Mesoporous cerium oxide supported ruthenium catalyst as well as preparation method and application thereof

Abstract

The invention relates to a mesoporous cerium oxide supported ruthenium catalyst and a preparation method and application thereof.The preparation method includes the steps that tri (2-aminoethyl) amine and aromatic aldehyde are subjected to an aldehyde-amine condensation polymerization reaction to form imine bonds, a porous organic cage-shaped polymer is obtained, the organic cage-shaped polymer serves as a template, cerium oxide crystals are synthesized through a hydrothermal reaction, and the mesoporous cerium oxide supported ruthenium catalyst is obtained. Roasting to remove the organic cage polymer to obtain a mesoporous cerium oxide carrier; ruthenium single atoms are dispersed and loaded in channels of the mesoporous cerium oxide carrier through a supercritical fluid deposition method, then reduction is carried out, and the mesoporous cerium oxide-loaded ruthenium catalyst which is low in ruthenium loading capacity, uniform in metal active center distribution, small in particle size and high in dispersity is obtained, can be used repeatedly without inactivation and is used for bisphenol A hydrogenation reaction, and the catalytic activity of the catalyst is improved. The conversion rate of bisphenol A and the selectivity of hydrogenated bisphenol A can be effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of multiphase catalyst hydrogenation, and in particular to a mesoporous cerium oxide-supported ruthenium catalyst and a preparation method and application thereof. Background Art

[0002] Hydrogenated bisphenol A, chemical name 2,2′-bis(4-hydroxycyclohexyl)propane, referred to as HBPA, is a saturated alicyclic diol prepared by hydrogenating the benzene ring of bisphenol A. It is mainly used to manufacture polycarbonate, epoxy resin, polyacrylic resin, etc. It can also be used to produce plasticizers, flame retardants, antioxidants, heat stabilizers, rubber antioxidants, pesticides, coatings and other fine chemical products. It can be further applied to high-value LED packaging, high-value electrical insulation materials, fan blade coatings, medical device components, composite materials and other fields.

[0003] The research focus on the preparation method of hydrogenated bisphenol A is mainly on the development of hydrogenation catalysts. At present, there are three main types of catalysts for the hydrogenation of bisphenol A: metal skeleton catalysts, homogeneous catalysts and precious metal supported catalysts. Metal skeleton catalysts were the first type of catalysts to be studied, represented by Raney nickel, but this type of catalyst has the defects of large metal usage, catalyst inability to withstand high temperatures, and short life; homogeneous catalysts have high activity, but are inconvenient to prepare and use, and are not suitable for industrial applications; while precious metal supported catalysts have relatively excellent activity and are easy to prepare. Therefore, the current research focus is mainly on precious metal supported catalysts.

[0004] At present, the active components of noble metal supported catalysts are mainly Ru and Rh, and the carrier is mainly activated carbon, aluminum oxide or silicon oxide. For example, CN1095690A discloses a method for reacting an organic compound in the presence of a catalyst, wherein the catalyst comprises 0.01 to 30 wt% of ruthenium as an active metal applied to a carrier, either alone or together with at least one metal of Group IB, VIIB or VIIIB, accounting for the total weight of the catalyst, wherein in the carrier, macropores with a pore size ranging from 50 nm to 10000 nm account for 10 to 50% of the carrier pore volume, and mesopores with a pore size of 2 to 50 nm account for 50 to 90% of the carrier pore volume, and the sum of the pore volumes is 100%. CN102921440A discloses a catalyst for preparing hydrogenated bisphenol A, the components and mass fractions of which are: 100 parts of modified composite alumina carrier, 1-3 parts of precious metal as active component; the modified composite alumina carrier is composed of 30-80 parts by mass of pseudo-boehmite, 10-40 parts by mass of aluminum hydroxide, 1-5 parts by mass of alkali metal elements, and 1-5 parts by mass of phosphorus; the active component is a multi-component, selected from two of Pd, Ru, and Rh. CN1375484A discloses a method for preparing 2,2'-di(4-hydroxycyclohexyl)propane, using silicon dioxide as a carrier, loading metal ruthenium as an active component, and carrying out hydrogenation reaction of bisphenol A, but the acidity of the carrier is relatively high, which will lead to dehydroxylation reaction of the product and affect the selectivity of the product.

[0005] Although the above-mentioned noble metal catalysts have certain catalytic activity in the hydrogenation reaction of bisphenol A, these catalysts have strict requirements on reaction temperature and reaction pressure, and their selectivity and stability need to be improved. Therefore, it is urgent to develop a new bisphenol A hydrogenation catalyst with mild reaction conditions, high reactivity, high selectivity and high stability. Summary of the invention

[0006] In view of the shortcomings of the prior art, the purpose of the present invention is to provide a mesoporous cerium oxide-supported ruthenium catalyst and a preparation method and application thereof. The mesoporous cerium oxide-supported ruthenium catalyst has good activity, mild reaction conditions, the conversion rate and selectivity of the obtained hydrogenation product are close to 100%, the stability is excellent, and it has good industrial application prospects.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing a mesoporous cerium oxide-supported ruthenium catalyst, the preparation method comprising the following steps:

[0009] (1) mixing and heating tri(2-aminoethyl)amine, aromatic aldehyde, organic solvent and acid catalyst, and subjecting the obtained mixture to solid-liquid separation to obtain an organic cage polymer;

[0010] (2) subjecting the organic cage polymer obtained in step (1) to a hydrothermal reaction with a cerium source, subjecting the obtained mixture to solid-liquid separation, and calcining the obtained solid phase to obtain a mesoporous cerium oxide carrier;

[0011] (3) dispersing the ruthenium salt aqueous solution and the mesoporous cerium oxide carrier obtained in step (2) under the action of a supercritical fluid, and sequentially drying and reducing the obtained solid phase to obtain the mesoporous cerium oxide-supported ruthenium catalyst.

[0012] The present invention provides a method for preparing a mesoporous cerium oxide supported ruthenium catalyst. The method comprises the following steps: using tri(2-aminoethyl)amine and aromatic aldehyde to undergo an aldehyde-amine polycondensation reaction to form an imine bond, thereby obtaining a porous organic cage polymer. The porous cage structure is conducive to material transport, effectively controls the size of active metals, and significantly enhances catalytic efficiency. The organic cage polymer is further used as a template to synthesize cerium oxide crystals by a hydrothermal reaction, and the organic cage polymer is calcined to remove the organic cage polymer to obtain a mesoporous cerium oxide carrier. Ruthenium single atoms are dispersed and loaded in the pores of the mesoporous cerium oxide carrier by a supercritical fluid deposition method, and then reduced to obtain a mesoporous cerium oxide supported ruthenium catalyst with low ruthenium loading, uniform distribution of metal active centers, small particle size, and high dispersion. The reaction heat generated by a single catalytic site is easily diffused to the surroundings, thereby effectively reducing side reactions caused by the accumulation of reaction heat, and reducing the catalyst deactivation rate and other problems.

[0013] Preferably, the aromatic aldehyde in step (1) comprises any one of o-phthalaldehyde, terephthalaldehyde, 4,4'-biphenyldicarboxaldehyde or 2,5-diethoxyterephthalaldehyde, preferably terephthalaldehyde.

[0014] Preferably, the acid catalyst in step (1) comprises any one of glacial acetic acid, p-toluenesulfonic acid or phosphoric acid.

[0015] Preferably, the molar ratio of tris(2-aminoethyl)amine, aromatic aldehyde and acid catalyst in step (1) is 1:(0.8-2.7):(2-5), for example, it can be 1:0.8:2, 1:1.5:2.5, 1:2:3, 1:2.4:3.5 or 1:2.7:5, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 1:(1.5-2.4):(2.5-3.5).

[0016] Preferably, the organic solvent in step (1) comprises any one of acetonitrile, chloroform, o-dichlorobenzene, tetrahydrofuran or dichloromethane, preferably acetonitrile.

[0017] Preferably, the ratio of tris(2-aminoethyl)amine to organic solvent in step (1) is (0.1-1) mol:1L, for example, 0.1 mol:1L, 0.25 mol:1L, 0.3 mol:1L, 0.4 mol:1L or 1 mol:1L, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable, preferably (0.25-0.4) mol:1L.

[0018] Preferably, the mixing and heating in step (1) is carried out under nitrogen protection.

[0019] Preferably, the heating rate of the mixed heating in step (1) is 10-40°C / min, for example, 10°C / min, 20°C / min, 25°C / min, 30°C / min or 40°C / min, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 20-30°C / min.

[0020] Preferably, the temperature of the mixed heating in step (1) is 140-220°C, for example, 140°C, 160°C, 170°C, 180°C or 220°C, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 160-180°C.

[0021] Preferably, the mixing and heating time in step (1) is 50-120 h, for example, 50 h, 60 h, 80 h, 90 h or 120 h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable, preferably 60-90 h.

[0022] Preferably, after the solid-liquid separation in step (1), the obtained solid phase is washed and vacuum dried in sequence.

[0023] Preferably, the washing is washing once with methanol and washing twice with distilled water in sequence.

[0024] Preferably, the vacuum drying temperature is 60-100°C, for example, 60°C, 70°C, 75°C, 80°C or 100°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 70-80°C.

[0025] Preferably, the vacuum drying time is 12-36 h, for example, 12 h, 18 h, 20 h, 24 h or 36 h, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 18-24 h.

[0026] Preferably, the organic cage polymer and the cerium source are ultrasonically dispersed before the hydrothermal reaction in step (2).

[0027] Preferably, 3-15 mL of 1-5 mol / L alkali solution is added during the ultrasonic dispersion.

[0028] The amount of the alkali solution used is 3-15 mL, for example, 3 mL, 5 mL, 8 mL, 10 mL or 15 mL, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0029] The concentration of the alkali solution is 1-5 mol / L, for example, 1 mol / L, 2 mol / L, 3 mol / L, 4 mol / L or 5 mol / L, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0030] Preferably, the alkali solution comprises sodium hydroxide solution.

[0031] The addition of the alkaline solution enables the prepared alkaline mesoporous cerium oxide support to work synergistically with the ruthenium catalytic sites to effectively reduce the generation of dehydration by-products and improve the selectivity of hydrogenated bisphenol A.

[0032] Preferably, the cerium source in step (2) is an aqueous solution of a cerium salt, and the cerium salt includes any one of cerium nitrate, cerium chloride, cerium sulfate or cerium acetate, preferably cerium nitrate.

[0033] Preferably, the concentration of the cerium salt in the cerium source in step (2) is 6.5-26 g / L, for example, 6.5 g / L, 9.8 g / L, 13.4 g / L, 17.5 g / L or 26 g / L, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0034] Preferably, the mass ratio of the cerium salt to the organic cage polymer in the cerium source in step (2) is 1:(0.5-2.4), for example, it can be 1:0.5, 1:0.8, 1:1, 1:1.5 or 1:2.4, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 1:(0.8-1.5).

[0035] Preferably, the temperature of the hydrothermal reaction in step (2) is 80-150°C, for example, 80°C, 100°C, 110°C, 120°C or 150°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable, preferably 100-120°C.

[0036] Preferably, the time of the hydrothermal reaction in step (2) is 2-8 h, for example, 2 h, 4 h, 5 h, 6 h or 8 h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable, preferably 4-6 h.

[0037] Preferably, after the solid-liquid separation in step (2), the obtained solid phase is washed and vacuum dried at 75-85°C in sequence, for example, it can be 75°C, 78°C, 80°C, 82°C or 85°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0038] Preferably, the washing is washing once with methanol and washing twice with distilled water in sequence.

[0039] Preferably, the specific steps of the calcination in step (2) include: heating to 580-620°C at a rate of 3-5°C / min in an argon atmosphere, calcining for 1.5-2.5h, and then continuing to calcine in an air atmosphere for 3.5-4.5h.

[0040] The heating rate of the calcination is 3-5°C / min, for example, 3°C / min, 3.5°C / min, 4°C / min, 4.5°C / min or 5°C / min, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0041] The temperature end point of the calcination is 580-620°C, for example, 580°C, 590°C, 600°C, 610°C or 620°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0042] The calcination time is 1.5-2.5 h, for example, 1.5 h, 1.8 h, 2 h, 2.2 h or 2.5 h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0043] The time for continued roasting is 3.5-4.5 hours, for example, 3.5 hours, 3.8 hours, 4 hours, 4.2 hours or 4.5 hours, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0044] Preferably, the calcination in step (2) is followed by natural cooling.

[0045] Preferably, the ruthenium salt in the ruthenium salt aqueous solution in step (3) comprises RuCl 3 ·3H 2 O.Ru(NO)(NO 3 ) x (OH) y or C 14 H 21 O 14 Ru 3 Any one of the following, wherein 0≤x≤3, 0≤y≤3, x+y=3, preferably RuCl 3 ·3H 2 O.

[0046] The 0≤x≤3 may be, for example, 0, 1, 2 or 3, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0047] The 0≤y≤3 may be, for example, 0, 1, 2 or 3, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0048] Preferably, the concentration of ruthenium salt in the ruthenium salt aqueous solution in step (3) is 0.1-2 g / L, for example, 0.1 g / L, 0.5 g / L, 1 g / L, 1.5 g / L or 2 g / L, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0049] Preferably, the mass ratio of ruthenium ions in the ruthenium salt aqueous solution in step (3) to the mesoporous cerium oxide carrier is (0.1-2):100, for example, it can be 0.1:100, 0.5:100, 0.8:100, 1:100 or 2:100, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably (0.5-1):100.

[0050] Preferably, the supercritical fluid in step (3) comprises carbon dioxide.

[0051] In the present invention, the ruthenium salt aqueous solution and the mesoporous cerium oxide carrier are added into a high-pressure reactor, and carbon dioxide is introduced into the high-pressure reactor through a compression pump for dispersion.

[0052] Preferably, the dispersion temperature in step (3) is 40-90°C, for example, 40°C, 50°C, 60°C, 70°C or 90°C, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 50-70°C.

[0053] Preferably, the dispersion pressure in step (3) is 8-13 MPa, for example, 8 MPa, 10 MPa, 10.5 MPa, 11 MPa or 13 MPa, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 10-11 MPa.

[0054] Preferably, the dispersion time in step (3) is 2-8 h, for example, 2 h, 4 h, 5 h, 6 h or 8 h, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 4-6 h.

[0055] Preferably, the drying temperature in step (3) is 75-85° C. and the drying time is 3-5 h.

[0056] The drying temperature is 75-85°C, for example, 75°C, 78°C, 80°C, 82°C or 85°C, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0057] The drying time is 3-5 hours, for example, 3 hours, 3.5 hours, 4 hours, 4.5 hours or 5 hours, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable.

[0058] Preferably, a mixture of hydrogen and argon is introduced during the reduction in step (3).

[0059] Preferably, the volume fraction of hydrogen in the mixed gas is 5%, and the remainder is argon.

[0060] Preferably, the reduction temperature in step (3) is 400-700°C, for example, 400°C, 500°C, 550°C, 600°C or 700°C, but is not limited to the listed values. Other values ​​not listed within the numerical range are also applicable, preferably 500-600°C.

[0061] Preferably, the reduction time in step (3) is 1-6 h, for example, 1 h, 2 h, 3 h, 4 h or 6 h, but is not limited to the listed values, and other values ​​not listed within the numerical range are also applicable, preferably 2-4 h.

[0062] In a second aspect, the present invention provides a mesoporous cerium oxide supported ruthenium catalyst, wherein the mesoporous cerium oxide supported ruthenium catalyst is prepared by the preparation method of the mesoporous cerium oxide supported ruthenium catalyst according to the first aspect;

[0063] The ruthenium loading of the mesoporous cerium oxide-supported ruthenium catalyst is 0.1-2wt%, for example, it can be 0.1wt%, 0.5wt%, 1wt%, 1.5wt% or 2wt%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0064] The mesoporous cerium oxide supported ruthenium catalyst provided by the present invention has a porous cage structure that is conducive to material transmission, effectively controls the size of active metals, and significantly enhances catalytic efficiency; the characteristics of single-atom catalysts are conducive to reducing the amount of precious metals used and reducing the cost of catalytic use; the alkaline carrier is conducive to slowing down the dehydroxylation side reaction during the hydrogenation process; the mesoporous cerium oxide supported ruthenium catalyst has mild reaction conditions, stable performance, and a long life, and can be applied multiple times without deactivation.

[0065] In a third aspect, the present invention provides an application of the mesoporous cerium oxide-supported ruthenium catalyst as described in the second aspect, wherein the mesoporous cerium oxide-supported ruthenium catalyst is used for the hydrogenation reaction of bisphenol A to synthesize hydrogenated bisphenol A.

[0066] The present invention uses the mesoporous cerium oxide supported ruthenium catalyst for bisphenol A hydrogenation reaction, which can effectively increase the conversion rate of bisphenol A hydrogenation to 100%, wherein the synergistic effect of the alkaline mesoporous cerium oxide carrier and the ruthenium catalytic site can effectively reduce the generation of dehydration by-products and increase the selectivity of hydrogenated bisphenol A to 99.87%.

[0067] Preferably, the raw material for the hydrogenation reaction further includes alcohol, and the alcohol includes any one of methanol, ethanol or isopropanol, preferably isopropanol.

[0068] Preferably, the mass concentration of bisphenol A in the alcoholic solution of bisphenol A is 1-50%, for example, it can be 1%, 10%, 15%, 20%, 30%, 40% or 50%, but is not limited to the listed values. Other unlisted values ​​within the numerical range are also applicable, preferably 10-20%.

[0069] Preferably, the mass of the mesoporous cerium oxide-supported ruthenium catalyst is 0.5-3% of the mass of bisphenol A, for example, it can be 0.5%, 1%, 1.5%, 2% or 3%, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable.

[0070] Preferably, the temperature of the hydrogenation reaction is 60-140°C, for example, 60°C, 80°C, 90°C, 100°C or 140°C, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 80-100°C.

[0071] Preferably, the hydrogen pressure of the hydrogenation reaction is 1-5 MPa, for example, 1 MPa, 2 MPa, 2.5 MPa, 3 MPa or 5 MPa, but is not limited to the listed values, and other unlisted values ​​within the numerical range are also applicable, preferably 2-3 MPa.

[0072] Compared with the prior art, the present invention has the following beneficial effects:

[0073] (1) The preparation method of the mesoporous cerium oxide supported ruthenium catalyst provided by the present invention comprises the following steps: using tri(2-aminoethyl)amine and aromatic aldehyde to undergo an aldehyde-amine condensation reaction to form an imine bond, thereby obtaining a porous organic cage polymer; the porous cage structure is conducive to material transport, effectively controls the size of active metals, and significantly enhances the catalytic efficiency; further, using the organic cage polymer as a template, a hydrothermal reaction is used to synthesize cerium oxide crystals; the organic cage polymer is calcined to remove the organic cage polymer, and a mesoporous cerium oxide carrier is obtained; and ruthenium single atoms are dispersed and loaded in the pores of the mesoporous cerium oxide carrier by a supercritical fluid deposition method, and then reduced to obtain a mesoporous cerium oxide supported ruthenium catalyst with low ruthenium loading, uniform distribution of metal active centers, small particle size, and high dispersion. The reaction heat generated by a single catalytic site is easily diffused to the surrounding area, which effectively reduces the side reactions caused by the accumulation of reaction heat and reduces the catalyst deactivation rate.

[0074] (2) The mesoporous cerium oxide supported ruthenium catalyst provided by the present invention has mild reaction conditions, stable performance, long service life, and can be applied multiple times without deactivation. It is used for the hydrogenation reaction of bisphenol A and can effectively increase the conversion rate of bisphenol A hydrogenation to 100%. The synergistic effect of the alkaline mesoporous cerium oxide support and the ruthenium catalytic sites can effectively reduce the formation of dehydration by-products and increase the selectivity of hydrogenated bisphenol A to 99.87%. BRIEF DESCRIPTION OF THE DRAWINGS

[0075] Figure 1 is a TEM image of the mesoporous cerium oxide-supported ruthenium catalyst provided in Example 1 of the present invention;

[0076] Figure 2 is a nitrogen adsorption-desorption curve diagram of the mesoporous cerium oxide-supported ruthenium catalyst provided in Example 1 of the present invention;

[0077] Figure 3 is a pore size distribution diagram of the mesoporous cerium oxide-supported ruthenium catalyst provided in Example 1 of the present invention;

[0078] Figure 4 The bisphenol A hydrogenation reaction is carried out using the mesoporous cerium oxide supported ruthenium catalyst provided in Example 1 of the present invention, and the conversion rate of bisphenol A and the selectivity of hydrogenated bisphenol A change at different cycle times. DETAILED DESCRIPTION

[0079] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0080] Example 1

[0081] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst, wherein the ruthenium loading amount of the mesoporous cerium oxide supported ruthenium catalyst is 0.5 wt %.

[0082] The preparation method of the mesoporous cerium oxide supported ruthenium catalyst comprises the following steps:

[0083] (1) Mixing and heating tri(2-aminoethyl)amine, terephthalaldehyde, acetonitrile and glacial acetic acid under nitrogen protection, the heating rate of the mixed heating is 25°C / min, the temperature is 170°C, and the time is 80 hours. After the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 75°C for 20 hours to obtain an organic cage polymer; the molar ratio of the tri(2-aminoethyl)amine, terephthalaldehyde and glacial acetic acid is 1:2:3; the amount ratio of the tri(2-aminoethyl)amine to acetonitrile is 0.3 mol:1L;

[0084] (2) The organic cage polymer, cerium nitrate aqueous solution and sodium hydroxide solution obtained in the ultrasonic dispersion step (1) are then subjected to hydrothermal reaction at 110° C. for 5 h, the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 80° C.; the temperature is increased to 600° C. at a rate of 4° C. / min under an argon atmosphere, and calcined for 2 h, and then further calcined in an air atmosphere for 4 h, and naturally cooled to obtain a mesoporous cerium oxide carrier; the concentration of cerium nitrate in the cerium nitrate aqueous solution is 9.8 g / L; the mass ratio of cerium nitrate to organic cage polymer in the cerium nitrate aqueous solution is 1:1; the amount of the sodium hydroxide solution is 8 mL, and the concentration is 1 mol / L;

[0085] (3) RuCl 3 ·3H 2 O and the mesoporous cerium oxide carrier obtained in step (2) are dispersed at 60° C. and 10.5 MPa for 5 h under the action of carbon dioxide; the obtained solid phase is dried at 80° C. for 4 h, and then reduced by introducing a mixture of 5% hydrogen and argon at a temperature of 550° C. for 3 h to obtain the mesoporous cerium oxide supported ruthenium catalyst; the RuCl 3 ·3H 2 RuCl in aqueous solution 3 ·3H 2 O concentration is 0.1 g / L; the RuCl 3 ·3H 2 The mass ratio of ruthenium ions in the aqueous solution of O to the mesoporous ceria support is 0.5:100.

[0086] The TEM image of the mesoporous cerium oxide supported ruthenium catalyst obtained in this example is as follows: Figure 1 As shown in the figure, it can be seen from the circled part that the ruthenium element is evenly distributed on the mesoporous cerium oxide carrier. The nitrogen adsorption and desorption curve of the mesoporous cerium oxide supported ruthenium catalyst is shown in Figure 2 The pore size distribution diagram is shown in Figure 3As shown in the figure, it can be seen that the specific surface area of ​​the prepared mesoporous cerium oxide supported ruthenium catalyst is 70m 2 / g, pore size distribution is 5-60nm, pore volume is 0.28cm 3 / g.

[0087] The mesoporous cerium oxide-supported ruthenium catalyst, bisphenol A and isopropanol are subjected to hydrogenation reaction at 90° C. and 2.5 MPa, wherein the mass concentration of bisphenol A in the alcohol solution of bisphenol A is 15%, and the mass of the mesoporous cerium oxide-supported ruthenium catalyst is 2% of the mass of bisphenol A, to synthesize hydrogenated bisphenol A.

[0088] Example 2

[0089] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst, wherein the ruthenium loading amount of the mesoporous cerium oxide supported ruthenium catalyst is 1 wt %.

[0090] The preparation method of the mesoporous cerium oxide supported ruthenium catalyst comprises the following steps:

[0091] (1) Mixing and heating tri(2-aminoethyl)amine, o-phthalaldehyde, tetrahydrofuran and glacial acetic acid under nitrogen protection, the heating rate of the mixed heating is 20°C / min, the temperature is 160°C, the time is 90h, the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 70°C for 24h to obtain an organic cage polymer; the molar ratio of tri(2-aminoethyl)amine, o-phthalaldehyde and glacial acetic acid is 1:1.5:2.5; the amount ratio of tri(2-aminoethyl)amine to tetrahydrofuran is 0.25mol:1L;

[0092] (2) The organic cage polymer, cerium chloride aqueous solution and sodium hydroxide solution obtained in the ultrasonic dispersion step (1) are then subjected to hydrothermal reaction at 100° C. for 6 h, the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 75° C.; the temperature is increased to 580° C. at a rate of 3° C. / min under an argon atmosphere, and roasted for 2.5 h, and then further roasted in an air atmosphere for 4.5 h, and naturally cooled to obtain a mesoporous cerium oxide carrier; the concentration of cerium chloride in the cerium chloride aqueous solution is 13.4 g / L; the mass ratio of cerium chloride to organic cage polymer in the cerium chloride aqueous solution is 1:0.8; the amount of the sodium hydroxide solution is 5 mL, and the concentration is 3 mol / L;

[0093] (3) RuCl 3 ·3H 2O and the mesoporous cerium oxide carrier obtained in step (2) are dispersed at 50° C. and 10 MPa for 6 h under the action of carbon dioxide; the obtained solid phase is dried at 75° C. for 5 h, and then reduced by introducing a mixture of 5% hydrogen and argon at a temperature of 500° C. for 4 h to obtain the mesoporous cerium oxide supported ruthenium catalyst; the RuCl 3 ·3H 2 RuCl in aqueous solution 3 ·3H 2 O concentration is 1g / L; the RuCl 3 ·3H 2 The mass ratio of ruthenium ions in the aqueous solution of O to the mesoporous ceria support is 1:100.

[0094] The mesoporous cerium oxide-supported ruthenium catalyst, bisphenol A and isopropanol are subjected to hydrogenation reaction at 80° C. and 3 MPa, wherein the mass concentration of bisphenol A in the alcohol solution of bisphenol A is 10%, and the mass of the mesoporous cerium oxide-supported ruthenium catalyst is 1% of the mass of bisphenol A, to synthesize hydrogenated bisphenol A.

[0095] Example 3

[0096] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst, wherein the ruthenium loading amount of the mesoporous cerium oxide supported ruthenium catalyst is 1.5 wt %.

[0097] The preparation method of the mesoporous cerium oxide supported ruthenium catalyst comprises the following steps:

[0098] (1) Mixing and heating tris(2-aminoethyl)amine, 4,4'-biphenyldicarboxaldehyde, o-dichlorobenzene and glacial acetic acid under nitrogen protection, the heating rate of the mixed heating is 30°C / min, the temperature is 180°C, the time is 60h, the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 80°C for 18h to obtain an organic cage polymer; the molar ratio of tris(2-aminoethyl)amine, 4,4'-biphenyldicarboxaldehyde and glacial acetic acid is 1:2.4:3.5; the amount ratio of tris(2-aminoethyl)amine to o-dichlorobenzene is 0.4mol:1L;

[0099] (2) The organic cage polymer, cerium chloride aqueous solution and sodium hydroxide solution obtained in the ultrasonic dispersion step (1) are then subjected to hydrothermal reaction at 120° C. for 4 h, the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 85° C.; the temperature is increased to 620° C. at a rate of 5° C. / min in an argon atmosphere, and calcined for 1.5 h, and then further calcined in an air atmosphere for 3.5 h, and naturally cooled to obtain a mesoporous cerium oxide carrier; the concentration of cerium chloride in the cerium chloride aqueous solution is 17.5 g / L; the mass ratio of cerium chloride to organic cage polymer in the cerium chloride aqueous solution is 1:1.5; the amount of the sodium hydroxide solution is 10 mL, and the concentration is 2 mol / L;

[0100] (3) RuCl 3 ·3H 2 O and the mesoporous cerium oxide carrier obtained in step (2) are dispersed at 70° C. and 11 MPa for 4 h under the action of carbon dioxide; the obtained solid phase is dried at 85° C. for 3 h, and then reduced by introducing a mixture of 5% hydrogen and argon at a temperature of 600° C. for 2 h to obtain the mesoporous cerium oxide supported ruthenium catalyst; the RuCl 3 ·3H 2 RuCl in aqueous solution 3 ·3H 2 O concentration is 1.5 g / L; the RuCl 3 ·3H 2 The mass ratio of ruthenium ions in the aqueous solution of O to the mesoporous ceria support is 1.5:100.

[0101] The mesoporous cerium oxide-supported ruthenium catalyst, bisphenol A and isopropanol are subjected to hydrogenation reaction at 100° C. and 2 MPa, wherein the mass concentration of bisphenol A in the alcohol solution of bisphenol A is 20%, and the mass of the mesoporous cerium oxide-supported ruthenium catalyst is 1.5% of the mass of bisphenol A, to synthesize hydrogenated bisphenol A.

[0102] Example 4

[0103] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst, wherein the ruthenium loading amount of the mesoporous cerium oxide supported ruthenium catalyst is 0.1 wt %.

[0104] The preparation method of the mesoporous cerium oxide supported ruthenium catalyst comprises the following steps:

[0105] (1) Mixing and heating tri(2-aminoethyl)amine, terephthalaldehyde, chloroform and p-toluenesulfonic acid under nitrogen protection, the heating rate of the mixed heating is 10°C / min, the temperature is 140°C, and the time is 120 hours. After the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 60°C for 36 hours to obtain an organic cage polymer; the molar ratio of the tri(2-aminoethyl)amine, terephthalaldehyde and p-toluenesulfonic acid is 1:0.8:2; the amount ratio of the tri(2-aminoethyl)amine to chloroform is 0.1 mol:1L;

[0106] (2) The organic cage polymer, cerium sulfate aqueous solution and sodium hydroxide solution obtained in the ultrasonic dispersion step (1) are then subjected to hydrothermal reaction at 80° C. for 8 h, the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 75° C.; the temperature is increased to 580° C. at a rate of 3° C. / min under an argon atmosphere, and roasted for 2.5 h, and then further roasted in an air atmosphere for 4.5 h, and naturally cooled to obtain a mesoporous cerium oxide carrier; the concentration of cerium sulfate in the cerium sulfate aqueous solution is 6.5 g / L; the mass ratio of cerium sulfate to organic cage polymer in the cerium sulfate aqueous solution is 1:0.5; the amount of the sodium hydroxide solution is 3 mL, and the concentration is 1 mol / L;

[0107] (3) RuCl 3 ·3H 2 O and the mesoporous cerium oxide carrier obtained in step (2) are dispersed at 40° C. and 8 MPa for 8 h under the action of carbon dioxide; the obtained solid phase is dried at 75° C. for 5 h, and then reduced by introducing a mixture of 5% hydrogen and argon at a temperature of 400° C. for 6 h to obtain the mesoporous cerium oxide supported ruthenium catalyst; the RuCl 3 ·3H 2 RuCl in aqueous solution 3 ·3H 2 O concentration is 0.1 g / L; the RuCl 3 ·3H 2 The mass ratio of ruthenium ions in the aqueous solution of O to the mesoporous cerium oxide support is 0.1:100.

[0108] The mesoporous cerium oxide-supported ruthenium catalyst, bisphenol A and isopropanol are subjected to hydrogenation reaction at 60° C. and 5 MPa, wherein the mass concentration of bisphenol A in the alcohol solution of bisphenol A is 1%, and the mass of the mesoporous cerium oxide-supported ruthenium catalyst is 3% of the mass of bisphenol A, to synthesize hydrogenated bisphenol A.

[0109] Example 5

[0110] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst, wherein the ruthenium loading amount of the mesoporous cerium oxide supported ruthenium catalyst is 2 wt %.

[0111] The preparation method of the mesoporous cerium oxide supported ruthenium catalyst comprises the following steps:

[0112] (1) Mixing and heating tri(2-aminoethyl)amine, 2,5-diethoxyterephthalaldehyde, dichloromethane and phosphoric acid under nitrogen protection, the heating rate of the mixed heating is 40°C / min, the temperature is 220°C, and the time is 50 hours. After the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 100°C for 12 hours to obtain an organic cage polymer; the molar ratio of the tri(2-aminoethyl)amine, 2,5-diethoxyterephthalaldehyde and phosphoric acid is 1:2.7:5; the amount ratio of the tri(2-aminoethyl)amine to dichloromethane is 1 mol:1L;

[0113] (2) The organic cage polymer, cerium acetate aqueous solution and sodium hydroxide solution obtained in the ultrasonic dispersion step (1) are then subjected to hydrothermal reaction at 150° C. for 2 h, the obtained mixture is filtered, the obtained solid phase is washed once with methanol and twice with distilled water, and then vacuum dried at 85° C.; the temperature is increased to 620° C. at a rate of 5° C. / min in an argon atmosphere, and calcined for 1.5 h, and then further calcined in an air atmosphere for 3.5 h, and naturally cooled to obtain a mesoporous cerium oxide carrier; the concentration of cerium acetate in the cerium acetate aqueous solution is 26 g / L; the mass ratio of cerium acetate to organic cage polymer in the cerium acetate aqueous solution is 1:2.4; the amount of the sodium hydroxide solution used is 10 mL, and the concentration is 5 mol / L;

[0114] (3) RuCl 3 ·3H 2 The aqueous solution of O and the mesoporous cerium oxide carrier obtained in step (2) are dispersed at 90° C. and 13 MPa for 2 h under the action of carbon dioxide; the obtained solid phase is dried at 85° C. for 3 h, and then reduced by introducing a mixture of 5% hydrogen and argon at a temperature of 700° C. for 1 h to obtain the mesoporous cerium oxide supported ruthenium catalyst; the RuCl 3 ·3H 2 RuCl in aqueous solution 3 ·3H 2 O concentration is 2g / L; the RuCl 3 ·3H 2 The mass ratio of ruthenium ions in the aqueous solution of O to the mesoporous ceria support is 2:100.

[0115] The mesoporous cerium oxide-supported ruthenium catalyst, bisphenol A and isopropanol are subjected to hydrogenation reaction at 140° C. and 1 MPa, wherein the mass concentration of bisphenol A in the alcohol solution of bisphenol A is 50%, and the mass of the mesoporous cerium oxide-supported ruthenium catalyst is 0.5% of the mass of bisphenol A, to synthesize hydrogenated bisphenol A.

[0116] Example 6

[0117] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 1 in that, in addition to the RuCl 3 ·3H 2 O was replaced by Ru(NO)(NO 3 ) 1 (OH) 2 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 0.5 wt %, the rest is the same as Example 1.

[0118] Example 7

[0119] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 2 in that, in addition to the RuCl 3 ·3H 2 O was replaced by Ru(NO)(NO 3 ) 2 (OH) 1 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 1 wt%, the rest is the same as Example 2.

[0120] Example 8

[0121] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 3 in that, in addition to the RuCl 3 ·3H 2 O was replaced by Ru(NO)(NO 3 ) 1.5 (OH) 1.5 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 1.5 wt%, the rest is the same as Example 3.

[0122] Example 9

[0123] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 4 in that, in addition to the RuCl 3 ·3H 2O was replaced by Ru(NO)(NO 3 ) 3 (OH) 0 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 0.1 wt%, the rest is the same as Example 4.

[0124] Example 10

[0125] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 5 in that, in addition to the RuCl 3 ·3H 2 O was replaced by Ru(NO)(NO 3 ) 0 (OH) 3 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 2 wt%, the rest is the same as Example 5.

[0126] Embodiment 11

[0127] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 1 in that, in addition to the RuCl 3 ·3H 2 O is replaced by C at one third of the molar amount 14 H 21 O 14 Ru 3 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 0.5 wt %, the rest is the same as Example 1.

[0128] Example 12

[0129] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 2 in that, in addition to the RuCl 3 ·3H 2 O is replaced by C at one third of the molar amount 14 H 21 O 14 Ru 3 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 1 wt%, the rest is the same as Example 2.

[0130] Embodiment 13

[0131] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 3 in that, in addition to the RuCl 3·3H 2 O is replaced by C at one third of the molar amount 14 H 21 O 14 Ru 3 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 1.5 wt%, the rest is the same as Example 3.

[0132] Embodiment 14

[0133] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 4 in that, in addition to the RuCl 3 ·3H 2 O is replaced by C at one third of the molar amount 14 H 21 O 14 Ru 3 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 0.1 wt%, the rest is the same as Example 4.

[0134] Embodiment 15

[0135] This embodiment provides a mesoporous cerium oxide supported ruthenium catalyst. The preparation method of the mesoporous cerium oxide supported ruthenium catalyst is different from that of embodiment 5 in that, in addition to the RuCl 3 ·3H 2 O is replaced by C at one third of the molar amount 14 H 21 O 14 Ru 3 Except for preparing a mesoporous cerium oxide-supported ruthenium catalyst with a ruthenium loading of 2 wt%, the rest is the same as Example 5.

[0136] Comparative Example 1

[0137] This comparative example provides a cerium oxide-supported ruthenium catalyst. The difference between the preparation method of the cerium oxide-supported ruthenium catalyst and that of Example 1 is that steps (1) and (2) are omitted, and the mass of the mesoporous cerium oxide carrier in step (3) is replaced by a commercially available cerium oxide carrier, and the rest is the same as that of Example 1.

[0138] Catalytic performance test: The mesoporous cerium oxide-supported ruthenium catalyst provided in Examples 1-15 and the cerium oxide-supported ruthenium catalyst provided in Comparative Example 1 were used for the hydrogenation reaction of bisphenol A to synthesize hydrogenated bisphenol A. After the reaction was completed, the mixture was filtered and a small amount of the filtrate was analyzed by gas chromatography. A SE-54 polar capillary (0.25 mm × 30 m × 0.5 μm) was selected and the measurement was carried out by a constant temperature method. The column temperature was 240°C, the FID detector, the detector temperature was 280°C, the injector temperature was 260°C, the carrier gas was used, and the injection volume was 0.5 μL. The product analysis was carried out by the peak area normalization method. The obtained bisphenol A conversion rate and hydrogenated bisphenol A selectivity are shown in Table 1.

[0139] Table 1

[0140] Bisphenol A conversion rate (%) Selectivity of hydrogenated bisphenol A (%) Example 1 100 99.87 Example 2 100 99.82 Example 3 100 99.78 Example 4 100 99.34 Example 5 100 99.56 Example 6 100 99.09 Example 7 100 99.75 Example 8 100 99.42 Example 9 100 99.63 Example 10 100 99.29 Embodiment 11 100 99.14 Example 12 100 99.51 Embodiment 13 100 99.81 Embodiment 14 100 99.19 Embodiment 15 100 99.68 Comparative Example 1 51.7 95.13

[0141] It can be seen from Table 1 that the mesoporous cerium oxide supported ruthenium catalyst prepared by the present invention can catalyze the hydrogenation reaction of bisphenol A, and the conversion rate of bisphenol A can reach 100%, and the selectivity of hydrogenated bisphenol A can reach 99.87%; while when the traditional cerium oxide carrier supported ruthenium is used as a catalyst to catalyze the hydrogenation reaction of bisphenol A, the conversion rate of bisphenol A and the selectivity of hydrogenated bisphenol A are significantly reduced.

[0142] Catalyst application evaluation: The single application process is the same as that in Example 1. The evaluation object is the mesoporous cerium oxide supported ruthenium catalyst prepared in Example 1. After a single application, the mesoporous cerium oxide supported ruthenium catalyst is recovered by filtration. The recovered mesoporous cerium oxide supported ruthenium catalyst is used for the next application evaluation. The conversion rate of bisphenol A and the selectivity of hydrogenated bisphenol A under different cycle times are shown in the figure below. Figure 4 As shown in the figure, it can be seen that the performance of the mesoporous cerium oxide supported ruthenium catalyst is stable, and there is no obvious decrease in activity and selectivity after repeated use.

[0143] In summary, the preparation method of the mesoporous cerium oxide supported ruthenium catalyst provided by the present invention utilizes tri(2-aminoethyl)amine and aromatic aldehyde to carry out aldehyde-amine condensation reaction to form imine bonds, thereby obtaining a porous organic cage polymer, wherein the porous cage structure is conducive to material transport, effectively controls the size of active metals, and significantly enhances the catalytic efficiency; further, the organic cage polymer is used as a template, cerium oxide crystals are synthesized by hydrothermal reaction, and the organic cage polymer is calcined to remove the organic cage polymer, thereby obtaining a mesoporous cerium oxide carrier; ruthenium single atoms are dispersed and loaded in the pores of the mesoporous cerium oxide carrier by supercritical fluid deposition method, and then reduced to obtain a mesoporous cerium oxide supported ruthenium catalyst with low ruthenium loading, uniform distribution of metal active centers, small particle size, and high dispersion, wherein the reaction heat generated by a single catalytic site is easily diffused to the surroundings, thereby effectively reducing the side reactions caused by the accumulation of reaction heat, and reducing the catalyst deactivation rate and other problems.

[0144] The mesoporous cerium oxide supported ruthenium catalyst provided by the present invention has mild reaction conditions, stable performance, long service life, can be applied multiple times without deactivation, and is used for bisphenol A hydrogenation reaction, which can effectively improve the conversion rate of bisphenol A hydrogenation to 100%. The synergistic effect of the alkaline mesoporous cerium oxide carrier and the ruthenium catalytic site can effectively reduce the generation of dehydration by-products and improve the selectivity of hydrogenated bisphenol A to 99.87%.

[0145] The applicant declares that the above is only a specific implementation mode of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention shall fall within the protection scope and disclosure scope of the present invention.

Claims

1. A method for preparing a mesoporous cerium oxide supported ruthenium catalyst, characterized in that: The preparation method comprises the following steps: (1) mixing and heating tri(2-aminoethyl)amine, aromatic aldehyde, organic solvent and acid catalyst, and subjecting the obtained mixture to solid-liquid separation to obtain an organic cage polymer; (2) subjecting the organic cage polymer obtained in step (1) to a hydrothermal reaction with a cerium source, subjecting the obtained mixture to solid-liquid separation, and calcining the obtained solid phase to obtain a mesoporous cerium oxide carrier; (3) dispersing the ruthenium salt aqueous solution and the mesoporous cerium oxide carrier obtained in step (2) under the action of a supercritical fluid, and sequentially drying and reducing the obtained solid phase to obtain the mesoporous cerium oxide-supported ruthenium catalyst.

2. The preparation method according to claim 1, characterized in that: The aromatic aldehyde in step (1) includes any one of o-phthalaldehyde, terephthalaldehyde, 4,4'-biphenyldicarboxaldehyde or 2,5-diethoxyterephthalaldehyde, preferably terephthalaldehyde; Preferably, the acid catalyst in step (1) comprises any one of glacial acetic acid, p-toluenesulfonic acid or phosphoric acid; Preferably, the molar ratio of tris(2-aminoethyl)amine, aromatic aldehyde and acid catalyst in step (1) is 1:(0.8-2.7):(2-5), preferably 1:(1.5-2.4):(2.5-3.5); Preferably, the organic solvent in step (1) comprises any one of acetonitrile, chloroform, o-dichlorobenzene, tetrahydrofuran or dichloromethane, preferably acetonitrile; Preferably, the ratio of tris(2-aminoethyl)amine to organic solvent in step (1) is (0.1-1) mol:1L, preferably (0.25-0.4) mol:1L.

3. The preparation method according to claim 1 or 2, characterized in that: The mixing and heating in step (1) is carried out under nitrogen protection; Preferably, the heating rate of the mixed heating in step (1) is 10-40°C / min, preferably 20-30°C / min; Preferably, the temperature of the mixed heating in step (1) is 140-220° C., preferably 160-180° C.; Preferably, the mixing and heating time in step (1) is 50-120 hours, preferably 60-90 hours; Preferably, after the solid-liquid separation in step (1), the obtained solid phase is sequentially washed and vacuum dried; Preferably, the vacuum drying temperature is 60-100°C, preferably 70-80°C; Preferably, the vacuum drying time is 12-36 hours, preferably 18-24 hours.

4. The preparation method according to any one of claims 1 to 3, characterized in that In step (2), the organic cage polymer and the cerium source are ultrasonically dispersed before the hydrothermal reaction; Preferably, 3-15 mL of 1-5 mol / L alkali solution is added during the ultrasonic dispersion; Preferably, the cerium source in step (2) is an aqueous solution of a cerium salt, and the cerium salt includes any one of cerium nitrate, cerium chloride, cerium sulfate or cerium acetate, preferably cerium nitrate; Preferably, the concentration of the cerium salt in the cerium source in step (2) is 6.5-26 g / L; Preferably, the mass ratio of the cerium salt to the organic cage polymer in the cerium source in step (2) is 1:(0.5-2.4), preferably 1:(0.8-1.5).

5. The preparation method according to any one of claims 1 to 4, characterized in that: The temperature of the hydrothermal reaction in step (2) is 80-150° C., preferably 100-120° C.; Preferably, the hydrothermal reaction time in step (2) is 2-8 h, preferably 4-6 h; Preferably, after the solid-liquid separation in step (2), the obtained solid phase is washed and vacuum dried at 75-85°C in sequence; Preferably, the specific steps of the calcination in step (2) include: heating to 580-620°C at a rate of 3-5°C / min in an argon atmosphere, calcining for 1.5-2.5h, and then continuing to calcine in an air atmosphere for 3.5-4.5h.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The ruthenium salt in the ruthenium salt aqueous solution in step (3) includes RuCl3·3H2O, Ru(NO)(NO3) x (OH) y or C 14 H 21 O 14 Any one of Ru3, wherein 0≤x≤3, 0≤y≤3, x+y=3, preferably RuCl3·3H2O; Preferably, the concentration of ruthenium salt in the ruthenium salt aqueous solution in step (3) is 0.1-2 g / L; Preferably, the mass ratio of ruthenium ions in the ruthenium salt aqueous solution to the mesoporous cerium oxide carrier in step (3) is (0.1-2):100, preferably (0.5-1):100; Preferably, the supercritical fluid in step (3) comprises carbon dioxide.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The dispersion temperature in step (3) is 40-90°C, preferably 50-70°C; Preferably, the dispersion pressure in step (3) is 8-13 MPa, preferably 10-11 MPa; Preferably, the dispersion time in step (3) is 2-8 hours, preferably 4-6 hours; Preferably, the drying temperature in step (3) is 75-85°C and the drying time is 3-5h; Preferably, a mixture of hydrogen and argon is introduced into the reduction in step (3); Preferably, the reduction temperature in step (3) is 400-700° C., preferably 500-600° C.; Preferably, the reduction time in step (3) is 1-6 h, preferably 2-4 h.

8. A mesoporous cerium oxide supported ruthenium catalyst, characterized in that: The mesoporous cerium oxide supported ruthenium catalyst is prepared by the preparation method of the mesoporous cerium oxide supported ruthenium catalyst according to any one of claims 1 to 7; The ruthenium loading amount of the mesoporous cerium oxide-supported ruthenium catalyst is 0.1-2 wt %.

9. A use of the mesoporous cerium oxide supported ruthenium catalyst as claimed in claim 8, characterized in that: The mesoporous cerium oxide-supported ruthenium catalyst is used for the hydrogenation reaction of bisphenol A to synthesize hydrogenated bisphenol A.

10. The use according to claim 9, characterized in that: The raw material for the hydrogenation reaction further includes alcohol, and the alcohol includes any one of methanol, ethanol or isopropanol, preferably isopropanol; Preferably, the mass concentration of bisphenol A in the alcohol solution of bisphenol A is 1-50%, preferably 10-20%; Preferably, the mass of the mesoporous cerium oxide-supported ruthenium catalyst is 0.5-3% of the mass of bisphenol A; Preferably, the temperature of the hydrogenation reaction is 60-140°C, preferably 80-100°C; Preferably, the hydrogen pressure of the hydrogenation reaction is 1-5 MPa, preferably 2-3 MPa.

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