Preparation method of formed Ru catalyst and continuous hydrogenation application

Abstract

The invention discloses a preparation method of a formed Ru catalyst and continuous hydrogenation application, and belongs to the technical field of catalysts. The preparation method comprises the steps of pretreatment, spraying of a ruthenium precursor aqueous solution, spraying of an auxiliary metal precursor aqueous solution, washing, soaking of an organic auxiliary agent aqueous solution, drying, reduction, drying and the like. The catalyst prepared by the preparation method is high in catalytic activity, the raw material conversion rate and the target product selectivity of the reaction for preparing the cyclohexane compound with the substituent group by carrying out hydrogenation reaction on the benzene ring compound with the substituent group are high, the service life is long, and the catalytic performance can be recovered after the catalyst is used for a long time and activated by hydrogen; the method has unexpected technical effects.

Description

Technical Field

[0001] The present invention relates to the field of catalytic technology, and in particular to a preparation method of a shaped Ru catalyst and its continuous hydrogenation application. Background Art

[0002] Benzene and its derivatives are one of the basic raw materials for petrochemical industry. Through its relative activity, a wide variety of phenyl derivatives can be synthesized by adding substituents. The hydrogenation reaction of benzene ring with retained substituents is an extremely important reaction. It not only solves health problems, but also plays an important role in the production of various aliphatic compounds. Such substances are also important fine chemicals and have been widely used as important intermediates for medicines and pesticides, or key starting materials for the synthesis of dyes, resins and polymers. Because benzene is carcinogenic, phenyl derivatives containing benzene rings are also potentially harmful to human health.

[0003] Therefore, there is still an urgent need for a catalyst that can be used for hydrogenating benzene ring compounds to prepare cyclohexane compounds and can retain the substituent groups. Summary of the invention

[0004] In order to solve the above technical problems, the present invention provides the following technical solutions.

[0005] In a first aspect, the present invention provides a method for preparing a catalyst.

[0006] A method for preparing a catalyst comprises the following steps:

[0007] (1) Pretreatment: The carrier is soaked in an inorganic alkali aqueous solution for a certain period of time for pretreatment, and then the carrier is taken out and dried to obtain a pretreated carrier;

[0008] (2) Spraying a ruthenium precursor aqueous solution: atomizing the ruthenium precursor aqueous solution and spraying it on the pretreated support obtained in step (1), aging it, and obtaining a solid A;

[0009] (3) Spraying the co-metal precursor aqueous solution: atomizing the co-metal precursor aqueous solution and spraying it on the solid A obtained in step (2), aging it, and obtaining a solid B;

[0010] (4) washing: washing the solid B with water to obtain a washed solid B;

[0011] (5) Soaking in an aqueous solution of an organic additive: Soaking the washed solid B obtained in step (4) in an aqueous solution of an organic additive for a certain period of time to separate the solid and the liquid to obtain a solid C;

[0012] (6) Drying: Drying the solid C obtained in step (5) to obtain a solid D;

[0013] (7) Reduction: dispersing the solid D obtained in step (6) in a solvent, and then reducing it with a reducing agent to obtain a solid E; or reducing the solid D obtained in step (6) with hydrogen to obtain a solid E;

[0014] (8) Drying: Drying the solid E obtained in step (7) to obtain the catalyst.

[0015] In some embodiments, the support includes at least one of aluminum oxide and silicon oxide.

[0016] In some embodiments, the carrier is in the shape of a sphere or a rod.

[0017] In some embodiments, the carrier is shaped as a sphere with a diameter of 1 mm to 5 mm. In some embodiments, the carrier is shaped as a sphere with a diameter of 1 mm, 2 mm, 3 mm, 4 mm, or 5 mm. In some embodiments, the carrier is shaped as a sphere with a diameter of 1 mm to 2 mm. In some embodiments, the carrier is shaped as a sphere with a diameter of 2 mm to 3 mm.

[0018] In some embodiments, the carrier is in the shape of a strip of 1 mm to 10 mm. In some embodiments, the carrier is in the shape of a strip of 1 mm, 2 mm, 3 mm, 4 mm, 5 mm, 6 mm, 7 mm, 8 mm, 9 mm or 10 mm. In some embodiments, the carrier is in the shape of a strip of 2 mm to 3 mm.

[0019] In some embodiments, the inorganic base in the aqueous solution of inorganic base is sodium hydroxide, potassium hydroxide, ammonia (NH 3 ·H 2 In some embodiments, the inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide and potassium hydroxide.

[0020] In some embodiments, the inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide, potassium hydroxide, and ammonia water, and the concentration of the inorganic base in the inorganic base aqueous solution is 0.0001mol / L-1.00mol / L. In some embodiments, the inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide and potassium hydroxide, and the concentration of the inorganic base in the inorganic base aqueous solution is 0.0001mol / L-1.00mol / L.

[0021] In some embodiments, the concentration of the inorganic base in the aqueous solution of inorganic base is 0.0001 mol / L, 0.0010 mol / L, 0.0050 mol / L, 0.0060 mol / L, 0.0070 mol / L, 0.0080 mol / L, 0.0090 mol / L, 0.010 mol / L, 0.011 mol / L, 0.012 mol / L, 0.013 mol / L, 0.014 mol / L, 0.015 mol / L, 0.016 mol In some embodiments, the concentration of the inorganic base in the inorganic base aqueous solution is 0.010mol / L-0.10mol / L.

[0022] In some embodiments, the inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide and potassium hydroxide, and the concentration of the inorganic base in the inorganic base aqueous solution is 0.0001mol / L, 0.0010mol / L, 0.0050mol / L, 0.0060mol / L, 0.0070mol / L, 0.0080mol / L, 0.0090mol / L, 0.010mol / L, 0.011mol / L, 0.012mol / L, 0.013mol / L, 0.014mol / L, 0.0 15mol / L, 0.016mol / L, 0.017mol / L, 0.018mol / L, 0.019mol / L, 0.020mol / L, 0.030mol / L, 0.040mol / L, 0.050mol / L, 0.06 0mol / L, 0.070mol / L, 0.080mol / L, 0.090mol / L, 0.10mol / L, 0.20mol / L, 0.30mol / L, 0.40mol / L, 0.50mol / L or 1.00mol / L.

[0023] In some embodiments, the inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide and potassium hydroxide, and the concentration of the inorganic base in the inorganic base aqueous solution is 0.010 mol / L-0.10 mol / L.

[0024] In some embodiments, the certain time of step (1) is 2 hours to 5 hours. In some embodiments, the certain time of step (1) is 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours.

[0025] In some embodiments, the ruthenium precursor in the ruthenium precursor aqueous solution is at least one of ruthenium trichloride, a hydrate of ruthenium trichloride, ruthenium acetate, or a hydrate of ruthenium acetate.

[0026] In some embodiments, the concentration of the ruthenium element of the ruthenium precursor in the ruthenium precursor aqueous solution is 0.1mol / L-3.0mol / L. In some embodiments, the concentration of the ruthenium element of the ruthenium precursor in the ruthenium precursor aqueous solution is 0.1mol / L, 0.2mol / L, 0.3mol / L, 0.4mol / L, 0.5mol / L, 0.6mol / L, 0.7mol / L, 0.8mol / L, 0.9mol / L, 1.0mol / L, 1.1mol / L, 1.2mol / L, 1.3mol / L, 1.4mol / L, 1.5mol / L, 2.0mol / L, 2.5mol / L or 3.0mol / L.

[0027] In some embodiments, the co-metal precursor in the co-metal precursor aqueous solution is at least one of calcium chloride, cobalt chloride or nickel chloride.

[0028] In some embodiments, the concentration of the co-metal element in the co-metal precursor aqueous solution is 0.1 mol / L-2.0 mol / L. In some embodiments, the concentration of the co-metal element in the co-metal precursor aqueous solution is 0.1 mol / L, 0.2 mol / L, 0.3 mol / L, 0.4 mol / L, 0.5 mol / L, 0.6 mol / L, 0.7 mol / L, 0.8 mol / L, 0.9 mol / L, 1.0 mol / L, 1.1 mol / L, 1.2 mol / L, 1.3 mol / L, 1.4 mol / L, 1.5 mol / L or 2.0 mol / L.

[0029] In some embodiments, the mass ratio of the ruthenium element of the ruthenium precursor in the ruthenium precursor aqueous solution to the pretreated carrier is 0.2:100.0-5.0:100.0. In some embodiments, the mass ratio of the ruthenium element of the ruthenium precursor in the ruthenium precursor aqueous solution to the pretreated carrier is 0.2:100.0, 0.5:100.0, 1.0:100.0, 1.5:100.0, 2.0:100.0, 2.5:100.0, 3.0:100.0, 3.5:100.0, 4.0:100.0, 4.5:100.0 or 5.0:100.0. In some embodiments, the mass ratio of the ruthenium element of the ruthenium precursor in the ruthenium precursor aqueous solution to the pretreated carrier is 1.0:100.0-3.0:100.0.

[0030] In some embodiments, the mass ratio of the co-metal element of the co-metal precursor in the co-metal precursor aqueous solution to the pretreated carrier is 0.1:100.0-2.0:100.0. In some embodiments, the mass ratio of the co-metal element of the co-metal precursor in the co-metal precursor aqueous solution to the pretreated carrier is 0.1:100.0, 0.2:100.0, 0.3:100.0, 0.4:100.0, 0.5:100.0, 0.6:100.0, 0.7:100.0, 0.8:100.0, 0.9:100.0, 1.0:100.0, 1.1:100.0, 1.2:100.0, 1.3:100.0, 1.4:100.0, 1.5:100.0, 1.6:100.0, 1.7:100.0, 1.8:100.0, 1.9:100.0 or 2.0:100.0. In some embodiments, the mass ratio of the co-metal element of the co-metal precursor in the co-metal precursor aqueous solution to the pretreated carrier is 0.2:100.0-0.5:100.0.

[0031] In some embodiments, the washing with water in step (4) is washing with water 3 to 5 times (eg, 3 times, 4 times, or 5 times).

[0032] In some embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) includes at least one of ethylenediamine, triethylamine, methylamine, acetic acid, benzoic acid, ethanol, methanol or benzyl alcohol.

[0033] In some preferred embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) is at least one of ethylenediamine, benzoic acid and methanol.

[0034] In some embodiments, the content of organic additive in the organic additive aqueous solution in step (5) is 0.1mol / L-3.0mol / L. In some embodiments, the content of organic additive in the organic additive aqueous solution in step (5) is 0.1mol / L, 0.2mol / L, 0.3mol / L, 0.4mol / L, 0.5mol / L, 0.6mol / L, 0.7mol / L, 0.8mol / L, 0.9mol / L, 1.0mol / L, 1.1mol / L, 1.2mol / L, 1.3mol / L, 1.4mol / L, 1.5mol / L, 2.0mol / L, 2.5mol / L or 3.0mol / L. In some embodiments, the content of organic additive in the organic additive aqueous solution in step (5) is 0.2mol / L-1.0mol / L.

[0035] In some embodiments, the certain time of step (5) is 3 hours to 6 hours (such as 3 hours, 4 hours, 5 hours or 6 hours).

[0036] In some embodiments, the solvent of step (7) is water.

[0037] In some embodiments, the reducing agent is at least one of sodium borohydride, sodium formate or hydrogen. In some embodiments, the reducing agent is at least one of sodium borohydride and sodium formate.

[0038] In some embodiments, the molar ratio of the reducing agent to the ruthenium element in the ruthenium precursor aqueous solution is 1: 1-10: 1. In some embodiments, the molar ratio of the reducing agent to the ruthenium element in the ruthenium precursor aqueous solution is 1: 1, 2: 1, 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1 or 10: 1.

[0039] In some embodiments, the reduction time in step (7) is 1 hour to 3 hours (eg, 1 hour, 2 hours or 3 hours).

[0040] In some embodiments, the drying temperature of step (1) is 90° C.-150° C. In some embodiments, the drying temperature of step (1) is 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., or 150° C.

[0041] In some embodiments, the drying time of the drying step (1) is 10h-24h. In some embodiments, the drying time of the drying step (1) is 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h.

[0042] In some embodiments, the drying temperature of step (6) is 90° C.-150° C. In some embodiments, the drying temperature of step (6) is 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., or 150° C.

[0043] In some embodiments, the drying time of the drying step (6) is 10h-24h. In some embodiments, the drying time of the drying step (6) is 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h.

[0044] In some embodiments, the drying temperature of step (8) is 90° C.-150° C. In some embodiments, the drying temperature of step (8) is 90° C., 95° C., 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., or 150° C.

[0045] In some embodiments, the drying time of the drying step (8) is 10h-24h. In some embodiments, the drying time of the drying step (8) is 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h.

[0046] In some embodiments, the aging time of the aging in step (2) and step (3) is independently selected from 1 h to 3 h. In some embodiments, the aging time of the aging in step (2) and step (3) is independently selected from 1 h, 2 h or 3 h.

[0047] In some embodiments, the aging of step (2) and step (3) is performed independently in an air atmosphere at 30°C-40°C. In some embodiments, the aging of step (2) and step (3) is performed independently in an air atmosphere at 30°C, 31°C, 32°C, 33°C, 34°C, 35°C, 36°C, 37°C, 38°C, 39°C or 40°C.

[0048] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes at least one of ethylenediamine, triethylamine, and methylamine; and the reducing agent is sodium borohydride.

[0049] In some preferred embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) is ethylenediamine; and the reducing agent is sodium borohydride.

[0050] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is ethylenediamine; the reducing agent is sodium borohydride; and the co-metal precursor in the co-metal precursor aqueous solution in step (3) is calcium chloride.

[0051] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes at least one of acetic acid and benzoic acid; and the reducing agent is sodium borohydride.

[0052] In some preferred embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) is benzoic acid; and the reducing agent is sodium borohydride.

[0053] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is benzoic acid; the reducing agent is sodium borohydride, and the auxiliary metal precursor in the auxiliary metal precursor aqueous solution in step (3) is nickel chloride; or

[0054] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes at least one of ethanol, methanol or benzyl alcohol; and the reducing agent is sodium formate.

[0055] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes methanol; and the reducing agent is sodium formate.

[0056] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes methanol; the reducing agent is sodium formate; and the co-metal precursor in the co-metal precursor aqueous solution in step (3) is cobalt chloride.

[0057] In a second aspect, the present invention provides a catalyst prepared according to the aforementioned method.

[0058] A catalyst prepared according to the preparation method described in the first aspect.

[0059] In a third aspect, the present invention provides a catalyst prepared by the aforementioned preparation method or an application of the aforementioned catalyst.

[0060] A use of the catalyst prepared by the preparation method of the first aspect or the catalyst of the second aspect in catalyzing the hydrogenation reaction of benzene ring compounds to prepare cyclohexane compounds.

[0061] In some embodiments, the benzene ring compound to be reacted has a non-hydrogen substituent on the benzene ring, and the type and position of the non-hydrogen substituent remain unchanged after the reaction.

[0062] In some embodiments, the non-hydrogen substituent is at least one of an amino group, an ester group, a carboxyl group, or a hydroxyl group.

[0063] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect includes at least one of ethylenediamine, triethylamine, and methylamine; the reducing agent is sodium borohydride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents.

[0064] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect is ethylenediamine; the reducing agent is sodium borohydride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents.

[0065] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect is ethylenediamine; the reducing agent is sodium borohydride; the co-metal precursor in the co-metal precursor aqueous solution in step (3) is calcium chloride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents.

[0066] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect includes at least one of acetic acid and benzoic acid; the reducing agent is sodium borohydride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0067] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect is benzoic acid; the reducing agent is sodium borohydride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0068] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the first aspect is benzoic acid; the reducing agent is sodium borohydride, and the co-metal precursor in the co-metal precursor aqueous solution in step (3) is nickel chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0069] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect includes at least one of ethanol, methanol or benzyl alcohol; the reducing agent is sodium formate; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0070] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect is methanol; the reducing agent is sodium formate; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0071] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the first aspect includes methanol; the reducing agent is sodium formate; the co-metal precursor in the co-metal precursor aqueous solution in step (3) is cobalt chloride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0072] In some embodiments, the benzene ring compound with an amino substituent includes at least one of 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, and p-phenylenediamine; the cyclohexane compound with an amino substituent includes at least one of 1,2-cyclohexyldimethylamine, 1,3-cyclohexyldimethylamine, 1,4-cyclohexyldimethylamine, 1-methyl-2,4-cyclohexyldiamine, 4,4'-methylenebis(cyclohexylamine), and 1,4-cyclohexyldiamine.

[0073] In some embodiments, the benzene ring compound with an ester substituent includes dimethyl terephthalate; the cyclohexane compound with an ester substituent includes dimethyl 1,4-cyclohexyldicarboxylate;

[0074] In some embodiments, the benzene ring compound with a carboxyl substituent includes terephthalic acid, and the cyclohexane compound with a carboxyl substituent includes 1,4-cyclohexanedicarboxylic acid;

[0075] In some embodiments, the benzene ring compound with a hydroxyl substituent includes bisphenol A; and the cyclohexane compound with a hydroxyl substituent is 2,2-bis(4-hydroxycyclohexyl)propane.

[0076] In a fourth aspect, the present invention provides a method for preparing cyclohexane compounds by catalyzing the hydrogenation reaction of benzene ring compounds.

[0077] A method for preparing cyclohexane compounds by catalyzing the hydrogenation reaction of benzene ring compounds, comprising: reacting the benzene ring compounds with hydrogen in a reaction solvent in the presence of the catalyst prepared by the preparation method of the first aspect or the catalyst of the second aspect to obtain the cyclohexane compounds.

[0078] In some embodiments, the benzene ring compound to be reacted has a non-hydrogen substituent on the benzene ring, and the type and position of the non-hydrogen substituent remain unchanged after the reaction.

[0079] In some embodiments, the non-hydrogen substituent is at least one of an amino group, an ester group, a carboxyl group, or a hydroxyl group.

[0080] In some embodiments, the method comprises:

[0081] S1: loading the catalyst prepared by the preparation method described in the first aspect or the catalyst described in the second aspect into a fixed bed reactor;

[0082] S2: introducing hydrogen into a fixed bed reactor for pretreatment;

[0083] S3: introducing hydrogen gas and a benzene ring compound dissolved in a reaction solvent to react and obtain a cyclohexane compound.

[0084] In some embodiments, the benzene ring compound includes one of 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, bisphenol A, terephthalic acid, dimethyl terephthalate, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane or p-phenylenediamine; the cyclohexane compound includes one of 1,2-cyclohexyldimethylamine, 1,3-cyclohexyldimethylamine, 1,4-cyclohexyldimethylamine, 2,2-bis(4-hydroxycyclohexyl)propane, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexyldicarboxylic acid dimethyl ester, 1-methyl-2,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), and 1,4-cyclohexanediamine.

[0085] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect includes at least one of ethylenediamine, triethylamine, and methylamine; the reducing agent is sodium borohydride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents.

[0086] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method described in the first aspect is ethylenediamine; the reducing agent is sodium borohydride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents.

[0087] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the first aspect is ethylenediamine; the reducing agent is sodium borohydride; the co-metal precursor in the co-metal precursor aqueous solution in step (3) is calcium chloride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents.

[0088] In some embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) described in the first aspect includes at least one of acetic acid and benzoic acid; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0089] In some preferred embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) described in step (5) described in the first aspect is benzoic acid; the reducing agent is sodium borohydride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0090] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) described in the first aspect is benzoic acid; the reducing agent is sodium borohydride, and the co-metal precursor in the co-metal precursor aqueous solution in step (3) is nickel chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0091] In some embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) described in step (5) described in the first aspect comprises at least one of ethanol, methanol or benzyl alcohol; the reducing agent is sodium formate; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0092] In some preferred embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) described in step (5) described in the first aspect is methanol; the reducing agent is sodium formate; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0093] In some preferred embodiments, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) described in step (5) of the first aspect comprises methanol; the reducing agent is sodium formate; the co-metal precursor in the aqueous solution of the co-metal precursor in step (3) is cobalt chloride; and the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0094] In some embodiments, the benzene ring compound with an amino substituent includes at least one of 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, and p-phenylenediamine; the cyclohexane compound with an amino substituent includes at least one of 1,2-cyclohexyldimethylamine, 1,3-cyclohexyldimethylamine, 1,4-cyclohexyldimethylamine, 1-methyl-2,4-cyclohexyldiamine, 4,4'-diamino-dicyclohexylmethane, and 1,4-cyclohexyldiamine.

[0095] In some embodiments, the benzene ring compound with an ester substituent includes dimethyl terephthalate; and the cyclohexane compound with an ester substituent includes dimethyl 1,4-cyclohexyldicarboxylate.

[0096] In some embodiments, the benzene ring compound with a carboxyl substituent includes terephthalic acid, and the cyclohexane compound with a carboxyl substituent includes 1,4-cyclohexanedicarboxylic acid.

[0097] In some embodiments, the benzene ring compound with a hydroxyl group substituent includes bisphenol A; and the cyclohexane compound with a hydroxyl group substituent is 2,2-bis(4-hydroxycyclohexyl)propane.

[0098] In some embodiments, the reaction solvent is at least one of methanol, ethanol, tetrahydrofuran, water, ethylene dichloride, isopropanol, tetrachloroethylene or toluene.

[0099] In some embodiments, the reaction temperature of the reaction is 80° C.-250° C. In some embodiments, the reaction temperature of the reaction is 80° C., 90° C., 100° C., 110° C., 120° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 170° C., 180° C., 190° C., 200° C., 210° C., 220° C., 230° C., 240° C., or 250° C.

[0100] In some embodiments, the reaction is carried out at a hydrogen pressure of 3.0 MPa-8.0 MPa. In some embodiments, the reaction is carried out at a hydrogen pressure of 3.0 MPa, 4.0 MPa, 5.0 MPa, 6.0 MPa, 7.0 MPa or 8.0 MPa.

[0101] In some embodiments, the mass ratio of the benzene ring compound to the reaction solvent is 0.05:1.00-0.50:1.00. In some embodiments, the mass ratio of the benzene ring compound to the reaction solvent is 0.05:1.00, 0.11:1.00, 0.12:1.00, 0.13:1.00, 0.14:1.00, 0.15:1.00, 0.16:1.00, 0.17:1.00, 0.18:1.00, 0.19:1.00, 0.20:1.00, 0.30:1.00, 0.40:1.00 or 0.50:1.00. In some embodiments, the mass ratio of the benzene ring compound to the reaction solvent is 0.10:1.00-0.15:1.00.

[0102] In some embodiments, the temperature of the pretreatment in step S2 is 100° C.-200° C. In some embodiments, the temperature of the pretreatment in step S2 is 100° C., 105° C., 110° C., 115° C., 120° C., 125° C., 130° C., 135° C., 140° C., 145° C., 150° C., 155° C., 160° C., 165° C., 170° C., 175° C., 180° C., 185° C., 190° C., or 200° C.

[0103] In some embodiments, the pre-treated hydrogen pressure in step S2 is 3.0 MPa-10.0 MPa. In some embodiments, the pre-treated hydrogen pressure in step S2 is 3.0 MPa, 4.0 MPa, 5.0 MPa, 6.0 MPa, 7.0 MPa, 8.0 MPa, 9.0 MPa or 10.0 MPa.

[0104] In some embodiments, the pretreatment time of the pretreatment in step S2 is 8h-24h. In some embodiments, the pretreatment time of the pretreatment in step S2 is 8h, 9h, 10h, 11h, 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h.

[0105] In some embodiments, the mass space velocity of the benzene ring compound in step S3 is 0.05g / (g·h)-2.00g / (g·h) based on the mass of the benzene ring compound. In some embodiments, the mass space velocity of the benzene ring compound in step S3 is 0.05g / (g·h), 0.10g / (g·h), 0.15g / (g·h), 0.20g / (g·h), 0.25g / (g·h), 0.30g / (g·h), 0.40g / (g·h), 0.50g / (g·h), 0.60g / (g·h), 0.70g / (g·h). h), 0.80g / (g·h), 0.90g / (g·h), 1.00g / (g·h), 1.10g / (g·h), 1.20g / (g·h), 1.30g / (g·h), 1.40g / (g·h), 1.50g / (g·h), 1.60g / (g·h), 1.70g / (g·h), 1.80g / (g·h), 1.90g / (g·h) or 2.00g / (g·h). In some embodiments, the mass space velocity of the benzene ring compound in step S3 is 0.20g / (g·h)-1.00g / (g·h) based on the mass of the benzene ring compound.

[0106] In some embodiments, the molar ratio of the hydrogen introduced in step S3 to the benzene ring compound introduced is 5: 1-150: 1. In some embodiments, the molar ratio of the hydrogen introduced in step S3 to the benzene ring compound introduced is 5: 1, 10: 1, 15: 1, 20: 1, 25: 1, 30: 1, 35: 1, 40: 1, 45: 1, 55: 1, 60: 1, 65: 1, 70: 1, 75: 1, 80: 1, 85: 1, 90: 1, 95: 1, 100: 1, 110: 1, 120: 1, 130: 1, 140: 1 or 150: 1.

[0107] Beneficial Effects

[0108] Compared with the prior art, a certain embodiment of the present invention has at least one of the following beneficial effects:

[0109] (1) Compared with not pretreating the support, the present invention uses an inorganic alkali aqueous solution to pretreat the support, which is beneficial to improving the raw material conversion rate and target product selectivity of the reaction of the obtained catalyst for hydrogenating substituted benzene ring compounds to prepare substituted cyclohexane compounds.

[0110] (2) Compared with the use of other organic additives, the use of ethylenediamine as an organic additive in the present invention is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents by the obtained catalyst.

[0111] (3) Compared with other reducing agents, the use of sodium borohydride as a reducing agent in the present invention is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents by the obtained catalyst.

[0112] (4) Compared with the use of other co-metals, the use of calcium as a co-metal in the present invention is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents by the obtained catalyst.

[0113] (5) Compared with the use of other organic additives, the use of benzoic acid as an organic additive is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of the obtained catalyst for hydrogenating benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0114] (6) Compared with other reducing agents, the use of sodium borohydride as a reducing agent is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents by the obtained catalyst.

[0115] (7) Compared with the use of other co-metals, the use of nickel as a co-metal is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of the obtained catalyst for the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0116] (8) Compared with the use of other organic additives, the use of methanol as an organic additive is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of the obtained catalyst for the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0117] (9) Compared with other reducing agents, the use of sodium formate as a reducing agent is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents by the obtained catalyst.

[0118] (10) Compared with the use of other co-metals, the use of cobalt as a co-metal is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents by the obtained catalyst.

[0119] (11) The catalyst provided by the present invention has a high raw material conversion rate and target product selectivity in the reaction of hydrogenating substituted benzene ring compounds to prepare substituted cyclohexane compounds. The catalyst provided by the present invention has good stability and a long service life. After long-term use, the catalytic performance can be restored after being activated by hydrogen, which has unexpectedly excellent technical effects.

[0120] Terminology

[0121] In the description of the present invention, “plurality” means two or more than two, unless otherwise clearly and specifically defined.

[0122] The term "room temperature" means ambient temperature, referring to a temperature between about 10°C and about 30°C, or between about 20°C and 30°C, or about 25°C.

[0123] The term "wt%" means percent by mass.

[0124] The term "h" or "hr" means hours.

[0125] The term "g / (g·h)" is a mass space velocity unit, which indicates how many grams of raw materials are processed per gram of catalyst per hour (the raw material mass in this unit in the present invention does not include the solvent (reaction solvent)).

[0126] The term "pinch feeding" refers to removing unstable data at the initial stage of the reaction (data before 3 hours are unstable data).

[0127] The term "stable operation" means that the reaction is stable 3 hours after the start of the reaction.

[0128] The "element" mentioned in the present invention is calculated on a single atom basis.

[0129] In the description of this specification, the description with reference to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" etc. means that the specific features, structures, materials or characteristics described in conjunction with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials or characteristics described may be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art may combine and combine the different embodiments or examples described in this specification and the features of the different embodiments or examples, without contradiction.

[0130] In the following, all numbers disclosed herein are approximate, regardless of whether the word "about" or "approximately" is used. The value of each number may vary by 1%, 2%, 5%, 7%, 8%, 10%, 15% or 20%. Whenever a number with a value of N is disclosed, any number with a value of N+ / -1%, N+ / -2%, N+ / -3%, N+ / -5%, N+ / -7%, N+ / -8%, N+ / -10%, N+ / -15% or N+ / -20% will be explicitly disclosed, where "+ / -" means plus or minus. DETAILED DESCRIPTION

[0131] In order to enable those skilled in the art to better understand the technical solution of the present invention, some non-limiting embodiments are further disclosed below to further describe the present invention in detail.

[0132] The reagents used in the present invention can be purchased from the market or prepared by the method described in the present invention.

[0133] Example 1: Preparation method of catalyst 1

[0134] (1) Pretreatment: a spherical alumina carrier with a particle size of 1 mm to 2 mm was immersed in a 0.010 mol / L potassium hydroxide aqueous solution for 3 h for pretreatment, and then the carrier was taken out and dried at 120° C. for 12 h to obtain a pretreated carrier;

[0135] (2) Spraying a ruthenium precursor aqueous solution: a ruthenium trichloride aqueous solution (wherein the ruthenium element concentration is 0.5 mol / L) is atomized and sprayed on the pretreated support obtained in step (1), and aged at 35° C. for 2 h to obtain a solid A; the mass ratio of the ruthenium element in the ruthenium trichloride aqueous solution to the pretreated support is 2.0:100.0;

[0136] (3) Spraying an aqueous solution of a metal precursor: a calcium chloride aqueous solution (wherein the calcium concentration is 0.2 mol / L) is atomized and sprayed on the solid A obtained in step (2), and aged at 35° C. for 2 h to obtain a solid B; the mass ratio of the calcium element in the calcium chloride aqueous solution to the pretreated carrier is 0.2:100.0;

[0137] (4) Washing: washing solid B with water three times to obtain washed solid B;

[0138] (5) Soaking in an organic additive aqueous solution: Soak the washed solid B obtained in step (4) in a 0.5 mol / L ethylenediamine aqueous solution for 3 h, and separate the solid from the liquid to obtain a solid C;

[0139] (6) Drying: Drying the solid C obtained in step (5) at 120° C. for 12 h to obtain a solid D;

[0140] (7) Reduction: The solid D obtained in step (6) is dispersed in water, and then reduced with a 0.5 mol / L sodium borohydride aqueous solution (the molar ratio of sodium borohydride in the 0.5 mol / L sodium borohydride aqueous solution to the ruthenium element in the ruthenium trichloride aqueous solution is 3:1) for 2 h to obtain a solid E;

[0141] (8) Drying: The solid E obtained in step (7) was dried at 120° C. for 12 h to obtain catalyst 1.

[0142] Example 2: Preparation method of catalyst 2

[0143] (1) Pretreatment: a strip-shaped alumina carrier with a diameter of 2 mm to 3 mm was immersed in a 0.010 mol / L sodium hydroxide aqueous solution for 2 h for pretreatment, and then the carrier was taken out and dried at 120° C. for 12 h to obtain a pretreated carrier;

[0144] (2) Spraying a ruthenium precursor aqueous solution: a ruthenium trichloride aqueous solution (wherein the ruthenium element concentration is 0.5 mol / L) is atomized and sprayed on the pretreated support obtained in step (1), and aged at 35° C. for 2 h to obtain a solid A; the mass ratio of the ruthenium element in the ruthenium trichloride aqueous solution to the pretreated support is 1.0:100.0;

[0145] (3) Spraying an aqueous solution of a metal precursor: a nickel chloride aqueous solution (wherein the nickel concentration is 0.1 mol / L) is atomized and sprayed on the solid A obtained in step (2), and aged at 35° C. for 2 h to obtain a solid B; the mass ratio of the nickel element in the nickel chloride aqueous solution to the pretreated support is 0.5:100.0;

[0146] (4) Washing: washing the solid B with water for 5 times to obtain a washed solid B;

[0147] (5) Soaking in an organic additive aqueous solution: Soak the washed solid B obtained in step (4) in a 0.2 mol / L benzoic acid aqueous solution for 5 h, separate the solid and the liquid, and obtain a solid C;

[0148] (6) Drying: Drying the solid C obtained in step (5) at 100° C. for 12 h to obtain a solid D;

[0149] (7) Reduction: The solid D obtained in step (6) is dispersed in water, and then reduced with a 0.5 mol / L sodium borohydride aqueous solution (the molar ratio of sodium borohydride in the 0.5 mol / L sodium borohydride aqueous solution to the ruthenium element in the ruthenium trichloride aqueous solution is 3:1) for 2 h to obtain a solid E;

[0150] (8) Drying: Dry the solid E obtained in step (7) at 100° C. for 12 h to obtain catalyst 2.

[0151] Example 3: Preparation method of catalyst 3

[0152] (1) Pretreatment: The spherical alumina carrier of 2 mm to 3 mm was pretreated by soaking it in a 0.10 mol / L sodium hydroxide aqueous solution for 2 h, and then the carrier was taken out and dried at 120° C. for 12 h to obtain a pretreated carrier;

[0153] (2) Spraying a ruthenium precursor aqueous solution: a ruthenium trichloride aqueous solution (wherein the ruthenium element concentration is 0.5 mol / L) is atomized and sprayed on the pretreated support obtained in step (1), and aged at 35° C. for 2 h to obtain a solid A; the mass ratio of the ruthenium element in the ruthenium trichloride aqueous solution to the pretreated support is 3.0:100.0;

[0154] (3) Spraying an aqueous solution of a metal precursor: a cobalt chloride aqueous solution (wherein the cobalt concentration is 0.1 mol / L) is atomized and sprayed on the solid A obtained in step (2), and aged at 35° C. for 2 h to obtain a solid B; the mass ratio of the cobalt element in the cobalt chloride aqueous solution to the pretreated support is 0.2:100.0;

[0155] (4) Washing: washing solid B with water for 5 times to obtain washed solid B;

[0156] (5) Soaking in an organic additive aqueous solution: Soak the washed solid B obtained in step (4) in a 1.0 mol / L methanol aqueous solution for 6 h, and separate the solid from the liquid to obtain a solid C;

[0157] (6) Drying: Drying the solid C obtained in step (5) at 140° C. for 10 h to obtain a solid D;

[0158] (7) Reduction: The solid D obtained in step (6) is dispersed in water, and then reduced with a 0.5 mol / L sodium formate aqueous solution (the molar ratio of sodium formate in the 0.5 mol / L sodium formate aqueous solution to the ruthenium element in the ruthenium trichloride aqueous solution is 5:1) for 3 h to obtain a solid E;

[0159] (8) Drying: The solid E obtained in step (7) was dried at 140° C. for 10 h to obtain catalyst 3.

[0160] Test Example 1: Catalytic Performance Investigation of Catalyst

[0161] Catalytic performance of catalyst 1: 20 g of catalyst 1 obtained in Example 1 was filled in a 20 ml fixed bed, and after hydrogen replaced the gas therein, the temperature was raised to 120° C., the hydrogen pressure was increased to 5.0 MPa, and the temperature and pressure were maintained for 10 h. 100 g of m-phenylenediamine was dissolved in 1000 g of tetrahydrofuran to prepare a 10 wt % raw material solution; the raw material solution was passed through a 20 ml fixed bed at a mass space velocity (the mass space velocity was calculated based on the mass of the raw material (benzene ring compound) in the raw material solution) of 0.20 g / (g·h). The catalyst 1 was introduced into a fixed bed reactor and hydrogen at a pressure of 4.0 MPa was continuously introduced to react at 150°C. During the reaction, the molar ratio of the hydrogen introduced to the benzene ring compound was 20:1. The conversion rate of the raw material m-xylylenediamine in the obtained reaction liquid was 99.9%, and the selectivity of the target product 1,3-cyclohexylenediamine was 95.2%. After the catalyst 1 was stably operated for 168 hours, the conversion rate of the raw material m-xylylenediamine was 99.8%, and the selectivity of the target product 1,3-cyclohexylenediamine was 95.0%. After catalyst 1 was stably operated for 1200 hours, the conversion rate of raw material meta-xylylenediamine was 96.5%, and the selectivity of target product 1,3-cyclohexylenediamine was 97.3%; due to long-term service, the performance of catalyst 1 declined. After hydrogen replaced the gas therein, the temperature was raised to 150°C, the hydrogen pressure was increased to 5MPa, and the temperature and pressure were maintained for 10 hours to reactivate catalyst 1 and then feed it again for reaction. The conversion rate of raw material meta-xylylenediamine in the obtained reaction liquid was 99.5%, and the selectivity of target product 1,3-cyclohexylenediamine was 98.5%.

[0162] Catalytic performance of catalyst 2: 20 g of catalyst 2 obtained in Example 2 was filled in a 20 ml fixed bed, and after hydrogen replaced the gas therein, the temperature was raised to 150° C., the hydrogen pressure was increased to 5.0 MPa, and the temperature and pressure were maintained for 24 h. 100 g of dimethyl terephthalate was dissolved in 1000 g of tetrahydrofuran to prepare a 10 wt % raw material solution; the raw material solution was passed into the fixed bed at a mass space velocity (the mass space velocity was calculated based on the mass of the raw material (benzene ring compound) in the raw material solution) of 0.30 g / (g·h). Hydrogen gas at a pressure of 5.0 MPa was introduced into the reactor for reaction at 140°C. During the reaction, the molar ratio of the hydrogen gas introduced to the benzene ring compound introduced was 5:1. The conversion rate of the raw material dimethyl terephthalate in the obtained reaction liquid was 99.9%, and the selectivity of the target product 1,4-cyclohexyldicarboxylic acid dimethyl ester was 97.5%. After the catalyst 2 was stably operated for 168 hours, the conversion rate of the raw material dimethyl terephthalate was 99.6%, and the selectivity of the target product 1,4-cyclohexyldicarboxylic acid dimethyl ester was 97.3%. After catalyst 2 was stably operated for 1200 hours, the conversion rate of raw material dimethyl terephthalate was 94.5%, and the selectivity of target product 1,4-cyclohexyl dimethyl carboxylate was 98.2%; due to long-term service, the performance of catalyst 2 declined. After hydrogen replaced the gas therein, the temperature was raised to 150°C, the hydrogen pressure was increased to 5MPa, and the catalyst 2 was reactivated by maintaining the temperature and pressure for 10 hours. After that, the catalyst 2 was fed again for reaction. The conversion rate of dimethyl terephthalate of the obtained feed hydrogenation liquid raw material was 99.5%, and the selectivity of target product 1,4-cyclohexyl dimethyl carboxylate was 98.5%.

[0163] Catalytic performance of catalyst 3: 20 g of catalyst 3 obtained in Example 3 was filled in a 20 ml fixed bed, and after hydrogen replaced the gas therein, the temperature was raised to 180° C., the hydrogen pressure was increased to 6.0 MPa, and the temperature and pressure were maintained for 12 h. 150 g of bisphenol A was dissolved in 1000 g of isopropanol to prepare a 15 wt% raw material solution; the raw material solution was passed into the fixed bed at a mass space velocity (the mass space velocity was calculated based on the mass of the raw material (benzene ring compound) in the raw material solution) of 0.50 g / (g·h). Hydrogen at a pressure of 4.0 MPa was introduced into the reactor for reaction at 140° C. During the reaction, the molar ratio of the hydrogen introduced to the benzene ring compound introduced was 30:1. The conversion rate of the resulting feed hydrogenation liquid raw material bisphenol A was 99.9%, and the selectivity of the target product 2,2-bis(4-hydroxycyclohexyl)propane was 98.3%. After the catalyst 3 was stably operated for 168 hours, the conversion rate of the raw material bisphenol A was 99.2%, and the selectivity of the target product 2,2-bis(4-hydroxycyclohexyl)propane was 98.0%. After catalyst 3 was stably operated for 1200 hours, the conversion rate of raw material bisphenol A was 97.2%, and the selectivity of target product 2,2-bis(4-hydroxycyclohexyl)propane was 94.1%; due to long-term service, the performance of catalyst 3 declined. After hydrogen replaced the gas therein, the temperature was raised to 150°C, the hydrogen pressure was increased to 5MPa, and the temperature and pressure were maintained for 10 hours to reactivate catalyst 3 and then feed it again for reaction. The conversion rate of raw material bisphenol A of the obtained pinch-feed hydrogenation liquid was 99.2%, and the selectivity of target product 2,2-bis(4-hydroxycyclohexyl)propane was 98.1%.

[0164] Conclusion: The catalyst provided by the present invention has high catalytic performance, high raw material conversion rate, high selectivity for the target product of benzene ring hydrogenation, good catalyst stability, long service life, and can restore catalytic performance after long-term use by hydrogen activation, and has unexpected excellent technical effects.

[0165] Test Example 2: Catalyst 1 catalyzes the preparation of 1-methyl-2,4-cyclohexanediamine from 2,4-diaminotoluene

[0166] 20 g of catalyst 1 obtained in Example 1 was loaded into a 20 ml fixed bed. After hydrogen replaced the gas therein, the temperature was raised to 120°C and the hydrogen pressure was increased to 5.0 MPa. The temperature and pressure were maintained for 10 h. 80 g of 2,4-Diaminotoluene is dissolved in 1000g of methanol to prepare a raw material solution with a content of 8wt%. The raw material solution is introduced into a fixed bed reactor at a mass space velocity (the mass space velocity is calculated based on the mass of the raw material (benzene ring compound) in the raw material solution) of 1.00g / (g·h), and hydrogen gas at a pressure of 4.0MPa is introduced to react at 140°C. During the reaction, the molar ratio of the introduced hydrogen gas to the introduced benzene ring compound is 20:1. The conversion rate of the obtained feed hydrogenation liquid raw material 2,4-diaminotoluene is 99.9%, and the selectivity of the target product 1-methyl-2,4-cyclohexanediamine is 96.3%. After the catalyst 1 is stably operated for 168h, the conversion rate of the raw material 2,4-diaminotoluene is 99.8%, and the selectivity of the target product 1-methyl-2,4-cyclohexanediamine is 95.0%.

[0167] Test Example 3: Catalyst 1 catalyzes the preparation of 4,4'-diamino-dicyclohexylmethane from 4,4'-diaminodiphenyl

[0168] 20 g of catalyst 1 obtained in Example 1 was loaded into a 20 ml fixed bed. After hydrogen replaced the gas therein, the temperature was raised to 120°C and the hydrogen pressure was increased to 5.0 MPa. The temperature and pressure were maintained for 10 h. 130 g of 4,4'-Diaminodiphenyl was dissolved in 1000g of tetrahydrofuran to prepare a 13wt% raw material solution; the raw material solution was introduced into a fixed bed reactor at a mass space velocity of 0.50g / (g·h) and hydrogen was introduced at a pressure of 6.0MPa to react at 140°C, the molar ratio of the introduced hydrogen to the introduced benzene ring compound was 20:1, the conversion rate of the obtained feed hydrogenation liquid raw material 4,4'-diaminodiphenyl was 99.6%, the selectivity of the target product 4,4'-diamino-dicyclohexylmethane was 95.4%, and after the catalyst 1 was stably operated for 168hr, the conversion rate of the raw material 4,4'-diaminodiphenyl was 99.1%, and the selectivity of the target product 4,4'-diamino-dicyclohexylmethane was 95.1%.

[0169] Test Example 4: Preparation of 1,4-cyclohexanediamine by using p-phenylenediamine catalyzed by catalyst 1

[0170] 20g of catalyst 1 obtained in Example 1 was filled in a 20ml fixed bed. After hydrogen replaced the gas therein, the temperature was raised to 150°C, the hydrogen pressure was increased to 5.0MPa, and the temperature and pressure were maintained for 10h. 100g of p-phenylenediamine was dissolved in 1000g of ultrapure water to prepare a 10wt% raw material solution; the raw material solution was introduced into a fixed bed reactor at a mass space velocity (the mass space velocity was calculated based on the mass of the raw material (benzene ring compound) in the raw material solution) of 0.40g / (g·h) and hydrogen was introduced at a pressure of 6.0MPa to react at 160°C. The molar ratio of the introduced hydrogen to the introduced benzene ring compound was 50:1; the obtained feed hydrogenation liquid raw material p-phenylenediamine conversion rate was 99.9%, and the target product 1,4-cyclohexanediamine selectivity was 98.5%. After the catalyst 1 was stably operated for 168hr, the raw material p-phenylenediamine conversion rate was 99.6%, and the target product 1,4-cyclohexanediamine selectivity was 98.3%. After the catalyst was stably operated for 720 hours, the conversion rate of the raw material p-phenylenediamine was 97.8%, and the selectivity of the target product 1,4-cyclohexanediamine was 97.7%.

[0171] After catalyst 1 was stably operated for 1200 hours, the conversion rate of raw material p-phenylenediamine was 95.9%, and the selectivity of target product 1,4-cyclohexanediamine was 97.1%; due to long-term service, the performance of catalyst 1 declined. After hydrogen replaced the gas therein, the temperature was raised to 150°C, the hydrogen pressure was increased to 5MPa, and the catalyst 1 was reactivated by maintaining the temperature and pressure for 10 hours. After that, the catalyst 1 was fed again for reaction. The conversion rate of the obtained feed hydrogenation liquid raw material was 99.7%, and the selectivity of the target product 1,4-cyclohexanediamine was 98.3%.

[0172] Conclusion: The catalyst provided by the present invention has good stability and a long catalytic time. After long-term use, the catalytic performance can be restored after being activated by hydrogen, and it has unexpectedly excellent technical effects.

[0173] Comparative Example 1: Catalyst obtained without pretreatment of the carrier

[0174] Based on the preparation method of Example 2, a carrier without pretreatment was investigated. Except that step (1) did not use sodium hydroxide aqueous solution for pretreatment, the remaining operations were the same as Example 2 to obtain catalyst 4.

[0175] Catalyst 4 obtained in Comparative Example 1 was operated according to the operating method of "Catalytic Performance Investigation of Catalyst 2" in Experimental Example 1. The conversion rate of dimethyl terephthalate of the obtained feed hydrogenation liquid raw material was 92.5%, and the selectivity of the target product dimethyl 1,4-cyclohexyldicarboxylate was 91.3%.

[0176] Conclusion: Compared with not pretreating the carrier, the method of pretreating the carrier with an inorganic alkali aqueous solution in the present invention is beneficial to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating substituted benzene ring compounds to prepare substituted cyclohexane compounds by the obtained catalyst.

[0177] Comparative Examples 2-5: Investigation of aqueous solutions of organic additives in catalyst 1

[0178] Based on the preparation method of Example 1, the organic auxiliary agent aqueous solution was replaced by the 0.5 mol / L ethylenediamine aqueous solution with the organic auxiliary agent aqueous solution described in Table 1, and the remaining operations were the same as in Example 1 to obtain catalysts prepared by treating with different organic auxiliary agent aqueous solutions. The obtained catalysts were respectively tested according to the "Catalytic Performance Test of Catalyst 1" in Test Example 1 to test the raw material conversion rate and target product selectivity during feeding. The results are shown in Table 1.

[0179] Table 1: Investigation of aqueous solutions of different organic additives

[0180]

[0181] Conclusion: Compared with the use of other organic additives, the use of ethylenediamine as an organic additive in the present invention is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents by the obtained catalyst.

[0182] Comparative Example 6-Comparative Example 7: Investigation of reduction method of catalyst 1

[0183] Based on the preparation method of Example 1, the 0.5 mol / L sodium borohydride aqueous solution in the preparation method of Catalyst 1 was replaced by the reducing agent aqueous solution described in Table 2, and the molar ratio of the reducing agent in the reducing agent aqueous solution to the ruthenium element in the ruthenium trichloride aqueous solution was the same as that in Example 1. The remaining operations were the same as those in Example 1 to obtain catalysts with different reduction modes. The obtained catalysts were respectively tested according to the "Catalytic Performance Test of Catalyst 1" in Test Example 1 to test the feed conversion rate and target product selectivity after pinching the feed and stable operation for 1200 hours. The results are shown in Table 2.

[0184] Table 2: Investigation of different restoration methods

[0185]

[0186] Conclusion: Compared with other reducing agents, the use of sodium borohydride as a reducing agent in the present invention is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents by the obtained catalyst.

[0187] Comparative Examples 8-11: Investigation of the Metal Promoter of Catalyst 1

[0188] Based on the preparation method of Example 1, the calcium chloride aqueous solution in the preparation method of catalyst 1 is replaced with the metal precursor aqueous solution described in Table 3; and the mass ratio of the metal element to the pretreated carrier in the replaced metal precursor aqueous solution is still 0.2:100.0 (if the metal precursor aqueous solution is not a blank aqueous solution), and the remaining operations are the same as in Example 1; catalysts obtained by using different metal precursor aqueous solutions are obtained. The obtained catalysts are respectively tested according to the "Catalytic Performance Test of Catalyst 1" in Test Example 1, and the raw material conversion rate and target product selectivity after feeding are tested. The results are shown in Table 3.

[0189] Table 3: Investigation of different auxiliary metals

[0190]

[0191]

[0192] Conclusion: Compared with the use of other co-metals, the use of calcium as a co-metal in the present invention is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents by the obtained catalyst.

[0193] Comparative Example 12-Comparative Example 15: Investigation of Catalyst 2 Organic Auxiliary Aqueous Solution

[0194] Based on the preparation method of Example 2, the organic auxiliary agent aqueous solution was replaced by the 0.2 mol / L benzoic acid aqueous solution with the organic auxiliary agent aqueous solution described in Table 4, and the remaining operations were the same as in Example 2 to obtain catalysts prepared by treating with different organic auxiliary agent aqueous solutions. The obtained catalysts were respectively tested according to the "Catalytic Performance Test of Catalyst 2" in Test Example 1 to test the raw material conversion rate and target product selectivity after feeding. The results are shown in Table 4.

[0195] Table 4: Investigation of aqueous solutions of different organic additives

[0196]

[0197] Conclusion: Compared with other organic additives, the use of benzoic acid as an organic additive is more conducive to improving the raw material conversion rate and target product selectivity of the obtained catalyst in the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0198] Comparative Example 16-Comparative Example 17: Investigation of reduction method of catalyst 2

[0199] Based on the preparation method of Example 2, the 0.5 mol / L sodium borohydride aqueous solution in the preparation method of Catalyst 2 was replaced by the reducing agent aqueous solution described in Table 5, and the molar ratio of the reducing agent in the reducing agent aqueous solution to the ruthenium element in the ruthenium trichloride aqueous solution was the same as that in Example 2. The remaining operations were the same as those in Example 2 to obtain catalysts with different reduction modes. The obtained catalysts were respectively tested according to the "Catalytic Performance Test of Catalyst 2" in Test Example 1 to test the feed conversion rate and target product selectivity after pinching the feed and stable operation for 1200 hours. The results are shown in Table 5.

[0200] Table 5: Investigation of different restoration methods

[0201]

[0202] Conclusion: Compared with other reducing agents, the use of sodium borohydride as a reducing agent is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents over the obtained catalyst.

[0203] Comparative Examples 18-21: Investigation of Catalyst 2 Co-Metal

[0204] Based on the preparation method of Example 2, the nickel chloride aqueous solution in the preparation method of catalyst 2 is replaced with the metal precursor aqueous solution described in Table 6; and the mass ratio of the metal element to the pretreated carrier in the replaced metal precursor aqueous solution is still 0.5:100.0 (if the metal precursor aqueous solution is not a blank aqueous solution), and the remaining operations are the same as in Example 2; the catalysts obtained by using different metal precursor aqueous solutions are obtained. The obtained catalysts are respectively tested according to the "Catalytic Performance Test of Catalyst 2" in Test Example 1, and the raw material conversion rate and target product selectivity after feeding are tested. The results are shown in Table 6.

[0205] Table 6: Investigation of different auxiliary metals

[0206]

[0207]

[0208] Conclusion: Compared with the use of other co-metals, the use of nickel as a co-metal is more conducive to improving the raw material conversion rate and target product selectivity of the obtained catalyst in the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents.

[0209] Comparative Example 22-Comparative Example 25: Investigation of Catalyst 3 Organic Auxiliary Aqueous Solution

[0210] Based on the preparation method of Example 3, the organic auxiliary agent aqueous solution was replaced by the 1.0 mol / L methanol aqueous solution with the organic auxiliary agent aqueous solution described in Table 7, and the remaining operations were the same as in Example 3 to obtain catalysts prepared by treating with different organic auxiliary agent aqueous solutions. The obtained catalysts were respectively tested according to the "Catalytic Performance Investigation of Catalyst 3" in Test Example 1 to investigate the raw material conversion rate and target product selectivity after feeding. The results are shown in Table 7.

[0211] Table 7: Investigation of aqueous solutions of different organic additives

[0212]

[0213] Conclusion: Compared with other organic additives, the use of methanol as an organic additive is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents by the obtained catalyst.

[0214] Comparative Example 26-Comparative Example 27: Investigation of reduction method of catalyst 3

[0215] Based on the preparation method of Example 3, the 0.5 mol / L sodium formate aqueous solution in the preparation method of Catalyst 3 was replaced by the reducing agent aqueous solution described in Table 8, and the molar ratio of the reducing agent in the reducing agent aqueous solution to the ruthenium element in the ruthenium trichloride aqueous solution was the same as that in Example 3. The remaining operations were the same as those in Example 3 to obtain catalysts with different reduction modes. The obtained catalysts were respectively tested according to the "Catalytic Performance Test of Catalyst 3" in Test Example 1 to test the feed conversion rate and target product selectivity after pinching the feed and stable operation for 1200 hours. The results are shown in Table 8.

[0216] Table 8: Investigation of different restoration methods

[0217]

[0218] Conclusion: Compared with other reducing agents, the use of sodium formate as a reducing agent is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents by the obtained catalyst.

[0219] Comparative Examples 28-31: Investigation of Catalyst 3 Co-Metal

[0220] Based on the preparation method of Example 3, the aqueous cobalt chloride solution in the preparation method of Catalyst 3 is replaced by the aqueous solution of the metal precursor described in Table 9; and the mass ratio of the metal element to the pretreated carrier in the replaced aqueous solution of the metal precursor is still 0.2:100.0 (if the aqueous solution of the metal precursor is not a blank aqueous solution), and the remaining operations are the same as in Example 3; the catalysts obtained by using different aqueous solutions of metal precursors are obtained. The obtained catalysts are respectively tested according to the "Catalytic Performance Test of Catalyst 3" in Test Example 1, and the raw material conversion rate and target product selectivity after pinching the feeding and stable operation for 1200 hours are tested. The results are shown in Table 9.

[0221] Table 9: Investigation of different auxiliary metals

[0222]

[0223] Conclusion: Compared with the use of other co-metals, the use of cobalt as a co-metal is more conducive to improving the raw material conversion rate and target product selectivity of the reaction of hydrogenating benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents by the obtained catalyst.

[0224] The method of the present invention has been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the methods and applications described herein within the content, spirit and scope of the present invention to implement and apply the technology of the present invention. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters. It is particularly important to point out that all similar replacements and modifications are obvious to those skilled in the art, and they are all considered to be included in the present invention.

Claims

1. A method for preparing a catalyst, wherein The following steps are involved: (1) Pretreatment: The carrier is soaked in an inorganic alkali aqueous solution for a certain period of time for pretreatment, and then the carrier is taken out and dried to obtain a pretreated carrier; (2) Spraying a ruthenium precursor aqueous solution: atomizing the ruthenium precursor aqueous solution and spraying it on the pretreated support obtained in step (1), aging it, and obtaining a solid A; (3) Spraying the co-metal precursor aqueous solution: atomizing the co-metal precursor aqueous solution and spraying it on the solid A obtained in step (2), aging it, and obtaining a solid B; (4) washing: washing the solid B with water to obtain a washed solid B; (5) Soaking in an aqueous solution of an organic additive: Soaking the washed solid B obtained in step (4) in an aqueous solution of an organic additive for a certain period of time to separate the solid and the liquid to obtain a solid C; (6) Drying: Drying the solid C obtained in step (5) to obtain a solid D; (7) Reduction: dispersing the solid D obtained in step (6) in a solvent, and then reducing it with a reducing agent to obtain a solid E; or reducing the solid D obtained in step (6) with hydrogen to obtain a solid E; (8) Drying: Drying the solid E obtained in step (7) to obtain the catalyst.

2. The preparation method according to claim 1, wherein the carrier comprises at least one of aluminum oxide and silicon oxide; and / or The carrier is in the shape of a sphere or a strip; and / or The carrier is in the shape of a sphere with a diameter of 1mm-5mm or 1mm-2mm; or the carrier is in the shape of a strip with a diameter of 1mm-10mm or 2mm-3mm.

3. The preparation method according to any one of claims 1 to 2, wherein the inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide, potassium hydroxide and ammonia water; and / or The inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide, potassium hydroxide and ammonia water, and the concentration of the inorganic base in the inorganic base aqueous solution is 0.0001mol / L-1.00mol / L or 0.010mol / L-0.10mol / L; and / or The certain time of step (1) is 2 hours to 5 hours; and / or The ruthenium precursor in the ruthenium precursor aqueous solution is at least one of ruthenium trichloride, a hydrate of ruthenium trichloride, ruthenium acetate or a hydrate of ruthenium acetate; and / or The concentration of ruthenium element in the ruthenium precursor aqueous solution is 0.1 mol / L-3.0 mol / L; and / or The co-metal precursor in the co-metal precursor aqueous solution is at least one of calcium chloride, cobalt chloride or nickel chloride; and / or The concentration of the co-metal element in the co-metal precursor aqueous solution is 0.1 mol / L-2.0 mol / L; and / or The mass ratio of the ruthenium element of the ruthenium precursor in the ruthenium precursor aqueous solution to the pretreated carrier is 0.2:100.0-5.0:100.0 or 1.0:100.0-3.0:100.0; and / or The mass ratio of the co-metal element in the co-metal precursor aqueous solution to the pretreated carrier is 0.1:100.0-2.0:100.0 or 0.2:100.0-0.5:100.0; and / or The washing with water in step (4) is performed 3 to 5 times.

4. The preparation method according to any one of claims 1 to 3, wherein the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) comprises at least one of ethylenediamine, triethylamine, methylamine, acetic acid, benzoic acid, ethanol, methanol or benzyl alcohol; preferably at least one of ethylenediamine, benzoic acid and methanol; and / or The content of the organic additive in the aqueous solution of the organic additive in step (5) is 0.1 mol / L-3.0 mol / L; and / or The specific time of step (5) is 3 hours to 6 hours.

5. The preparation method according to any one of claims 1 to 4, wherein the solvent in step (7) is water; and / or The reducing agent is at least one of sodium borohydride, sodium formate or hydrogen; and / or The molar ratio of the reducing agent to the ruthenium element in the ruthenium precursor aqueous solution is 1:1-10:1; and / or The reduction time in step (7) is 1 hour to 3 hours; and / or The drying temperature in step (1) is 90° C.-150° C.; and / or The drying time of the drying in step (1) is 10h-24h; and / or The drying temperature in step (6) is 90° C.-150° C.; and / or The drying time of the drying in step (6) is 10h-24h; and / or The drying temperature in step (8) is 90° C.-150° C.; and / or The drying time of step (8) is 10h-24h; and / or The aging time of the aging in step (2) and step (3) is independently selected from 1 h to 3 h or 2 h; and / or The aging in step (2) and step (3) is performed independently by placing the sample in an air atmosphere at 30°C-40°C for aging.

6. The preparation method according to any one of claims 1 to 5, wherein the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) comprises at least one of ethylenediamine, triethylamine and methylamine; the reducing agent is sodium borohydride; preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is ethylenediamine; the reducing agent is sodium borohydride; preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is ethylenediamine; the reducing agent is sodium borohydride; the co-metal precursor in the co-metal precursor aqueous solution in step (3) is calcium chloride; or The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes at least one of acetic acid and benzoic acid; the reducing agent is sodium borohydride; preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is benzoic acid; the reducing agent is sodium borohydride; preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is benzoic acid; the reducing agent is sodium borohydride, and the co-metal precursor in the co-metal precursor aqueous solution in step (3) is nickel chloride; or The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes at least one of ethanol, methanol or benzyl alcohol; the reducing agent is sodium formate; preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes methanol; the reducing agent is sodium formate; preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes methanol; the reducing agent is sodium formate; the co-metal precursor in the co-metal precursor aqueous solution in step (3) is cobalt chloride.

7. A catalyst prepared according to the preparation method according to any one of claims 1 to 6.

8. Use of the catalyst prepared by the preparation method according to any one of claims 1 to 6 or the catalyst according to claim 7 in catalyzing the hydrogenation reaction of benzene ring compounds to prepare cyclohexane compounds; Optionally, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method according to any one of claims 1 to 6 comprises at least one of ethylenediamine, triethylamine and methylamine; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) in the preparation method according to any one of claims 1 to 6 is ethylenediamine; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents; or Preferably, in the preparation method according to any one of claims 1 to 6, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is ethylenediamine; the reducing agent is sodium borohydride; the auxiliary metal precursor in the auxiliary metal precursor aqueous solution in step (3) is calcium chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents; or Optionally, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method according to any one of claims 1 to 6 comprises at least one of acetic acid and benzoic acid; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) in the preparation method according to any one of claims 1 to 6 is benzoic acid; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) is benzoic acid; the reducing agent is sodium borohydride, and the auxiliary metal precursor in the aqueous solution of the auxiliary metal precursor in step (3) is nickel chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents; or Optionally, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method according to any one of claims 1 to 6 comprises at least one of ethanol, methanol or benzyl alcohol; the reducing agent is sodium formate; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents; or Preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method according to any one of claims 1 to 6 is methanol; the reducing agent is sodium formate; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method according to any one of claims 1 to 6 comprises methanol; the reducing agent is sodium formate; the auxiliary metal precursor in the aqueous solution of the auxiliary metal precursor in step (3) is cobalt chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents; or Optionally, the benzene ring compound with an amino substituent includes at least one of 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, and p-phenylenediamine; the cyclohexane compound with an amino substituent includes at least one of 1,2-cyclohexyldimethylamine, 1,3-cyclohexyldimethylamine, 1,4-cyclohexyldimethylamine, 1-methyl-2,4-cyclohexyldiamine, 4,4'-methylenebis(cyclohexylamine), and 1,4-cyclohexyldiamine; or Optionally, the benzene ring compound with an ester substituent includes dimethyl terephthalate; the cyclohexane compound with an ester substituent includes dimethyl 1,4-cyclohexyldicarboxylate; Optionally, the benzene ring compound with a carboxyl substituent includes terephthalic acid, and the cyclohexane compound with a carboxyl substituent includes 1,4-cyclohexanedicarboxylic acid; Optionally, the benzene ring compound with a hydroxyl substituent includes bisphenol A; and the cyclohexane compound with a hydroxyl substituent is 2,2-bis(4-hydroxycyclohexyl)propane.

9. A method for preparing cyclohexane compounds by catalyzing the hydrogenation reaction of benzene ring compounds, It is characterized in that include: In the presence of the catalyst prepared by the preparation method according to any one of claims 1 to 6 or the catalyst according to claim 7, reacting the benzene ring compound with hydrogen in a reaction solvent to obtain a cyclohexane compound; or, The method comprises: S1: Filling the catalyst prepared by the preparation method according to any one of claims 1 to 6 or the catalyst according to claim 7 into a fixed bed reactor; S2: introducing hydrogen into a fixed bed reactor for pretreatment; S3: introducing hydrogen gas and a benzene ring compound dissolved in a reaction solvent to react and obtain a cyclohexane compound.

10. The method according to claim 9, It is characterized in that The benzene ring compound includes one of 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, bisphenol A, terephthalic acid, dimethyl terephthalate, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane or p-phenylenediamine; the cyclohexane compound includes one of 1,2-cyclohexyldimethylamine, 1,3-cyclohexyldimethylamine, 1,4-cyclohexyldimethylamine, 2,2-bis(4-hydroxycyclohexyl)propane, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexyldicarboxylic acid dimethyl ester, 1-methyl-2,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine) and 1,4-cyclohexanediamine; and / or Optionally, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method according to any one of claims 1 to 6 comprises at least one of ethylenediamine, triethylamine and methylamine; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) in the preparation method according to any one of claims 1 to 6 is ethylenediamine; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents; or Preferably, in the preparation method according to any one of claims 1 to 6, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is ethylenediamine; the reducing agent is sodium borohydride; the auxiliary metal precursor in the auxiliary metal precursor aqueous solution in step (3) is calcium chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with amino substituents to prepare cyclohexane compounds with amino substituents; or Optionally, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method according to any one of claims 1 to 6 comprises at least one of acetic acid and benzoic acid; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) in the preparation method according to any one of claims 1 to 6 is benzoic acid; the reducing agent is sodium borohydride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) is benzoic acid; the reducing agent is sodium borohydride, and the auxiliary metal precursor in the aqueous solution of the auxiliary metal precursor in step (3) is nickel chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents; or Optionally, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method according to any one of claims 1 to 6 comprises at least one of ethanol, methanol or benzyl alcohol; the reducing agent is sodium formate; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents; and / or Preferably, the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) of the preparation method according to any one of claims 1 to 6 is methanol; the reducing agent is sodium formate; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents; or Preferably, the organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) of the preparation method described in any one of claims 1 to 6 comprises methanol; the reducing agent is sodium formate; the auxiliary metal precursor in the aqueous solution of the auxiliary metal precursor in step (3) is cobalt chloride; the catalyst prepared by the preparation method is used to catalyze the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents; or Optionally, the benzene ring compound with an amino substituent includes at least one of 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, and p-phenylenediamine; the cyclohexane compound with an amino substituent includes at least one of 1,2-cyclohexyldimethylamine, 1,3-cyclohexyldimethylamine, 1,4-cyclohexyldimethylamine, 1-methyl-2,4-cyclohexanediamine, 4,4'-diamino-dicyclohexylmethane, and 1,4-cyclohexanediamine; and / or Optionally, the benzene ring compound with an ester substituent includes dimethyl terephthalate; the cyclohexane compound with an ester substituent includes dimethyl 1,4-cyclohexyldicarboxylate; and / or Optionally, the benzene ring compound with a carboxyl substituent includes terephthalic acid, and the cyclohexane compound with a carboxyl substituent includes 1,4-cyclohexanedicarboxylic acid; and / or Optionally, the benzene ring compound with a hydroxyl substituent includes bisphenol A; the cyclohexane compound with a hydroxyl substituent is 2,2-bis(4-hydroxycyclohexyl)propane; and / or Optionally, the reaction solvent is at least one of methanol, ethanol, tetrahydrofuran, water, ethylene dichloride, isopropanol, tetrachloroethylene or toluene; and / or Optionally, the reaction temperature of the reaction is 80°C-250°C; and / or Optionally, the reaction is carried out under a hydrogen pressure of 3.0 MPa-8.0 MPa; and / or Optionally, the mass ratio of the benzene ring compound to the reaction solvent is 0.05:1.00-0.50:1.00 or 0.10:1.00-0.15:1.00; and / or Optionally, the pretreatment temperature in step S2 is 100° C.-200° C.; and / or Optionally, the pre-treated hydrogen pressure in step S2 is 3.0 MPa-10.0 MPa; and / or Optionally, the pretreatment time of the pretreatment in step S2 is 8h-24h; and / or Optionally, the mass space velocity of the benzene ring compound added in step S3 is 0.05 g / (g·h)-2.00 g / (g·h) calculated based on the mass of the benzene ring compound; Optionally, in step S3, the molar ratio of the hydrogen gas introduced to the benzene ring compound introduced is 5:1-150:1.

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