Preparation method of a shaped Ru catalyst and its continuous hydrogenation application

Abstract

The present invention discloses a preparation method and continuous hydrogenation application of a shaped Ru catalyst, belonging to the field of catalyst technology. The preparation method comprises the steps of pretreatment, spraying a ruthenium precursor aqueous solution, spraying a metal promoter aqueous solution, washing, soaking in an organic additive aqueous solution, drying, reducing, and drying. The catalyst prepared by the preparation method has high catalytic activity, high raw material conversion rate and target product selectivity in the reaction of hydrogenating substituted benzene ring compounds to prepare substituted cyclohexane compounds, long service life, and can restore catalytic performance after long-term use through hydrogen activation, thus having unexpected technical effects.

Description

Technical Field

[0001] The present invention relates to the field of catalysis 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 essential raw materials for the petrochemical industry. Their relative reactivity allows the addition of substituents to synthesize a wide variety of phenyl derivatives. The hydrogenation of benzene rings while retaining the substituents is a crucial reaction, not only addressing health concerns but also playing a crucial role in the production of various aliphatic compounds. These compounds are also important fine chemicals, widely used as important intermediates in pharmaceuticals and pesticides, and as key starting materials for the synthesis of dyes, resins, and polymers. Because benzene is carcinogenic, phenyl derivatives containing benzene rings also pose potential health risks.

[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 onto 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 organic additive aqueous solution: Soaking the washed solid B obtained in step (4) in an organic additive aqueous solution for a certain period of time, and performing solid-liquid separation to obtain a solid C;

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

[0013] (7) Reduction: dispersing the solid D obtained in step (6) in a solvent and 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 comprises at least one of alumina and silica.

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

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

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

[0019] In some embodiments, the inorganic base in the inorganic base aqueous solution is at least one of sodium hydroxide, potassium hydroxide, and ammonia (NH3·H2O). 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 0.0001 mol / L-1.00 mol / 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 0.0001 mol / L-1.00 mol / 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 / L. / L, 0.017 mol / L, 0.018 mol / L, 0.019 mol / L, 0.020 mol / L, 0.030 mol / L, 0.040 mol / L, 0.050 mol / L, 0.060 mol / L, 0.070 mol / L, 0.080 mol / L, 0.090 mol / L, 0.10 mol / L, 0.20 mol / L, 0.30 mol / L, 0.40 mol / L, 0.50 mol / L or 1.00 mol / L. In some embodiments, the concentration of the inorganic base in the aqueous inorganic base solution is 0.010 mol / L-0.10 mol / 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 aqueous ruthenium precursor solution is 0.1 mol / L-3.0 mol / L. In some embodiments, the concentration of the ruthenium element of the ruthenium precursor in the aqueous ruthenium precursor 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, 2.0 mol / L, 2.5 mol / L or 3.0 mol / 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 support 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 support 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 support 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 support 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 support 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 support is 0.2:100.0-0.5:100.0.

[0031] In some embodiments, the washing with water in step (4) is performed 3 to 5 times (such as 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 the organic additive in the organic additive aqueous solution in step (5) is 0.1mol / L-3.0mol / L. In some embodiments, the content of the 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 the 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. to 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 10 hours to 24 hours. In some embodiments, the drying time of the drying step (1) is 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours.

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

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

[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 in step (2) and step (3) is performed independently in an air atmosphere at 30° C. to 40° C. In some embodiments, the aging in 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 organic auxiliary agent aqueous solution 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 organic auxiliary agent aqueous solution 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 above method.

[0058] A catalyst prepared according to the preparation method of 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 aqueous solution of the organic auxiliary agent 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; 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-cyclohexanedimethylamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, 1-methyl-2,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), and 1,4-cyclohexanediamine.

[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 comprises: 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: filling 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 the fixed bed reactor for pretreatment;

[0083] S3: introducing hydrogen gas and a benzene ring compound dissolved in a reaction solvent to react to 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-cyclohexanedimethylamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, 2,2-bis(4-hydroxycyclohexyl)propane, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic 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 aqueous solution of the organic auxiliary agent 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) 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 organic auxiliary agent aqueous solution in step (5) described in step (5) 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.

[0092] In some preferred embodiments, the organic auxiliary agent in the organic auxiliary agent aqueous solution 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 organic auxiliary agent aqueous solution in step (5) in 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; 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-cyclohexanedimethylamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, 1-methyl-2,4-cyclohexanediamine, 4,4'-diamino-dicyclohexylmethane, and 1,4-cyclohexanediamine.

[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 substituent includes bisphenol A; and the cyclohexane compound with a hydroxyl substituent is 2,2-bis(4-hydroxycyclohexyl)propane.

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

[0099] In some embodiments, the reaction temperature is 80° C. to 250° C. In some embodiments, the reaction temperature 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 to 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 8 hours to 24 hours. In some embodiments, the pretreatment time of the pretreatment in step S2 is 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours or 24 hours.

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

[0106] In some embodiments, the molar ratio of the hydrogen gas introduced in step S3 to the introduced benzene ring compound is 5: 1-150: 1. In some embodiments, the molar ratio of the hydrogen gas introduced in step S3 to the introduced benzene ring compound 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 hydrogenating substituted benzene ring compounds to prepare substituted cyclohexane compounds by the obtained catalyst.

[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 hydrogenating benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents by the obtained catalyst.

[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 hydrogenating benzene ring compounds with ester substituents or carboxyl substituents to prepare cyclohexane compounds with ester substituents or carboxyl substituents by the obtained catalyst.

[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 hydrogenating benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents by the obtained catalyst.

[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 using 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, and has unexpected excellent technical effects.

[0120] Terminology

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

[0122] The term "room temperature" means ambient temperature, which refers 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 percentage 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 "pinching" refers to removing unstable data at the initial stage of the reaction (data before 3 h 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 reference terms "one embodiment", "some embodiments", "example", "specific example", or "some examples" mean 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 can be combined in any one or more embodiments or examples in a suitable manner. In addition, those skilled in the art can combine and combine different embodiments or examples described in this specification and features of different embodiments or examples without contradiction.

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

[0131] In order to enable those skilled in the art to better understand the technical solutions of the present invention, some non-limiting embodiments are further disclosed below to further illustrate 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 of Catalyst 1

[0134] (1) Pretreatment: A spherical alumina support with a particle size of 1 mm to 2 mm was pretreated by soaking it in a 0.010 mol / L potassium hydroxide aqueous solution for 3 h. The support was then taken out and dried at 120° C. for 12 h to obtain a pretreated support.

[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 onto the pretreated support obtained in step (1), and aged at 35° C. for 2 h to obtain solid A; the mass ratio of 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 onto 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 support 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 perform solid-liquid separation to obtain a solid C;

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

[0140] (7) Reduction: The solid D obtained in step (6) was 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 was 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 of Catalyst 2

[0143] (1) Pretreatment: A strip-shaped alumina support with a diameter of 2 mm to 3 mm was pretreated by soaking it in a 0.010 mol / L sodium hydroxide aqueous solution for 2 h. The support was then taken out and dried at 120° C. for 12 h to obtain a pretreated support.

[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 onto the pretreated support obtained in step (1), and aged at 35° C. for 2 h to obtain solid A; the mass ratio of 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 onto 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 solid B with water five times to obtain 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, and perform solid-liquid separation to obtain a solid C;

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

[0149] (7) Reduction: The solid D obtained in step (6) was 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 was 3:1) for 2 h to obtain a solid E;

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

[0151] Example 3: Preparation of Catalyst 3

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

[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 onto the pretreated support obtained in step (1), and aged at 35° C. for 2 h to obtain solid A; the mass ratio of 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 onto 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 five 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 perform solid-liquid separation to obtain a solid C;

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

[0158] (7) Reduction: The solid D obtained in step (6) was 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 was 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 replacement of 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-xylenediamine was dissolved in 1000 g of tetrahydrofuran to prepare a 10 wt% raw material solution; the raw material solution was passed through a 0.20 g / (g·h) 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) 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-xylenediamine 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-xylenediamine was 99.8%, and the selectivity of the target product 1,3-cyclohexylenediamine was 95.0%. After 1200 hours of stable operation of catalyst 1, the conversion rate of the raw material m-xylenediamine was 96.5%, and the selectivity of the target product 1,3-cyclohexylenediamine was 97.3%. Due to long-term service, the performance of catalyst 1 had declined. After hydrogen was replaced with hydrogen, the temperature was raised to 150°C, the hydrogen pressure was increased to 5 MPa, and the temperature and pressure were maintained for 10 hours to reactivate catalyst 1. After that, the reaction was fed again. The conversion rate of the raw material m-xylenediamine in the resulting reaction solution was 99.5%, and the selectivity of the 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 into a 20 ml fixed bed. After hydrogen replacement of the gas therein, the temperature was raised to 150° C. and the hydrogen pressure was increased to 5.0 MPa. 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 (mass space velocity is calculated based on the mass of the raw material (benzene ring compound) in the raw material solution) of 0.30 g / (g·h). Hydrogen at a pressure of 5.0 MPa was introduced into the reactor and the reaction was carried out at 140° C. During the reaction, the molar ratio of the hydrogen introduced to the benzene ring compound introduced was 5:1. The conversion rate of the raw material dimethyl terephthalate in the resulting feed reaction liquid was 99.9%, and the selectivity of the target product 1,4-cyclohexyldimethylcarboxylate was 97.5%. After 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-cyclohexyldimethylcarboxylate was 97.3%. After 1200 hours of stable operation of catalyst 2, the conversion rate of raw material dimethyl terephthalate was 94.5%, and the selectivity of target product dimethyl 1,4-cyclohexyldicarboxylate was 98.2%. Due to long-term service, the performance of catalyst 2 has declined. After hydrogen was replaced with hydrogen, the temperature was raised to 150°C, the hydrogen pressure was increased to 5 MPa, and the temperature and pressure were maintained for 10 hours to reactivate catalyst 2. After that, the catalyst was fed again for reaction. The conversion rate of dimethyl terephthalate raw material of the obtained pinch-feed hydrogenation liquid was 99.5%, and the selectivity of target product dimethyl 1,4-cyclohexyldicarboxylate 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. After hydrogen replacement, the temperature was raised to 180° C. and the hydrogen pressure was increased to 6.0 MPa. 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 (mass space velocity is 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 and the reaction was carried out at 140° C. During the reaction, the molar ratio of the hydrogen introduced to the benzene ring compound was 30:1. The conversion rate of the resulting feedstock hydrogenation liquid bisphenol A was 99.9%, and the selectivity for the target product 2,2-bis(4-hydroxycyclohexyl)propane was 98.3%. After catalyst 3 was stably operated for 168 hours, the conversion rate of the feedstock bisphenol A was 99.2%, and the selectivity for the target product 2,2-bis(4-hydroxycyclohexyl)propane was 98.0%. After 1200 hours of stable operation of catalyst 3, 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 was replaced with hydrogen, the temperature was raised to 150°C, the hydrogen pressure was increased to 5 MPa, and the temperature and pressure were maintained for 10 hours to reactivate catalyst 3 and then feed it again for reaction. The resulting feed hydrogenation liquid raw material conversion rate of bisphenol A 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, with unexpected excellent technical effects.

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

[0166] 20g of catalyst 1 obtained in Example 1 was loaded into a 20ml fixed bed. After hydrogen replaced the gas therein, the temperature was raised to 120°C and the hydrogen pressure was increased to 5.0MPa. The temperature and pressure were kept constant for 10h. 80g of catalyst 1 was added. 2,4-Diaminotoluene is dissolved in 1000 g of methanol to prepare an 8 wt% raw material solution; 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 1.00 g / (g·h), and hydrogen is introduced at a pressure of 4.0 MPa to carry out a reaction at 140° C. During the reaction, the molar ratio of the introduced hydrogen 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 168 hours, 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'-diaminodiphenyl into 4,4'-diamino-dicyclohexylmethane

[0168] 20g of catalyst 1 obtained in Example 1 was loaded into a 20ml fixed bed. After hydrogen replaced the gas therein, the temperature was raised to 120°C and the hydrogen pressure was increased to 5.0MPa. The temperature and pressure were kept constant for 10h. 130g of 4,4'-Diaminodiphenyl was dissolved in 1000 g of tetrahydrofuran to prepare a 13 wt% raw material solution; the raw material solution was introduced into a fixed-bed reactor at a mass space velocity of 0.50 g / (g·h) and hydrogen was introduced at a pressure of 6.0 MPa for reaction at 140° C. The molar ratio of the introduced hydrogen to the introduced benzene ring compound was 20:1. The resulting feedstock hydrogenation liquid had a conversion rate of 99.6% for the 4,4'-diaminodiphenyl raw material and a selectivity of 95.4% for the target product 4,4'-diamino-dicyclohexylmethane. After 168 hours of stable operation of catalyst 1, the conversion rate of the raw material 4,4'-diaminodiphenyl was 99.1%, and the selectivity for 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] 20 g of catalyst 1 obtained in Example 1 was loaded into a 20 ml fixed bed reactor. After hydrogen replacement, the reactor was heated to 150°C and the hydrogen pressure was increased to 5.0 MPa. The temperature and pressure were maintained for 10 hours. 100 g of p-phenylenediamine was dissolved in 1000 g of ultrapure water to prepare a 10 wt% feed solution. This feed solution was introduced into the fixed bed reactor at a mass space velocity (MSV) of 0.40 g / (g·h) (the mass space velocity is calculated based on the mass of the feedstock (benzene ring compound) in the feed solution) and hydrogen was introduced at a pressure of 6.0 MPa. The reaction was carried out at 160°C, with a molar ratio of hydrogen to benzene ring compound of 50:1. The resulting feedstock hydrogenation liquid had a p-phenylenediamine conversion of 99.9% and a selectivity of 98.5% for the target product, 1,4-cyclohexanediamine. After 168 hours of stable operation of catalyst 1, the p-phenylenediamine conversion was 99.6%, and the selectivity for the target product, 1,4-cyclohexanediamine, 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 1200 hours of stable operation of catalyst 1, 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 has declined. After hydrogen was replaced with hydrogen, the temperature was raised to 150°C, the hydrogen pressure was increased to 5 MPa, and the temperature and pressure were maintained for 10 hours to reactivate catalyst 1. After that, the reaction was fed again. The resulting feed hydrogenation liquid had a raw material conversion rate of 99.7%, and the selectivity of target product 1,4-cyclohexanediamine was 98.3%.

[0172] Conclusion: The catalyst provided by the present invention has good stability, a long catalytic time, and can restore catalytic performance after long-term use by activation with hydrogen, which 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, the carrier was examined without pretreatment. Except that the sodium hydroxide aqueous solution was not used for pretreatment in step (1), the remaining operations were the same as in 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 Test Example 1. The conversion rate of dimethyl terephthalate of the resulting 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 support, the method of pretreating the support 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 treatment with different organic auxiliary agent aqueous solutions. The obtained catalysts were respectively tested according to the "Catalytic Performance Investigation of Catalyst 1" in Test Example 1 to investigate 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 Examples 6-7: Investigation of Reduction Methods 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 in Example 1. The remaining operations were the same as in Example 1 to obtain catalysts with different reduction modes. The obtained catalysts were respectively tested according to the "Catalytic Performance Investigation of Catalyst 1" in Test Example 1, and the raw material conversion rate and target product selectivity after pinching the feed and stable operation for 1200 hours were tested. The results are shown in Table 2.

[0184] Table 2: Investigation of different reduction 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 using the obtained catalyst.

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

[0188] Based on the preparation method of Example 1, the calcium chloride aqueous solution in the preparation method of Catalyst 1 was replaced with the co-metal precursor aqueous solutions described in Table 3. The mass ratio of the co-metal element to the pretreated support in the replaced co-metal precursor aqueous solutions remained at 0.2:100.0 (if the co-metal precursor aqueous solution was not a blank aqueous solution). The remaining operations were the same as in Example 1. Catalysts obtained using different co-metal precursor aqueous solutions were obtained. The resulting catalysts were tested according to the "Catalytic Performance Test of Catalyst 1" in Test Example 1, and the feed conversion rate and target product selectivity after dosing were 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 using the obtained catalyst.

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

[0194] Based on the preparation method of Example 2, the organic auxiliary aqueous solution was replaced by the 0.2 mol / L benzoic acid aqueous solution with the organic auxiliary aqueous solution described in Table 4, and the remaining operations were the same as in Example 2 to obtain catalysts prepared after treatment with different organic auxiliary aqueous solutions. The obtained catalysts were respectively tested according to the "Catalytic Performance Investigation of Catalyst 2" in Test Example 1 to investigate 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 in Example 2. The remaining operations were the same as in Example 2 to obtain catalysts with different reduction modes. The obtained catalysts were respectively tested according to the "Catalytic Performance Investigation of Catalyst 2" in Test Example 1, and the raw material conversion rate and target product selectivity after pinching the feed and stable operation for 1200 hours were tested. The results are shown in Table 5.

[0200] Table 5: Investigation of different reduction 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 cyclohexanes with ester substituents or carboxyl substituents over the obtained catalyst.

[0203] Comparative Examples 18-21: Investigation of the Metal Promoter in Catalyst 2

[0204] Based on the preparation method of Example 2, the nickel chloride aqueous solution in the preparation method of Catalyst 2 was replaced with the co-metal precursor aqueous solutions described in Table 6. The mass ratio of the co-metal element to the pretreated support in the replaced co-metal precursor aqueous solution remained at 0.5:100.0 (if the co-metal precursor aqueous solution was not a blank aqueous solution). The remaining operations were the same as in Example 2. Catalysts obtained using different co-metal precursor aqueous solutions were obtained. The obtained catalysts were tested according to the "Catalytic Performance Test of Catalyst 2" in Test Example 1, and the feed conversion rate and target product selectivity after feeding were 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 Examples 22-25: 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 after treatment 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 in Example 3 to obtain catalysts with different reduction modes. The obtained catalysts were respectively tested according to the "Catalytic Performance Investigation of Catalyst 3" in Test Example 1, and the raw material conversion rate and target product selectivity after pinching the feed and stable operation for 1200 hours were tested. The results are shown in Table 8.

[0216] Table 8: Investigation of different reduction 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 using the obtained catalyst.

[0219] Comparative Examples 28-31: Investigation of the Metal Promoter in Catalyst 3

[0220] Based on the preparation method of Example 3, the cobalt chloride aqueous solution in the preparation method of Catalyst 3 was replaced with the co-metal precursor aqueous solutions described in Table 9. The mass ratio of the co-metal element to the pretreated support in the replaced co-metal precursor aqueous solutions remained at 0.2:100.0 (if the co-metal precursor aqueous solution was not a blank aqueous solution). The remaining operations were the same as in Example 3. Catalysts obtained using different co-metal precursor aqueous solutions were obtained. The resulting catalysts were tested according to the "Catalytic Performance Test of Catalyst 3" in Test Example 1. The feed conversion rate and target product selectivity after feed and stable operation for 1200 hours were 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 obtained catalyst in the hydrogenation reaction of benzene ring compounds with hydroxyl substituents to prepare cyclohexane compounds with hydroxyl substituents.

[0224] The methods of the present invention have been described through preferred embodiments. It is apparent that those skilled in the art will be able to modify or appropriately alter and combine the methods and applications described herein within the scope, spirit, and spirit of the present invention to implement and apply the technology of the present invention. Those skilled in the art may refer to the disclosure herein and appropriately modify the process parameters to achieve the desired effect. It is particularly important to note that all similar substitutions and modifications apparent to those skilled in the art are considered encompassed by the present invention.

Claims

1. A method for preparing a catalyst, comprising the following steps: (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 an aqueous solution of a metal co-precursor: atomizing the aqueous solution of a metal co-precursor and spraying it on the solid A obtained in step (2), aging it, and obtaining a solid B; the metal co-precursor in the aqueous solution of the metal co-precursor is at least one of calcium chloride, cobalt chloride, or nickel chloride; (4) Washing: washing solid B with water to obtain washed solid B; (5) Soaking in an organic additive aqueous solution: Soaking the washed solid B obtained in step (4) in an organic additive aqueous solution for a certain period of time, separating the solid and the liquid, and obtaining a solid C; wherein the organic additive in the organic additive aqueous solution in step (5) includes at least one of ethylenediamine, benzoic acid, and methanol; (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 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 1 mm to 5 mm; or the carrier is in the shape of a strip with a diameter of 1 mm to 10 mm.

3. The preparation method according to claim 1, wherein the carrier is in the shape of a sphere with a diameter of 1 mm to 2 mm; or the carrier is in the shape of a strip with a diameter of 2 mm to 3 mm.

4. 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 concentration of the inorganic base in the inorganic base aqueous solution is 0.0001 mol / L-1.00 mol / L; and / or The specific 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 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 support is 0.2:100.0-5.0:100.0; and / or The mass ratio of the co-metal element in the co-metal precursor aqueous solution to the pretreated support is 0.1:100.0-2.0:100.0; and / or The step (4) of washing with water is washing with water 3 to 5 times.

5. The preparation method according to any one of claims 1 to 2, wherein the concentration of the inorganic base in the inorganic base aqueous solution is 0.010 mol / L to 0.10 mol / L; and / or The mass ratio of the ruthenium element of the ruthenium precursor in the ruthenium precursor aqueous solution to the pretreated support is 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 support is 0.2:100.0-0.5:100.

0.

6. The preparation method according to any one of claims 1 to 2, 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.

7. The preparation method according to any one of claims 1 to 2, wherein the solvent in step (7) is water; and / or The reducing agent is at least one of sodium borohydride and sodium formate; 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 step (1) is 10 h-24 h; and / or The drying temperature in step (6) is 90°C-150°C; and / or The drying time of the drying step (6) is 10 h-24 h; and / or The drying temperature in step (8) is 90°C-150°C; and / or The drying time of the drying step (8) is 10 h-24 h; and / or The aging time of the aging in step (2) and step (3) is independently selected from 1 h to 3 h; and / or The aging in step (2) and step (3) is performed independently by placing the product in an air atmosphere at 30°C-40°C for aging.

8. The preparation method according to any one of claims 1-2, wherein the aging time in step (2) and step (3) is 2 hours.

9. The preparation method according to any one of claims 1 to 2, wherein the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is ethylenediamine; the reducing agent is sodium borohydride; or The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) is benzoic acid; the reducing agent is sodium borohydride; or The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes methanol; and the reducing agent is sodium formate.

10. The preparation method according to any one of claims 1 to 2, wherein 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) 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 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.

11. A catalyst prepared according to the preparation method according to any one of claims 1 to 10.

12. Use of the catalyst prepared by the preparation method according to any one of claims 1 to 10 or the catalyst according to claim 11 in catalyzing the hydrogenation reaction of benzene ring compounds to prepare cyclohexane compounds.

13. The use according to claim 12, wherein the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) comprises 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; or The organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) includes 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 The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes 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.

14. The use according to claim 12, wherein the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) 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; or The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) 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 The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) 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.

15. The use according to claim 12, wherein 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; 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; or 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; 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 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; 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.

16. The use according to any one of claims 13 to 15, wherein the benzene ring compound with an amino substituent comprises at least one of 1,2-phenylenediamine, 1,3-phenylenediamine, 1,4-phenylenediamine, 2,4-diaminotoluene, 4,4'-diaminodiphenylmethane, and p-phenylenediamine; and the cyclohexane compound with an amino substituent comprises at least one of 1,2-cyclohexanedimethylamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, 1-methyl-2,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine), and 1,4-cyclohexanediamine; The benzene ring compound with an ester substituent includes dimethyl terephthalate; the cyclohexane compound with an ester substituent includes dimethyl 1,4-cyclohexyldicarboxylate; The benzene ring compound with a carboxyl substituent includes terephthalic acid, and the cyclohexane compound with a carboxyl substituent includes 1,4-cyclohexanedicarboxylic acid; 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.

17. A method for preparing cyclohexane compounds by catalyzing the hydrogenation reaction of benzene ring compounds, characterized in that: include: In the presence of the catalyst prepared by the preparation method according to any one of claims 1 to 10 or the catalyst according to claim 11, a benzene ring compound is reacted with hydrogen in a reaction solvent to obtain a cyclohexane compound.

18. The method according to claim 17, characterized in that: The method comprises: S1: filling the catalyst into a fixed bed reactor; S2: introducing hydrogen into the fixed bed reactor for pretreatment; S3: introducing hydrogen gas and a benzene ring compound dissolved in a reaction solvent to react to obtain a cyclohexane compound.

19. The method according to any one of claims 17-18, 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-cyclohexanedimethylamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, 2,2-bis(4-hydroxycyclohexyl)propane, 1,4-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid dimethyl ester, 1-methyl-2,4-cyclohexanediamine, 4,4'-methylenebis(cyclohexylamine) or 1,4-cyclohexanediamine.

20. The method according to claim 17, wherein the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) comprises 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; or The organic auxiliary agent in the aqueous solution of the organic auxiliary agent in step (5) includes 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 The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) includes 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.

21. The method according to claim 17, wherein the organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) 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; or The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) 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 The organic auxiliary agent in the organic auxiliary agent aqueous solution in step (5) 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.

22. The method according to claim 17, wherein 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; 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; or 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; 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 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; 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.

23. The method according to any one of claims 20 to 22, wherein 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-cyclohexanedimethylamine, 1,3-cyclohexanedimethylamine, 1,4-cyclohexanedimethylamine, 1-methyl-2,4-cyclohexanediamine, 4,4'-diamino-dicyclohexylmethane, and 1,4-cyclohexanediamine; and / or 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 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 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.

24. The method according to any one of claims 17-18, wherein the reaction solvent is at least one of methanol, ethanol, tetrahydrofuran, water, dichloroethane, isopropanol, tetrachloroethylene or toluene; and / or The reaction temperature of the reaction is 80°C-250°C; and / or The reaction is carried out under a hydrogen pressure of 3.0 MPa-8.0 MPa; and / or The mass ratio of the benzene ring compound to the reaction solvent is 0.05:1.00-0.50:1.

00.

25. The method according to claim 18, wherein the temperature of the pretreatment in step S2 is 100°C-200°C; and / or The pre-treated hydrogen pressure in step S2 is 3.0 MPa-10.0 MPa; and / or The pretreatment time of the pretreatment in step S2 is 8h-24h; and / or Calculated based on the mass of the benzene ring compound, the mass space velocity of the benzene ring compound in step S3 is 0.05 g / (g·h)-2.00 g / (g·h); The molar ratio of the hydrogen gas introduced in step S3 to the benzene ring compound introduced is 5:1-150:

1.

26. The method according to any one of claims 17-18, wherein the mass ratio of the benzene ring compound to the reaction solvent is 0.10:1.00-0.15:1.00.

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