Preparation method and application method of a hydrogenation catalyst

Abstract

The present invention relates to the field of catalytic hydrogenation, and specifically relates to a preparation method and an application method of a hydrogenation catalyst. The technical key points are as follows: The composite support Ni-Ce-Al2O3 is prepared by the ion co-precipitation method, and then Ru is loaded on the composite support Ni-Ce-Al2O3 by the incipient wetness impregnation method; the specific surface area of the composite support Ni-Ce-Al2O3 is 150-200 m 2 / g, the pore volume is 0.6-0.8 cm 2 / g, and the average pore diameter is 8.5-9.5 nm. The present invention selects a suitable support and catalyst for the catalytic hydrogenation process, and the preparation process is simple and suitable for continuous production. The modification of the support enables the catalyst to have a suitable pore channel for the raw material molecules to pass through, and under the synergistic effect of the active component and the composite support, it has high activity.

Description

Technical Field

[0001] The present invention relates to the field of catalytic hydrogenation, and particularly relates to a preparation method and an application method of a hydrogenation catalyst. Background Art

[0002] The process for synthesizing hydrogenated bisphenol compounds by catalytic hydrogenation of bisphenol compounds can adopt continuous or batch hydrogenation. The selected catalysts are mainly divided into three types: noble metal supported catalysts, metal skeleton catalysts, and alkaline earth metal catalysts.

[0003] Most of the existing processes for synthesizing hydrogenated bisphenol A use supported noble metal catalysts, with batch hydrogenation in a high-pressure reaction kettle or continuous hydrogenation in a tubular fixed bed. The reaction kettle hydrogenation process belongs to batch non-continuous reaction. Generally, the technical quality indicators of the products obtained from batch reactions are relatively poor in stability, and at the same time, there are disadvantages such as high production costs, and it is impossible to ensure large-scale industrial production.

[0004] The tubular fixed bed catalytic hydrogenation process belongs to continuous hydrogenation, and the products obtained have advantages such as stable quality and low energy consumption. However, the hydrogenation process of bisphenol A is a strongly exothermic reaction. Under high-load reaction conditions, the temperature rise of the catalyst bed cannot be avoided, and too high a temperature will cause the side reactions to intensify. Therefore, in the current production technology, the proportion of trans isomers is usually 40-50%. There are three isomers of hydrogenated bisphenol compounds, and the trans isomer has more extensive application value. It can produce a synergistic effect and better mechanical properties in polymers, such as increasing the softening point of polymers.

[0005] Therefore, there is a need in the art to develop a preparation method of a hydrogenation catalyst that can produce hydrogenated bisphenol compounds with a high trans ratio at a relatively low cost.

[0006] In view of the above-mentioned defects of the existing hydrogenation catalytic reactions, based on the rich experience and professional knowledge in this field for many years, the inventor of the present invention, in combination with theoretical analysis, conducted research and innovation to develop a preparation method and an application method of a hydrogenation catalyst. Summary of the Invention

[0007] The object of the present invention is to provide a preparation method of a hydrogenation catalyst, which selects a suitable carrier and catalyst for the catalytic hydrogenation process. The preparation process is simple and suitable for continuous production. The modification of the carrier enables the catalyst to have suitable pores for the raw material molecules to pass through. Under the synergistic action of the active component and the composite carrier, it has high activity.

[0008] The above technical object of the present invention is achieved through the following technical solutions:

[0009] A preparation method of a hydrogenation catalyst provided by the present invention uses the ion co-precipitation method to prepare a composite support Ni-Ce-Al2O3, and then uses the incipient wetness impregnation method to load Ru on the composite support Ni-Ce-Al2O3; the specific surface area of the composite support Ni-Ce-Al2O3 is 150~200m 2 / g, the pore volume is 0.6~0.8cm 2 / g, and the average pore diameter is 8.5~9.5nm.

[0010] The present invention uses the co-precipitation method to modify the support to prepare a composite support, which helps to better design the structure of the catalyst during the preparation of the catalyst. Certain pores can be generated through calcination decomposition while increasing the strength of the support, effectively reducing the agglomeration of particles, further increasing the pore volume and pore diameter of the support, making the surface of the catalyst have no obvious accumulation phenomenon, and the specific surface area of the formed catalyst is relatively large.

[0011] The present invention modifies the support to prepare a composite support, which changes the pore structure of the catalyst, enables the catalyst to have appropriate pores for the raw material bisphenol A to pass through, changes the activity of the catalyst, and at the same time the catalyst has a high load. Using this catalyst can obtain hydrogenated bisphenol products with a high trans ratio.

[0012] Further, the composite support Ni-Ce-Al2O3 is modified.

[0013] Further, the content of Ni in the composite support Ni-Ce-Al2O3 is 0.2~0.5wt%, the content of Ce is 0.2~0.5wt%, and the loading amount of Ru is 0.2~1wt%.

[0014] Further, the specific operation of preparing the composite support Ni-Ce-Al2O3 by the ion co-precipitation method is as follows: Dissolve Ni(NO3)2·6H2O and Ce(NO3)3·6H2O in water, stir evenly, then stir evenly with the powdered Al2O3 support, and adjust the pH to 7~8 with an aqueous Na2CO3 solution to obtain a suspension. Place the suspension in a water bath, heat and stir for crystallization, then filter, wash, and dry to obtain a solid powder; dry the solid powder, crush it, sieve it, tablet it, and calcine it to obtain the composite support Ni-Ce-Al2O3.

[0015] Further, the particle size of the prepared porous Al2O3 support is 40 mesh, and it is prepared by mixing pseudoboehmite with citric acid, sodium carboxymethyl cellulose and water.

[0016] Further, the temperature of the water bath is 60~80°C.

[0017] Further, the tablet is a cylinder with φ3×3mm.

[0018] Further, the calcination is carried out in a muffle furnace at a temperature of 600 - 800 °C.

[0019] Further, Ru is loaded on the composite support Ni - Ce - Al2O3 by the incipient wetness impregnation method, and the specific operation is as follows:

[0020] An aqueous solution of the ruthenium source is added to the composite support Ni - Ce - Al2O3, and stirring is continued until sufficient mixing and impregnation are achieved. After impregnation, it is dried and calcined to obtain a hydrogenation catalyst precursor;

[0021] The hydrogenation catalyst precursor is reduced with hydrogen to obtain a hydrogenation catalyst.

[0022] Further, the calcination temperature is 200 - 400 °C.

[0023] Further, the specific operation of reducing the hydrogenation catalyst precursor with hydrogen is as follows: The catalyst is placed in a reduction furnace, and hydrogen is continuously introduced for temperature-programmed reduction. The reduction temperature is 100 - 300 °C, and the reduction time is 1 - 3 h.

[0024] Further, the ruthenium source is ruthenium chloride.

[0025] The second object of the present invention is to provide an application method of a hydrogenation catalyst, which has the same technical effects.

[0026] The above technical object of the present invention is achieved by the following technical solutions:

[0027] The application method of the hydrogenation catalyst provided by the present invention is to dissolve a bisphenol compound in an organic solvent and continuously introduce hydrogen, and continuously prepare a high trans - ratio hydrogenated bisphenol product under the action of a hydrogenation catalyst in a fixed - bed reactor.

[0028] Further, the bisphenol compound is bisphenol A, bisphenol S or bisphenol F.

[0029] Further, the process conditions of the hydrogenation catalytic reaction are: reaction temperature 110 - 160 °C, liquid hourly space velocity 0.18 - 0.36 h -1 , reaction pressure 4 - 6 MPa.

[0030] In summary, the present invention has the following beneficial effects:

[0031] In the present invention, the addition of nickel in the composite support inhibits the hydrogenation of C=O in the raw materials, reduces the formation of deep hydrogenation products of bisphenol compounds, and simultaneously reduces the formation of polymers; while the addition of cerium inhibits the aggregation of ruthenium components, making the active components more uniformly dispersed on the surface of the support. The synergistic effect of the two improves the activity of the product. By high-temperature calcination of the composite support, the proportion of the trans isomer of the hydrogenated bisphenol product is further increased, and high activity is still maintained while reducing the content of the active component ruthenium, which reduces the production cost to a certain extent. This is because the internal energy of the cis isomer is relatively high, and it can often be converted into the trans isomer by heating. That is, at high temperatures, sufficient energy is supplied to achieve isomerization due to the relationship of thermodynamic equilibrium. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] Figure 1 are SEM images of Ru / Al2O3 and Ru / Ni-Ce-Al2O3;

[0033] Figure 2 are XRD patterns of Ru / Al2O3 and Ru / Ni-Ce-Al2O3. (A) is 0.5% Ru / Al2O3, (B) is 0.5% Ru / 0.2% Ni-Al2O3, (C) is 0.5% Ru / 0.2% Ce-Al2O3, (D) is 0.5% Ru / 0.2% Ni-0.2% Ce-Al2O3, (E) is 0.2% Ru / 0.2% Ni-0.2% Ce-Al2O3, (F) is 0.5% Ru / 0.5% Ni-0.5% Ce-Al2O3. DETAILED DESCRIPTION OF THE INVENTION

[0034] To further elaborate on the technical means and effects adopted by the present invention to achieve the intended invention purpose, a preparation method and an application method of a hydrogenation catalyst according to the present invention are described in detail below in terms of its specific implementation manners, features and effects.

[0035] Example 1

[0036] (1) Preparation of the hydrogenation catalyst:

[0037] S1. First, weigh 19.73 g of a porous powder alumina support, place the solid powder in an oven at 90 °C to dry, crush it with a mortar, press it into cylindrical composite supports with a diameter of φ3×3 mm, and place them in a muffle furnace for calcination at 700 °C for 3 h;

[0038] S2. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. Add it to the composite support while stirring, and continue stirring until fully mixed;

[0039] S3. Immerse for 2 h at room temperature, stir with a glass rod during this period, after immersion, dry overnight in an oven at 105 °C to obtain a solid complex. Put the solid complex into a muffle furnace, heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, after completion, press into tablets, and then reduce at 140 °C in a reduction furnace for 2 h, continuously introduce hydrogen during this period, and a hydrogenation catalyst is prepared.

[0040] (2) Carry out a hydrogenation catalytic reaction using the above catalyst:

[0041] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , continuously introduce hydrogen during the reaction process, and carry out a catalytic reaction on bisphenol A, bisphenol S and bisphenol F.

[0042] Example 2

[0043] (1) Preparation of the hydrogenation catalyst:

[0044] S1. First, weigh 19.73 g of a powdered alumina support for standby, then weigh 0.20 g of Ni(NO3)2·6H2O into a beaker and add 15 mL of deionized water to stir and dissolve;

[0045] S2. Add the dried powdered Al2O3 support and stir evenly, place it in a water bath at 70 °C, heat and stir, then filter, wash and dry. Place the solid powder in an oven at 90 °C to dry, crush it with a mortar, and press it into a cylindrical composite support with a diameter of φ3×3 mm. After that, calcine at 700 °C for 3 h to obtain a composite support;

[0046] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. While stirring, add it to the composite support and continue stirring until fully mixed; immerse for 2 h at room temperature, stir with a glass rod during this period, after immersion, dry overnight in an oven at 105 °C to obtain a solid complex. Put the solid complex into a muffle furnace, heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce at 140 °C in a reduction furnace for 2 h, continuously introduce hydrogen during this period, and a hydrogenation catalyst is prepared.

[0047] (2) Carry out a hydrogenation catalytic reaction using the above catalyst:

[0048] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , continuously introduce hydrogen during the reaction process, and carry out a catalytic reaction on bisphenol A, bisphenol S and bisphenol F.

[0049] Example 3

[0050] (1) Preparation of hydrogenation catalyst:

[0051] S1. First, weigh 19.61 g of powdered alumina support for standby. Then, weigh 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0052] S2. Add the dried powdered Al2O3 support, stir evenly, place it in a water bath at 70 °C, heat and stir, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a diameter of φ3×3 mm. After that, calcine it at 700 °C for 3 h to obtain the composite support.

[0053] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. While stirring, add it to the composite support and continue stirring until fully mixed. Immerse it at room temperature for 2 h, stir with a glass rod during this period, and then place it in an oven at 105 °C to dry overnight to obtain a solid complex.

[0054] S4. Put the solid complex into a muffle furnace, heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h, continuously introducing hydrogen during this period, to obtain a solid catalyst.

[0055] (2) Hydrogenation catalytic reaction using the above catalyst:

[0056] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , and continuously introduce hydrogen during the reaction process to carry out the catalytic reaction on bisphenol A bisphenol S and bisphenol F.

[0057] Example 4

[0058] (1) Preparation of hydrogenation catalyst:

[0059] S1. First, weigh 19.41 g of powdered alumina support for standby. Then, weigh 0.20 g of Ni(NO3)2·6H2O and 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0060] S2. Add the dried powdered Al2O3 support, stir evenly, place it in a water bath at 70 °C, heat and stir, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a diameter of φ3×3 mm. After that, calcine it at 700 °C for 3 h to obtain the composite support.

[0061] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature, dissolve it in 15 mL of deionized water, add it to the composite support while stirring, and continue stirring until fully mixed; impregnate at room temperature for 2 h, stir with a glass rod during this period, and place it in an oven at 105 °C to dry overnight to obtain a solid complex;

[0062] S4. Put the solid complex into a muffle furnace, heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h, continuously introducing hydrogen during this period to obtain a solid catalyst.

[0063] (2)Hydrogenation reaction:

[0064] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , continuously introduce hydrogen during the reaction process, and carry out a catalytic reaction on bisphenol A, bisphenol S and bisphenol F.

[0065] Example 5

[0066] (1)Preparation of hydrogenation catalyst:

[0067] Same as Example 4.

[0068] (2)Hydrogenation reaction of styrene-butadiene-styrene block polymer:

[0069] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 110 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , continuously introduce hydrogen during the reaction process, and carry out a catalytic reaction on bisphenol A, bisphenol S and bisphenol F.

[0070] Example 6

[0071] (1)Preparation of hydrogenation catalyst:

[0072] Same as Example 4.

[0073] (2)Hydrogenation reaction of styrene-butadiene-styrene block polymer:

[0074] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 110 °C, the reaction pressure to 4 Mpa, and the space velocity to 0.3 h -1 , continuously introduce hydrogen during the reaction process, and carry out a catalytic reaction on bisphenol A, bisphenol S and bisphenol F.

[0075] Example 7

[0076] (1)Preparation of hydrogenation catalyst:

[0077] Same as Example 4.

[0078] (2) Hydrogenation reaction of styrene-butadiene-styrene block polymer:

[0079] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature at 110 °C, the reaction pressure at 4 Mpa, and the space velocity at 0.18 h -1 , and continuously introduce hydrogen during the reaction process to carry out catalytic reaction on bisphenol A bisphenol S and bisphenol F.

[0080] Example 8

[0081] (1) Preparation of hydrogenation catalyst:

[0082] S1. First, weigh 18.92 g of powdered alumina support for standby. Then, weigh 0.50 g of Ni(NO3)2·6H2O and 0.31 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0083] S2. Add the dried powdered Al2O3 support and stir evenly. Place it in a water bath at 70 °C, heat and stir, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with φ3×3 mm. Then, calcine it at 700 °C for 3 h to obtain the composite support.

[0084] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. While stirring, add it to the composite support and continue stirring until fully mixed. Immerse it at room temperature for 2 h, stir with a glass rod during this period, and then place it in an oven at 105 °C to dry overnight to obtain a solid complex.

[0085] S4. Put the solid complex into a muffle furnace, heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h, continuously introducing hydrogen during this period, to obtain a solid catalyst.

[0086] (2) Hydrogenation reaction:

[0087] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature at 130 °C, the reaction pressure at 6 Mpa, and the space velocity at 0.3 h -1 , and continuously introduce hydrogen during the reaction process to carry out catalytic reaction on bisphenol A bisphenol S and bisphenol F.

[0088] Example 9

[0089] (1) Preparation of hydrogenation catalyst:

[0090] S1. First, weigh 19.14 g of powdered alumina support for standby. Then, weigh 0.20 g of Ni(NO3)2·6H2O and 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0091] S2. Add the dried powdered Al2O3 support and stir evenly. Place it in a water bath and heat and stir at 70 °C, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a size of φ3×3 mm. After that, calcine it at 700 °C for 3 h to obtain the composite support.

[0092] S3. Weigh 0.54 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. While stirring, add it to the composite support and continue stirring until fully mixed. Immerse it at room temperature for 2 h, stir with a glass rod during this period, and then dry it overnight in an oven at 105 °C to obtain a solid complex.

[0093] S4. Put the solid complex into a muffle furnace, heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h. Continuously introduce hydrogen during this period to obtain a solid catalyst.

[0094] (2) Hydrogenation reaction of styrene-butadiene-styrene block copolymer:

[0095] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature at 130 °C, the reaction pressure at 6 Mpa, and the space velocity at 0.3 h -1 , and continuously introduce hydrogen during the reaction process to carry out the catalytic reaction on bisphenol A bisphenol S and bisphenol F.

[0096] Example 10

[0097] (1) Preparation of hydrogenation catalyst:

[0098] S1. First, weigh 19.57 g of powdered alumina support for standby. Then, weigh 0.20 g of Ni(NO3)2·6H2O and 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0099] S2. Add the dried powdered Al2O3 support and stir evenly. Place it in a water bath and heat and stir at 70 °C, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a size of φ3×3 mm. After that, calcine it at 700 °C for 3 h to obtain the composite support.

[0100] S3. Weigh 0.11 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. While stirring, add it to the composite support and continue stirring until fully mixed. Immerse it at room temperature for 2 h, during which stir with a glass rod. After immersion, place it in an oven at 105 °C and dry overnight to obtain a solid composite.

[0101] S4. Put the solid composite into a muffle furnace and heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h, continuously introducing hydrogen gas during this period to obtain a solid catalyst.

[0102] (2) Hydrogenation reaction:

[0103] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , and continuously introduce hydrogen gas during the reaction process to carry out a catalytic reaction on bisphenol A, bisphenol S, and bisphenol F.

[0104] Example 11

[0105] (1) Preparation of hydrogenation catalyst:

[0106] S1. First, weigh 19.41 g of powdered alumina support for standby. Then, weigh 0.20 g of Ni(NO3)2·6H2O and 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0107] S2. Add the dried powdered Al2O3 support and stir evenly. Place it in a water bath at 70 °C, heat and stir, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a diameter of φ3×3 mm. After that, calcine it at 600 °C for 3 h to obtain the composite support.

[0108] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. While stirring, add it to the composite support and continue stirring until fully mixed. Immerse it at room temperature for 2 h, during which stir with a glass rod. After immersion, place it in an oven at 105 °C and dry overnight to obtain a solid composite.

[0109] S4. Put the solid composite into a muffle furnace and heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h, continuously introducing hydrogen gas during this period to obtain a solid catalyst.

[0110] (2) Hydrogenation reaction:

[0111] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , and continuously introduce hydrogen during the reaction process to carry out the catalytic reaction on bisphenol A, bisphenol S, and bisphenol F.

[0112] Example 12

[0113] (1) Preparation of the hydrogenation catalyst:

[0114] S1. First, weigh 19.41 g of the powdered alumina support for standby. Then, weigh 0.20 g of Ni(NO3)2·6H2O and 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0115] S2. Add the dried powdered Al2O3 support and stir evenly. Place it in a water bath at 70 °C, heat and stir, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a diameter of φ3×3 mm. After that, calcine it at 800 °C for 3 h to obtain the composite support.

[0116] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. While stirring, add it to the composite support and continue stirring until fully mixed. Immerse it at room temperature for 2 h, stir with a glass rod during this period, and then place it in an oven at 105 °C to dry overnight to obtain a solid complex.

[0117] S3. Put the solid complex into a muffle furnace, heat the muffle furnace to 300 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h, continuously introducing hydrogen during this period, to obtain the solid catalyst.

[0118] (2) Hydrogenation reaction:

[0119] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , and continuously introduce hydrogen during the reaction process to carry out the catalytic reaction on bisphenol A, bisphenol S, and bisphenol F.

[0120] Example 13

[0121] (1) Preparation of the hydrogenation catalyst:

[0122] S1. First, weigh 19.41 g of the powdered alumina support for standby. Then, weigh 0.20 g of Ni(NO3)2·6H2O and 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve.

[0123] S2. Add the dried powder Al2O3 support and stir evenly. Place it in a water bath at 70 °C, heat and stir, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a size of φ3×3 mm. After that, calcine it at 700 °C for 3 h to obtain the composite support;

[0124] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. Add it to the composite support while stirring continuously until fully mixed. Immerse it at room temperature for 2 h, stir with a glass rod during this period, and then dry it overnight in an oven at 105 °C to obtain a solid complex;

[0125] S4. Put the solid complex into a muffle furnace, heat the muffle furnace to 200 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it at 140 °C in a reduction furnace for 2 h, continuously introducing hydrogen gas during this period to obtain a solid catalyst.

[0126] (2) Hydrogenation reaction:

[0127] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature at 130 °C, the reaction pressure at 6 Mpa, and the space velocity at 0.3 h -1 , and continuously introduce hydrogen gas during the reaction process to carry out a catalytic reaction on bisphenol A, bisphenol S, and bisphenol F.

[0128] Example 14

[0129] (1) Preparation of hydrogenation catalyst:

[0130] S1. First, weigh 19.41 g of powder alumina support for standby. Then, weigh 0.20 g of Ni(NO3)2·6H2O and 0.12 g of Ce(NO3)3·6H2O into a beaker, add 15 mL of deionized water, and stir to dissolve;

[0131] S2. Add the dried powder Al2O3 support and stir evenly. Place it in a water bath at 70 °C, heat and stir, then filter, wash, and dry. Crush it with a mortar and press it into a cylindrical composite support with a size of φ3×3 mm. After that, calcine it at 700 °C for 3 h to obtain the composite support;

[0132] S3. Weigh 0.27 g of RuCl3·3H2O at room temperature and dissolve it in 15 mL of deionized water. Add it to the composite support while stirring continuously until fully mixed. Immerse it at room temperature for 2 h, stir with a glass rod during this period, and then dry it overnight in an oven at 105 °C to obtain a solid complex;

[0133] S4. Put the solid complex into a muffle furnace, heat the muffle furnace to 400 °C at a rate of 2 °C / min, calcine for 3 h, and then reduce it in a reduction furnace at 140 °C for 2 h. During this period, hydrogen is continuously introduced without interruption to obtain a solid catalyst.

[0134] (2) Hydrogenation reaction:

[0135] Load 20 mL of the above solid catalyst into a fixed bed, set the reaction temperature to 130 °C, the reaction pressure to 6 Mpa, and the space velocity to 0.3 h -1 , and continuously introduce hydrogen during the reaction process to carry out a catalytic reaction on bisphenol A, bisphenol S, and bisphenol F.

[0136] Test results

[0137] Table 1 shows the hydrogenation degree and selectivity of bisphenol A, bisphenol S, and bisphenol F in Examples 1 to 15.

[0138] Table 1. Hydrogenation degree and selectivity of bisphenol A, bisphenol S, and bisphenol F

[0139]

[0140] Through the data comparison in Table 1, the following conclusions are drawn:

[0141] Based on macroporous alumina, 0.2% Ni and 0.2% Ce are simultaneously added by the ion co - precipitation method to form a Ni - Ce - Al2O3 composite support. The composite support is calcined at 700 °C at high temperature. On this basis, 0.5% Ru is loaded by the incipient wetness impregnation method and further calcined at 200 °C. The catalyst prepared in this way has high activity for the hydrogenation of bisphenol compounds. The proportion of the trans - isomer of hydrogenated bisphenol A can reach up to 76% at most, and the trans - isomers of hydrogenated bisphenol F and hydrogenated bisphenol S also reach relatively high proportions.

[0142] The above is only a preferred embodiment of the present invention and does not impose any form of limitation on the present invention. Although the present invention has been shown above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art, without departing from the scope of the technical solution of the present invention, can make some changes or modifications to equivalent embodiments by using the technical content disclosed above. However, any simple modification, equivalent change, and modification made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A method for preparing a hydrogenation catalyst for catalyzing bisphenol compounds, characterized in that, The composite support Ni-Ce-Al2O3 was prepared by the ion co-precipitation method, and then Ru was loaded on the composite support Ni-Ce-Al2O3 by the incipient wetness impregnation method; the specific surface area of the composite support Ni-Ce-Al2O3 is 150-200 m 2 / g, the pore volume is 0.6-0.8 cm 2 / g, and the average pore diameter is 8.5-9.5 nm; the content of Ni in the composite support Ni-Ce-Al2O3 is 0.2-0.5 wt%, the content of Ce is 0.2-0.5 wt%, and the loading amount of Ru is 0.2-1 wt%.

2. The preparation method of a hydrogenation catalyst for catalyzing bisphenol compounds according to claim 1, characterized in that, The composite support is prepared by the ion co-precipitation method, modified by adding bimetals Ni and Ce, and the composite support is calcined at a high temperature, and the calcination temperature is 600-800 °C.

3. The preparation method of a hydrogenation catalyst for catalyzing bisphenol compounds according to claim 2, characterized in that, The specific operation for preparing the composite support Ni-Ce-Al2O3 by the ion co-precipitation method is as follows: Dissolve Ni(NO3)2·6H2O and Ce(NO3)3·6H2O in water, add the powdered Al2O3 support after stirring evenly, continue to stir evenly, and adjust the pH to 7-8 with an aqueous Na2CO3 solution to obtain a suspension. Place the suspension in a water bath, heat and stir for crystallization, then filter, wash, and dry to obtain a solid powder; dry the solid powder, crush it, sieve it, tablet it, and calcine it to obtain the composite support Ni-Ce-Al2O3.

4. The preparation method of a hydrogenation catalyst for catalyzing bisphenol compounds according to claim 1, characterized in that, The ruthenium is loaded on the composite support Ni-Ce-Al2O3 by the incipient wetness impregnation method, and the specific operation is as follows: Add an aqueous solution of the ruthenium source to the composite support Ni-Ce-Al2O3, and continuously stir until fully mixed and impregnated. After impregnation, dry and calcine it to obtain a hydrogenation catalyst precursor; Reduce the hydrogenation catalyst precursor with hydrogen to obtain the hydrogenation catalyst.

5. The preparation method of a hydrogenation catalyst for catalyzing bisphenol compounds according to claim 4, characterized in that, The ruthenium source is ruthenium chloride.

6. The preparation method of a hydrogenation catalyst for catalyzing bisphenol compounds according to claim 4, characterized in that, The hydrogen reduction temperature is 200-400 °C, and the reduction time is 1-3 h.

7. The application method of the hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 6, characterized in that, Dissolve the bisphenol compound in an organic solvent and continuously introduce hydrogen. Continuously prepare a high trans-proportion hydrogenated bisphenol product by using a fixed-bed reactor under the action of the hydrogenation catalyst.

8. The application method of the hydrogenation catalyst according to claim 7, characterized in that, The bisphenol compound is bisphenol A, bisphenol S or bisphenol F.

9. The application method of the hydrogenation catalyst according to claim 7, characterized in that, The process conditions are as follows: the reaction temperature is 110 - 160 °C, the liquid hourly space velocity is 0.18 - 0.36 h -1 , and the reaction pressure is 4 - 6 MPa.

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