) and sodium carbonate (102.5 g) are simultaneously pumped into a precipitation vessel under full stirring (450 rpm) for 1 hour at 90° C. The starting solution (tailing) in the precipitation vessel consists of 1600 ml of an aqueous solution of sodium carbonate (20 g). The final pH value is 7.8, therefore, within the range of 7.0 to 8.5.

[0205] Thus, after precipitation (addition of solution), after about 1 hour, the slurry was transferred to a filtering and washing apparatus. The total volume of the slurry after precipitation was 3000 ml. After filtering, washing (with about 40 to 60 L of H2O) and drying (overnight at 100°C), the amount of solid material was about 120 g.

[0206] A sample of the resulting product - calcined in static air at 375°C (5°C / min, 1.5 hours) - had a carbon content of 266 m 2 / g BET specific surface area, 0.91cm 3 Total pore volume / g, 0.25 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters of 2 to 5 nm, 0.80 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters ranging from 2 to 60 nm, 0.31 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters ranging from 20 to 80 nm. In addition, the calcined sample of the obtained product has a pore size of 4.1 cm 3 / g (ml / g) total intrusion volume.

[0207] The dried solid material is activated with hydrogen at 425°C for two hours and, if necessary, subsequently passivated.

[0208] The supported nickel catalyst obtained had a hydrogen adsorption capacity of 31.5 ml H2 / g catalyst. The reaction rate constant of the catalyst for hydrogenation of hydrocarbon resin (RRH) was determined to be 1.58 h -1 The activity of the catalyst was 116%.

[0209] Comparative Example 3: Preparation of hydrogenation catalyst

[0210] The setup according to reference example 3 was applied, whereby the following conditions were applied. 750 ml of an aqueous solution containing NiCl2 (132.2 g) and 750 ml of an aqueous solution containing sodium metasilicate (74.1 g) and sodium carbonate (102.5 g) were simultaneously pumped into a precipitation vessel under full stirring (450 rpm) at 90° C. for 1 hour. The starting solution (tailings) in the precipitation vessel consisted of 1600 ml of an aqueous sodium aluminate solution (11.7 g, concentration 51.2 g / kg). The final pH value was 7.7, thus, in the range of 7.0 to 8.5.

[0211] Thus, after precipitation (addition of solution), after about 1 hour, the slurry was transferred to a filtering and washing apparatus. The total volume of the slurry after precipitation was 3000 ml. After filtering, washing (with about 40 to 60 L of H2O) and drying (overnight at 100°C), the amount of solid material was about 120 g.

[0212] A sample of the resulting product - calcined in static air at 375°C (5°C / min, 1.5 hours) - had a carbon content of 420 m 2 / g BET specific surface area, 0.43cm 3 Total pore volume / g, 0.38 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters of 2 to 5 nm, 0.42 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters ranging from 2 to 60 nm, 0.02 cm 3 / g of the cumulative pore volume of the catalyst precursor with a pore size of 20 to 80 nm. In addition, the calcined sample of the obtained product has a pore size of 2.0 cm 3 / g (ml / g) total intrusion volume.

[0213] The dried solid material is activated with hydrogen at 425°C for two hours and, if necessary, passivated.

[0214] The activated mass thus obtained had a hydrogen adsorption capacity of 29.3 ml H2 / g catalyst. The reaction rate constant of the activated mass for hydrogenation of hydrocarbon resin (RRH) was determined to be 1.032 h -1The activity of the activated material was 76%.

[0215] Example 4: Preparation of hydrogenation catalyst

[0216] The application was based on the setup of reference example 3, whereby the following conditions were applied. 750 ml of an aqueous solution containing NiCl2 (132.2 g) and AlCl3 (5.4 g), and 750 ml of an aqueous solution containing sodium metasilicate (74.1 g) and sodium carbonate (102.5 g), and a third aqueous solution containing sodium aluminate solution (23.3 g of solution, concentration 51.6 g / kg) were simultaneously pumped into a precipitation vessel with sufficient stirring (450 rpm) for 1 hour at 90° C. The starting solution in the precipitation vessel (tailing) consisted of 1600 ml of a soda solution (20 g). The final pH value was 7.7, therefore, in the range of 7.0 to 8.5.

[0217] Thus, after precipitation (addition of solution), after about 1 hour, the slurry was transferred to a filtering and washing apparatus. The total volume of the slurry after precipitation was 3000 ml. After filtering, washing (with about 40 to 60 L of H2O) and drying (overnight at 100°C), the amount of solid material was about 120 g.

[0218] A sample of the resulting product - calcined in static air at 375°C (5°C / min, 1.5 hours) - had a 280 m 2 / g BET specific surface area, 0.91cm 3 Total pore volume / g, 0.24 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters of 2 to 5 nm, 0.71 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters ranging from 2 to 60 nm, 0.33 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters ranging from 20 to 80 nm. In addition, the calcined sample of the obtained product has a pore size of 4.1 cm 3 / g (ml / g) total intrusion volume.

[0219] The dried solid material is activated with hydrogen at 425°C for two hours and, if necessary, passivated.

[0220] The activated mass thus obtained had a hydrogen adsorption capacity of 29.4 ml H2 / g catalyst. The reaction rate constant of the activated mass for hydrogenation of hydrocarbon resin (RRH) was determined to be 1.529 h -1 The activity of the activated material was 112%.

[0221] Comparative Example 5: Preparation of hydrogenation catalyst precursor according to prior art

[0222] Comparative Example 5 was prepared according to Example 2 described in patent EP 1237651 B1.

[0223] A sample of the resulting product - calcined in static air at 375°C (5°C / min, 1.5 hours) - had a carbon content of 283 m 2 / g BET specific surface area, 0.46cm 3 Total pore volume / g, 0.24 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters of 2 to 5 nm, 0.53 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters ranging from 2 to 60 nm, 0.18 cm 3 / g of the cumulative pore volume of the catalyst precursor with pore diameters of 20 to 80 nm. In addition, the calcined sample of the obtained product has a pore size of 2.2 cm 3 / g (ml / g) total intrusion volume.

[0224] The resulting product had a hydrogen adsorption capacity of 24.4 ml H2 / g catalyst. The reaction rate constant of the resulting product of hydrogenated hydrocarbon resin (RRH) was determined to be 0.679 h -1 The activity of the product was 50%.

[0225] Example 6: Catalytic testing

[0226] The hydrogenation catalyst precursors of Examples 1, 2 and 4 and Comparative Examples 3 and 5 were tested according to the following procedure.

[0227] The hydrogenation test was conducted in a batch reactor HP-9 using a high sulfur C9 resin as feed (sulfur content of 125 ppm). The activity of the sample was compared with the commercial Ni 5338P catalyst. The conditions of the standard test were:

[0228] Stirring: 1100 rpm;

[0229] Pressure: 80 bar;

[0230] Temperature: 270℃;

[0231] Feed: 75 g resin / 75 g Exxsol D40;

[0232] Running time: 2 hours;

[0233] Catalyst loading: 1.0% on dry resin substrate.

[0234] The reaction rate of the catalyst for hydrogenating hydrocarbon resins (RRH) is expressed as a reaction rate constant, which is obtained by linear regression between 0% and 30% conversion and is expressed as 1 / h after 2 hours of hydrogenation. The hydrogenation activity is calculated by normalizing the RRH of the catalyst with the RRH of Example 1.

[0235] from Figures 1 to 3 As can be seen, surprisingly, the catalytic activity is found to be correlated with the total intrusion volume, in particular with the mesopore volume resulting from pores with an average pore size in the range of 200 to 800 angstroms. Table 1 below gives an overview of some relevant properties of the hydrogenation catalyst precursors of Examples 1, 2 and 4 and Comparative Examples 3 and 5, wherein the reaction rate of the catalyst for hydrogenating hydrocarbon resins (RRH) is represented by the reaction rate constant, obtained by linear regression between 0% and 30% conversion, expressed in 1 / h (the hydrogenation process is complete after 2 hours). The activity of the catalyst precursor according to Example 1 is 100%. From the results, it can be seen that the catalyst precursors according to Examples 2 and 4, both having a higher total intrusion volume of 4.1, show a higher activity in the hydrogenation reaction according to Example 6, compared to the catalyst precursor according to Example 1. The catalyst precursor according to Comparative Example 3, having a total pore volume of 0.43, shows a lower activity as does the catalyst precursor prepared according to the prior art of Comparative Example 5.

[0236] Comparative Example 7: Preparation of hydrogenation catalyst precursor according to prior art

[0237] The hydrogenation catalyst precursor was prepared according to Example 3 of WO 2014 / 128204 A1. The preparation method was followed, thereby scaling down the amount of the starting material by 17 times.

[0238] Under stirring in a container, 264.7 g of sodium carbonate (Na2CO3) and 55.7 g of water glass containing 13.2 wt% of silicon (Si) are dissolved in 2.65 l of deionized water. Then, the resulting mixture is heated to 90°C. Then, 1.41 l of a metal nitrate aqueous solution containing 102.9 g of nickel (Ni) (510.0 g of Ni(NO3)2·6H2O), 8.6 g of copper (Cu) (32.9 g of Cu(NO3)2·3H2O) and 8.4 g of aluminum (Al) (116.2 g of Al(NO3)3·9H2O) is added at a feed rate of 0.71 l / h over 2 hours. The metal nitrate solution is prepared in advance by dissolving nickel nitrate, copper nitrate and aluminum nitrate in water.

[0239] Then, the obtained slurry including the precipitate containing metals Ni, Cu, Al, Si, and Na was stirred for 2 hours at 90° C. Then, the pH value was measured to be 7.9.

[0240] Then, the slurry was filtered to recover the precipitate. The resulting filter cake (precipitate) was washed with deionized water until the conductivity of the washing water was a maximum of 100 microS / cm. The filter cake was then dried at 120° C. for 15 hours, and subsequently, a sample thereof was calcined at 400° C. for 2 hours. The resulting dried material was then ground into a powder.

[0241] The resulting product - calcined at 400 °C in static air (5 °C / min, 2 hours) - had a BET surface area of ​​259 m 2 / g, and the total pore volume is 0.56cm 3 / g.

[0242] In addition, the calcined sample of the obtained product had a 1.8 cm 3 / g (ml / g) total intrusion volume. BRIEF DESCRIPTION OF THE DRAWINGS

[0243] Figure 1 : shows the relative activity of the catalyst precursors according to Examples 1, 2 and 4 and Comparative Example 3 in relation to the total pore volume determined by Reference Example 2. The abscissa shows the total pore volume and the ordinate shows the relative activity in %, whereby the activity of the catalyst precursor according to Example 1 is set to 100%.

[0244] Figure 2 : shows the relative activity of the catalyst precursors according to Examples 1, 2 and 4 and Comparative Example 3 in relation to the total pore volume determined by Reference Example 1. The abscissa shows the total pore volume and the ordinate shows the relative activity in %, whereby the activity of the catalyst precursor according to Example 1 is set to 100%.

[0245] Figure 3 : shows the relationship between the relative activities of the catalyst precursors according to Examples 1, 2 and 4 and Comparative Example 3 and the total pore volume determined by Reference Example 1. The abscissa shows the total pore volume and the ordinate shows the relative activity in %, whereby the activity of the catalyst precursor according to Example 1 is set to 100%.

[0246] Citations

[0247] -WO 01 / 36093 A1

[0248] - WO 2004 / 035204

[0249] -US 9,045,410

[0250] - WO 2015 / 008247 A2

[0251] -WO 2014 / 128204 A1

Claims

1. A supported nickel catalyst precursor comprising Ni, Si, Al, and O, wherein: The catalyst precursor exhibited a total intrusion volume ranging from 2.5 to 6.5 cm 3 / g, wherein the total intrusion volume is measured by mercury intrusion porosimetry according to standard ASTM D 4284-12, and the cumulative pore volume of the catalyst precursor with a pore diameter of 20 to 80 nm ranges from 0.2 to 0.7 cm 3 / g, wherein the cumulative pore volume is determined by a nitrogen adsorption method using the BJH method.

2. The catalyst precursor according to claim 1, wherein The catalyst precursor exhibits a total pore volume ranging from 0.5 to 2 cm 3 / g, wherein the total pore volume is determined by a nitrogen adsorption method using the BJH method.

3. The catalyst precursor according to claim 1, wherein The cumulative pore volume of the catalyst precursor with a pore size of 20 to 80 nm ranges from 0.25 to 0.38 cm 3 / g.

4. The catalyst precursor according to claim 1, wherein The cumulative pore volume of the catalyst precursor with a pore size of 20 to 80 nm is in the range of 0.31 to 0.33 cm 3 / g.

5. The catalyst precursor of claim 2, wherein the total pore volume is determined according to DIN 66134 or ASTM D4641-12.

6. The catalyst precursor according to any one of claims 1 to 5, wherein The BET surface area of ​​the catalyst precursor is in the range of 200 to 350 m 2 / g, wherein the BET surface area is determined according to ISO 9277:2010.

7. The catalyst precursor according to any one of claims 1 to 5, wherein the cumulative pore volume is determined according to DIN 66134 or ASTM D4641-12.

8. A method for preparing a supported nickel catalyst precursor according to any one of claims 1 to 7, the method comprising: (1) preparing a first aqueous solution S1 containing one or more bases; (2) preparing a second aqueous solution S2 comprising one or more nickel-containing compounds and one or more aluminum-containing compounds; (3) preparing a third aqueous solution S3 containing one or more silicon-containing compounds; (4) optionally preparing a fourth aqueous solution S4 comprising one or more aluminum-containing compounds; (5) simultaneously feeding solutions S2 and S3 and optionally solution S4 into solution S1 to precipitate the supported nickel catalyst precursor, wherein the pH of the resulting mixture is in the range of 6.5 to 8.5; (6) Separating the supported nickel catalyst precursor from the mixture obtained in (5).

9. The method according to claim 8, wherein: A ratio S2:S3 of the total volume of the solution S2 to the total volume of the solution S3 respectively fed into the solution S1 is in the range of 0.05:1 to 1:0.

05.

10. The method according to claim 8, wherein: The ratio S2:S1 of the total volume of the solution S2 to the total volume of the solution S1 fed thereto is in the range of 0.01 to 5.

11. The method according to claim 9, wherein: The ratio S2:S1 of the total volume of the solution S2 to the total volume of the solution S1 fed thereto is in the range of 0.01 to 5.

12. The method according to claim 8, wherein: The ratio S3:S1 of the total volume of the solution S3 to the total volume of the solution S1 fed thereto is in the range of 0.01 to 5.

13. The method according to claim 9, wherein: The ratio S3:S1 of the total volume of the solution S3 to the total volume of the solution S1 fed thereto is in the range of 0.01 to 5.

14. The method according to claim 10, wherein: The ratio S3:S1 of the total volume of the solution S3 to the total volume of the solution S1 fed thereto is in the range of 0.01 to 5.

15. The method according to claim 11, wherein: The ratio S3:S1 of the total volume of the solution S3 to the total volume of the solution S1 fed thereto is in the range of 0.01 to 5.

16. The method according to any one of claims 8 to 15, wherein: The method further comprises: (7) Washing the supported nickel catalyst precursor obtained in (6).

17. The method according to any one of claims 8 to 15, wherein: The method further comprises: (8) Drying the supported nickel catalyst precursor obtained in (6).

18. The method according to claim 16, wherein: The method further comprises: (8) Drying the supported nickel catalyst precursor obtained in (7).

19. The method according to any one of claims 8 to 15 and 18, wherein: The method further comprises: (9) calcining the supported nickel catalyst precursor obtained in (6) or (8) to obtain a supported nickel catalyst precursor comprising a mixed oxide of NiO, SiO2 and Al2O3.

20. The method according to claim 16, wherein: The method further comprises: (9) Calcining the supported nickel catalyst precursor obtained in (7) to obtain a supported nickel catalyst precursor comprising a mixed oxide of NiO, SiO2 and Al2O3.

21. A supported nickel catalyst precursor obtained by the process according to any one of claims 8 to 18.

22. A supported nickel catalyst precursor obtained by the process according to claim 19 or 20, comprising a mixed oxide of NiO, SiO2 and Al2O3.

23. A method for preparing a supported nickel catalyst, comprising: (i) providing a supported nickel catalyst precursor according to claim 21 or 22; (ii) reducing the supported nickel catalyst precursor provided in (i) in a hydrogen atmosphere to obtain a supported nickel catalyst.

24. A supported nickel catalyst obtained by the method according to claim 23.

25. A method for hydrogenating aromatic compounds, which comprises (A) preparing a mixture of one or more aromatic compounds and a supported nickel catalyst precursor according to any one of claims 1 to 7 and 21 to 22 or a supported nickel catalyst according to claim 24; and (B) contacting the mixture obtained in (A) with hydrogen at a temperature in the range of 100 to 400°C.

26. Use of the supported nickel catalyst precursor according to any one of claims 1 to 7 and 21 to 22 or the supported nickel catalyst according to claim 24 in the hydrogenation of aromatic compounds.

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