CN115970707A - A kind of preparation method of hydrogenation catalyst and its application method - Google Patents

Abstract

The invention relates to the field of catalyst hydrogenation, in particular to the field of catalyst hydrogenation, and specifically relates to a preparation method of a hydrogenation catalystA preparation method and an application method thereof. The technical points are as follows: composite carrier Ni-Ce-Al prepared by adopting ion coprecipitation method ₂ O ₃ Then adopting an isometric impregnation method to load Ru on the composite carrier Ni-Ce-Al ₂ O ₃ C, removing; the composite carrier Ni-Ce-Al ₂ O ₃ The specific surface area of (A) is 150 to 200m ² (iv) a pore volume of 0.6 to 0.8cm ² (iii) a mean pore diameter of 8.5 to 9.5nm. The invention selects proper carrier and catalyst to carry out catalytic hydrogenation process, has simple preparation process and is suitable for continuous production. The modification of the carrier enables the catalyst to have a proper pore channel so that raw material molecules pass through, and the catalyst has higher activity under the synergistic effect of the active component and the composite carrier.

Description

A kind of preparation method of hydrogenation catalyst and its application method

technical field

The invention relates to the field of catalyst hydrogenation, in particular to a method for preparing a hydrogenation catalyst and an application method thereof.

Background technique

Continuous or intermittent hydrogenation can be used in the production process of catalytic hydrogenation of bisphenols to synthesize hydrogenated bisphenols. The catalysts selected are mainly divided into three types: noble metal supported catalysts, metal skeleton catalysts and alkaline earth metal catalysts. .

Most of the existing hydrogenated bisphenol A synthesis processes use supported noble metal catalysts to hydrogenate intermittently in high-pressure reactors or continuously hydrogenate in tubular fixed beds. The reactor hydrogenation process is a batch discontinuous reaction, and the products produced by the batch reaction generally have poor technical quality indicators and are accompanied by disadvantages such as high production costs, which cannot guarantee industrialized mass production.

The tubular fixed-bed catalytic hydrogenation process belongs to continuous hydrogenation, and the obtained product has the advantages of stable quality and low energy consumption. However, the bisphenol A hydrogenation process is a strong exothermic reaction. Under high-load reaction conditions, the catalyst The temperature rise of the bed is unavoidable, and too high temperature will cause side reactions to intensify, so in the current production technology, most of the trans-isomer ratios are usually 40-50%, and the hydrogenated bisphenols products have three isomers, of which The trans isomer has wider application value, it can produce synergistic effects and better mechanical properties in polymers, such as increasing the softening point of polymers.

Therefore, there is a need in the art to develop a method for preparing a hydrogenation catalyst that has a high trans ratio of hydrogenated bisphenols at a lower cost.

In view of the defects of the above-mentioned existing hydrogenation catalytic reaction, the inventors developed a method for preparing a hydrogenation catalyst and its application method based on years of rich experience and professional knowledge in such materials, combined with theoretical analysis, research and innovation.

Contents of the invention

The purpose of the present invention is to provide a method for preparing a hydrogenation catalyst, select a suitable carrier and catalyst to carry out the catalytic hydrogenation process, the preparation process is simple, and it is suitable for continuous production. The modification of the support enables the catalyst to have suitable pores to allow the raw material molecules to pass through, and under the synergistic effect of the active component and the composite support, it has a higher activity.

Above-mentioned technical purpose of the present invention is achieved through the following technical solutions:

The preparation method of a hydrogenation catalyst provided by the present invention is to prepare the composite carrier Ni-Ce-Al ₂ O ₃ by ion co-precipitation method, and then use the equal volume impregnation method to load Ru on the composite carrier Ni-Ce-Al ₂ O ₃ Above; the specific surface area of the composite carrier Ni-Ce-Al ₂ O ₃ 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.

The present invention uses the co-precipitation method to modify the carrier to prepare a composite carrier, which helps to better design the structure of the catalyst when preparing the catalyst. While increasing the strength of the carrier, it can produce certain pores through roasting and decomposition, effectively reducing particles. The agglomeration of the carrier further increases the pore volume and pore size of the carrier, so that there is no obvious accumulation on the surface of the catalyst, and the specific surface area of the catalyst after molding is larger.

The present invention prepares a composite carrier by modifying the carrier, changes the pore structure of the catalyst, makes the catalyst have suitable pores to allow the raw material bisphenol A to pass through, and changes the activity of the catalyst. At the same time, the catalyst has a high load, and the catalyst can be used to obtain high Trans proportional hydrogenation of bisphenols products.

Further, the composite support Ni-Ce-Al ₂ O ₃ is modified.

Further, the content of Ni in the composite carrier Ni-Ce-Al ₂ O ₃ is 0.2-0.5wt%, the content of Ce is 0.2-0.5wt%, and the loading amount of Ru is 0.2-1wt%.

Further, the specific operation of preparing the composite carrier Ni-Ce-Al ₂ O ₃ by the ion co-precipitation method is as follows: dissolve Ni(NO ₃ ) ₂ ·6H ₂ O and Ce(NO ₃ ) ₃ ·6H ₂ O in water, After stirring evenly, the powdered Al ₂ O ₃ carrier is stirred evenly, and the pH is adjusted to 7~8 with Na ₂ CO ₃ aqueous solution to obtain a suspension, the suspension is placed in a water bath, heated and stirred to crystallize, filtered, washed, and dried to obtain a solid powder ; The solid powder is dried, crushed, sieved, pressed into tablets, and calcined to obtain the composite carrier Ni-Ce-Al ₂ O ₃ .

Further, the particle size of the porous Al ₂ O ₃ carrier is 40 mesh, which is prepared by mixing pseudo-boehmite with citric acid, turmeric powder and water.

Further, the temperature of the water bath is 60-80°C.

Further, the compressed tablet is a cylinder of φ3×3mm.

Further, the roasting is carried out in a muffle furnace, and the roasting temperature is 600-800°C.

Further, Ru is loaded on the composite carrier Ni-Ce-Al ₂ O ₃ by equal volume impregnation method, and the specific operation is as follows:

adding the aqueous solution of the ruthenium source into the composite carrier Ni-Ce-Al ₂ O ₃ , stirring continuously until fully mixed and impregnated, drying and roasting it after impregnating to obtain a hydrogenation catalyst precursor;

The hydrogenation catalyst precursor is reduced by hydrogen to obtain the hydrogenation catalyst.

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

Further, the specific operation of using hydrogen to reduce the hydrogenation catalyst precursor is as follows: the catalyst is placed in the reduction furnace, and the hydrogen gas is continuously introduced into the reduction furnace to increase the temperature. The reduction temperature is 100-300 ° C, and the reduction time is 1-3 hours.

Further, the source of ruthenium is ruthenium chloride.

The second object of the present invention is to provide a hydrogenation catalyst application method, which has the same technical effect.

Above-mentioned technical purpose of the present invention is achieved by the following technical solutions:

The invention provides an application method of multiple hydrogenation catalysts, which is to dissolve bisphenol compounds in an organic solvent and continuously feed hydrogen, and use a fixed-bed reactor to continuously prepare hydrogenated bisphenol products with a high trans ratio under the action of a hydrogenation catalyst .

Further, the bisphenol compound is bisphenol A, bisphenol S or bisphenol F.

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

In summary, the present invention has the following beneficial effects:

In the present invention, the addition of nickel in the composite carrier can inhibit the hydrogenation of C=O in the raw material, reduce the generation of deep hydrogenation products of bisphenols, and reduce the generation of polymers; while the addition of cerium inhibits The aggregation of the ruthenium component makes the active component disperse more evenly on the surface of the carrier, and the synergistic effect of the two improves the activity of the product. By roasting the composite carrier at high temperature, the ratio of the trans isomer of the hydrogenated bisphenol product is further increased, and While reducing the ruthenium content of the active component, it still maintains a high activity, which reduces the production cost to a certain extent. This is due to the high internal energy of the cis-isomer, which can often be transformed into the trans-isomer by heating, that is, at high temperature, enough energy can be added to achieve isomerization, which is due to the relationship of thermodynamic equilibrium.

Description of drawings

Figure 1 is the SEM images of Ru /Al ₂ O ₃ and Ru /Ni-Ce-Al ₂ O ₃ ;

Figure 2 is the XRD pattern of Ru /Al ₂ O ₃ and Ru /Ni-Ce-Al ₂ O ₃ , (A) is 0.5 %Ru/Al ₂ O ₃ , (B) is 0.5 %Ru/0.2%Ni-Al ₂ O ₃ , (C) 0.5% Ru/0.2%Ce-Al ₂ O ₃ , (D) 0.5% Ru/0.2%Ni-0.2%Ce-Al ₂ O ₃ , (E) 0.2%Ru/0.2%Ni -0.2%Ce-Al ₂ O ₃ , (F) 0.5%Ru/0.5%Ni-0.5%Ce-Al ₂ O ₃ .

Detailed ways

In order to further explain the technical means and effects adopted by the present invention to achieve the intended purpose of the invention, the preparation method and application method of a hydrogenation catalyst proposed according to the present invention, its specific implementation, characteristics and effects are described in detail As later.

Example 1

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.73g of porous powdered alumina carrier, dry the solid powder in an oven at 90°C, crush it with a mortar, press into tablets to obtain a cylindrical composite carrier of φ3×3mm, and place it in a muffle furnace for 700 Roasting at ℃ for 3h;

S2. Dissolve 0.27g RuCl ₃ 3H ₂ O in 15mL deionized water at room temperature, add it to the composite carrier while stirring, and continue stirring until fully mixed;

S3. Immerse at room temperature for 2 hours, stir with a glass rod during the period, and dry overnight in an oven at 105°C after impregnation to obtain a solid composite. Put the solid composite into a muffle furnace, and set the muffle furnace at 2°C/ The temperature was raised to 300°C at a speed of 1 min, and roasted for 3 hours. After the completion, it was pressed into tablets and formed, and then reduced in a reduction furnace at 140°C for 2 hours. During this period, hydrogen was continuously fed to obtain a hydrogenation catalyst.

(2) Using the above-mentioned catalyst for hydrogenation catalytic reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , and continuously feed hydrogen during the reaction process. carry out a catalytic reaction.

Example 2

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.73g of powdered alumina carrier for later use, then weigh 0.20g of Ni(NO ₃ ) ₂ 6H ₂ O into a beaker and add 15mL of deionized water to stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, heat and stir in a water bath at 70°C, filter, wash, and dry, dry the solid powder in an oven at 90°C, and crush it with a mortar , pressed into tablets to obtain a cylindrical composite carrier of φ3×3mm, and then roasted at 700°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, stirring with a glass rod during the dipping Put it in an oven at 105°C and dry it overnight to obtain a solid composite. Put the solid composite into a muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, bake it for 3 hours, and then place it in a reduction furnace Reduction at 140°C for 2 hours, during which hydrogen gas was continuously fed in to prepare a hydrogenation catalyst.

(2) Using the above-mentioned catalyst for hydrogenation catalytic reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 3

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.61g powdered alumina carrier for later use, then weigh 0.12g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water to stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 700°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, stirring with a glass rod during the dipping Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace for 2h at 140°C, during which the Hydrogen to produce a solid catalyst.

(2) Using the above-mentioned catalyst for hydrogenation catalytic reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 4

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.41g powdered alumina carrier for later use, then weigh 0.20g Ni(NO ₃ ) ₂ 6H ₂ O and 0.12g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water Stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 700°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, stirring with a glass rod during the dipping Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace for 2h at 140°C, during which the Hydrogen to produce a solid catalyst.

(2) Hydrogenation reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 5

(1) Preparation of hydrogenation catalyst:

With embodiment 4.

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

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature to 110°C, the reaction pressure to 6Mpa, and the space velocity to 0.3h ^-1 , and continuously feed hydrogen during the reaction process to conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 6

(1) Preparation of hydrogenation catalyst:

With embodiment 4.

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

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 110°C, the reaction pressure at 4Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 7

(1) Preparation of hydrogenation catalyst:

With embodiment 4.

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

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 110°C, the reaction pressure at 4Mpa, and the space velocity at 0.18h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 8

(1) Preparation of hydrogenation catalyst:

S1. First weigh 18.92g powdered alumina carrier for later use, then weigh 0.50g Ni(NO ₃ ) ₂ 6H ₂ O and 0.31g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water Stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 700°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, keep stirring until fully mixed, and immerse at room temperature for 2 hours, stirring with a glass rod during the immersion Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace for 2h at 140°C, during which the Hydrogen to produce a solid catalyst.

(2) Hydrogenation reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 9

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.14g powdered alumina carrier for later use, then weigh 0.20g Ni(NO ₃ ) ₂ 6H ₂ O and 0.12g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water Stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 700°C for 3 hours to obtain a composite carrier;

S3. Dissolve 0.54g RuCl ₃ 3H ₂ O in 15mL deionized water at room temperature, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, during which time use a glass rod to stir, Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace for 2h at 140°C, during which the Hydrogen to produce a solid catalyst.

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

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 10

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.57g powdered alumina carrier for later use, then weigh 0.20g Ni(NO ₃ ) ₂ 6H ₂ O and 0.12g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water Stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 700°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.11g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL of deionized water, add it into the composite carrier while stirring, keep stirring until fully mixed, and immerse at room temperature for 2 hours, stirring with a glass rod during the immersion Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace for 2h at 140°C, during which the Hydrogen to produce a solid catalyst.

(2) Hydrogenation reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 11

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.41g powdered alumina carrier for later use, then weigh 0.20g Ni(NO ₃ ) ₂ 6H ₂ O and 0.12g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water Stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 600°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, stirring with a glass rod during the dipping Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace for 2h at 140°C, during which the Hydrogen to produce a solid catalyst.

(2) Hydrogenation reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 12

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.41g powdered alumina carrier for later use, then weigh 0.20g Ni(NO ₃ ) ₂ 6H ₂ O and 0.12g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water Stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 800°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, stirring with a glass rod during the dipping Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S3. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 300°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace for 2h at 140°C, during which the Hydrogen to produce a solid catalyst.

(2) Hydrogenation reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 13

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.41g powdered alumina carrier for later use, then weigh 0.20g Ni(NO ₃ ) ₂ 6H ₂ O and 0.12g Ce(NO ₃ ) ₃ 6H ₂ O into a beaker and add 15mL deionized water Stir to dissolve;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 700°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, stirring with a glass rod during the dipping Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 200°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace at 140°C for 2h, during which the Hydrogen to produce a solid catalyst.

(2) Hydrogenation reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Example 14

(1) Preparation of hydrogenation catalyst:

S1. First weigh 19.41g of powdered alumina carrier for later use, then weigh 0.20g of Ni(NO ₃ ) ₂ 6H ₂ O and 0.12g of Ce(NO ₃ ) ₃ 6H ₂ O in a beaker, add 15mL of deionized water and stir to dissolve ;

S2. Add the dried powdered Al ₂ O ₃ carrier and stir evenly, place it in a water bath at 70°C, heat and stir, filter, wash, dry, crush with a mortar, and press to obtain a cylindrical composite carrier of φ3×3mm , and then calcined at 700°C for 3 hours to obtain a composite carrier;

S3. Weigh 0.27g RuCl ₃ 3H ₂ O at room temperature and dissolve it in 15mL deionized water, add it into the composite carrier while stirring, and keep stirring until fully mixed; soak at room temperature for 2 hours, stirring with a glass rod during the dipping Finally, dry it overnight in an oven at 105°C to obtain a solid composite;

S4. Put the solid compound into the muffle furnace, raise the temperature of the muffle furnace to 400°C at a rate of 2°C/min, roast for 3h, and then reduce it in the reduction furnace at 140°C for 2h, during which the Hydrogen to produce a solid catalyst.

(2) Hydrogenation reaction:

Put 20mL of the above-mentioned solid catalyst into a fixed bed, set the reaction temperature at 130°C, the reaction pressure at 6Mpa, and the space velocity at 0.3h ^-1 , continuously feed hydrogen during the reaction process, and conduct bisphenol A, bisphenol S and bisphenol F Catalytic reaction.

Test Results

Table 1 shows the degree of hydrogenation and selectivity of bisphenol A, bisphenol S and bisphenol F in Examples 1-15.

Table 1. Bisphenol A bisphenol S and bisphenol F hydrogenation degree and selectivity

By comparing the data in Table 1, the following conclusions can be drawn:

On the basis of macroporous alumina, 0.2% Ni and 0.2% Ce were added simultaneously by ion co-precipitation method to form Ni-Ce-Al ₂ O ₃ composite carrier, and the composite carrier was calcined at 700°C at high temperature. The impregnation method was loaded with 0.5% Ru, and the calcination was continued at 200°C. The catalyst thus prepared had high activity for the hydrogenation of bisphenol compounds, and the trans-isomer ratio of hydrogenated bisphenol A was up to 76%, while hydrogenation The trans isomers of bisphenol F and hydrogenated bisphenol S also reached a higher proportion.

The above descriptions are only preferred embodiments of the present invention, and do not limit the present invention in any form. Although the present invention has been shown above with preferred embodiments, it is not intended to limit the present invention. Anyone familiar with this field Those skilled in the art, without departing from the scope of the technical solution of the present invention, may use the technical content disclosed above to make some changes or modify them into equivalent embodiments with equivalent changes. Technical Essence of the Invention Any simple modifications, equivalent changes and modifications made to the above embodiments still fall within the scope of the technical solutions of the present invention.

Claims (10)

1. The preparation method of the hydrogenation catalyst is characterized in that the composite carrier Ni-Ce-Al is prepared by adopting an ion coprecipitation method ₂ O ₃ Then adopting an isometric impregnation method to load Ru on the composite carrier Ni-Ce-Al ₂ O ₃ The above step (1); the composite carrier Ni-Ce-Al ₂ O ₃ The specific surface area of (A) is 150 to 200m ² (iii) a pore volume of 0.6 to 0.8 cm/g ² (iv) g, the average pore diameter is 8.5 to 9.5nm.

2. The preparation method of the hydrogenation catalyst according to claim 1, wherein the composite carrier is prepared by a coprecipitation method, bimetallic Ni and Ce are added for modification, and the composite carrier is calcined at a high temperature of 600 to 800 ℃.

3. The method for preparing a hydrogenation catalyst according to claim 1 or 2, wherein the composite carrier is Ni-Ce-Al ₂ O ₃ The content of Ni in the alloy is 0.2-0.5 wt%, the content of Ce in the alloy is 0.2-0.5 wt%, and the load of Ru is 0.2-1wt%.

4. The method for preparing a hydrogenation catalyst according to claims 1-2, wherein the composite carrier Ni-Ce-Al is prepared by the ion coprecipitation method ₂ O ₃ The specific operation is as follows: mixing Ni (NO) ₃ ) ₂ ·6H ₂ O and Ce (NO) ₃ ) ₃ ·6H ₂ Dissolving O in water, and stirring uniformly to obtain powder Al ₂ O ₃ The carrier is stirred uniformly and Na is added ₂ CO ₃ Adjusting the pH value of the aqueous solution to 7~8 to obtain a suspension, placing the suspension in a water bath kettle, heating, stirring, crystallizing, filtering, washing and drying to obtain solid powder; drying, crushing, sieving, tabletting and roasting the solid powder to obtain the composite carrier Ni-Ce-Al ₂ O ₃ 。

5. The preparation method of the hydrogenation catalyst according to claim 1, wherein the equal volume impregnation method is adopted to load Ru on the composite carrier Ni-Ce-Al ₂ O ₃ The method comprises the following specific operations:

adding the aqueous solution of ruthenium source into the composite carrier Ni-Ce-Al ₂ O ₃ Continuously stirring until the mixture is fully mixed and impregnated, and drying and roasting the impregnated mixture to obtain a hydrogenation catalyst precursor;

and reducing the hydrogenation catalyst precursor by using hydrogen to obtain the hydrogenation catalyst.

6. The method of claim 5, wherein the ruthenium source is ruthenium chloride.

7. The method for producing a hydrogen catalyst according to claim 5, wherein the hydrogen reduction temperature is 200 to 400 ℃ and the reduction time is 1 to 3 hours.

8. The application method of the hydrogenation catalyst obtained by the preparation method of 1~7, which is characterized in that bisphenol compound is dissolved in organic solvent, and hydrogen is continuously introduced, and a fixed bed reactor is adopted to continuously prepare high trans-ratio hydrogenated bisphenol product under the action of the hydrogenation catalyst.

9. The method for using a hydrogenation catalyst according to claim 8, wherein the bisphenol compound is bisphenol A, bisphenol S or bisphenol F.

10. The method for using a hydrogen catalyst according to claim 8, characterized in that the process conditions are: the reaction temperature is 110 to 160 ℃, and the liquid space velocity is 0.18 to 0.36h ^-1 The reaction pressure is 4 to 6MPa.

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