CN115920926A - Preparation method and application method of ruthenium hydrogenation catalyst - Google Patents

Abstract

The invention relates to the field of catalyst hydrogenation, in particular to a preparation method and an application method of a ruthenium hydrogenation catalyst. The technique thereofThe key points are as follows: using Ni (NO) ₃ ) ₂ ·6H ₂ O and (NH) ₄ )H ₂ W ₁₂ O ₄₀ ·xH ₂ Precipitation deposition of O on Al ₂ O ₃ Modifying the carrier and then roasting to obtain a metal modified carrier; loading ruthenium by using a metal modified carrier through an impregnation method, roasting, and reducing by using hydrogen to obtain the hydrogenation catalyst; wherein, the mass fraction of ruthenium is 0.5 percent, the mass fraction of Ni is 0.5 to 2.5 percent, the mass fraction of W is 0.5 to 2.5 percent, and the rest components are alumina carriers. The invention adopts ruthenium and alumina, and auxiliary agents of nickel and tungsten respectively on the selection of active components and carriers, and the synergistic effect among several metal elements improves the dispersion degree of the active components.

Description

A kind of preparation method and application method of ruthenium series hydrogenation catalyst

technical field

The invention relates to the field of catalyst hydrogenation, in particular to a preparation method and application method of a ruthenium-based hydrogenation catalyst.

Background technique

Ruthenium-based catalysts are widely used in the field of hydrogenation of benzene rings. Compared with hydrogenation catalysts such as iron, cobalt, and nickel, ruthenium-based catalysts are characterized by mild reaction conditions in hydrogenation, and the combination of additives can promote catalytic efficiency. The synergistic effect is often applied in petrochemical, pharmaceutical synthesis and other fields. With the development of new materials, the requirements for catalytic processes are gradually increasing, and the performance requirements for catalysts are also continuously improving.

In the benzene ring hydrogenation process in the prior art, the selected catalysts are divided into two types: ruthenium carbon, ruthenium and other noble metal composite catalysts. Among them, the total yield of ruthenium-carbon catalyst is low, only 63%; while the total yield of ruthenium and other noble metal composite catalysts can exceed 70%, but the amount of noble metal is large, the catalyst cost is high, and the reaction temperature is high, which is easy Cause the breakage of the ester group and affect the purity of the product.

In view of the defects of the above-mentioned existing benzene ring hydrogenation catalytic reaction, the present inventor, based on years of rich experience and professional knowledge in this type of material, cooperates with theoretical analysis, researches and innovates, and develops a preparation method and application of a ruthenium-based hydrogenation catalyst method.

Contents of the invention

The purpose of the present invention is to provide a preparation method and application method of a ruthenium-based hydrogenation catalyst, using ruthenium and alumina respectively, plus nickel and tungsten as additives, and the synergistic effect between several metal elements makes the dispersion of the active components be improved.

Based on the reaction kinetics of the hydrogenation of the catalyst on the benzene ring, hydrogen overflow occurs on the surface of the catalyst during the process, that is, hydrogen is activated on the metal surface and migrates outward from the metal surface with the assistance of aromatic hydrocarbon molecules. Since WOx has a strong acidity and _WOx has a strong affinity for the π bond in the benzene ring, it can improve the overall catalytic activity of the catalyst. Therefore, compared with Ru/Al ₂ O ₃ and Ru-Ni/Al ₂ O ₃ , more acidic sites can be provided to facilitate the reaction. The addition of nickel can produce a metal synergistic effect with ruthenium to reduce the reduction temperature of NiOx, and the nickel-based additives can promote the further complete hydrogenation of the incompletely hydrogenated intermediate cyclohexene species of the benzene ring and improve the hydrogenation selectivity. The combination between the free RuO ₂ and the auxiliary oxide weakens the interaction force between RuO ₂ and the support Al ₂ O ₃ , and the weakening of the force can improve the dispersion of the metal.

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

The preparation method of a ruthenium-based double-promoter hydrogenation catalyst provided by the present invention uses Ni(NO ₃ ) ₂ 6H ₂ O and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O to react Al _{The 2} O ₃ carrier is modified and roasted to obtain a metal-modified carrier; then the metal-modified carrier is used to load the ruthenium by an impregnation method and then roasted, and the hydrogenation catalyst is obtained after hydrogen reduction;

Wherein, the mass fraction of ruthenium is 0.5%, the mass fraction of Ni is 0.5-2.5%, the mass fraction of W is 0.5-2.5%, and the rest is alumina carrier.

In the present invention, two loads and two roasts are used, and the auxiliary agent is loaded prior to the active component because the catalyst obtained by one-time loaded roasting, the addition of the auxiliary agent and the active component at the same time will make the auxiliary agent occupy the active site or cover it to a certain extent. The active components thus affect the activity of the catalyst, and the two loading and calcinations can effectively avoid the occurrence of such a situation, and the temperature control in the two calcinations can make the catalyst have suitable texture properties and mechanical strength.

In the catalyst provided by the present invention, the addition of additives improves the overall acidity of the catalyst, increases the activity of the catalyst for the reaction, makes the reaction temperature condition milder, and avoids the breakage of the ester bond in the hydrogenation process due to temperature factors, which causes increased by-products. Under the same conditions, compared with Ru/Al ₂ O ₃ , Ru-Ni/Al ₂ O ₃ and Ru-W/Al ₂ O ₃ catalysts, the catalytic effect of dual promoters is better, and the relationship between promoters and activity The segmental roasting effect of the components is also better than the one-time loading effect.

Further, the specific operation of the precipitation deposition method is: dissolving Ni(NO ₃ ) ₂ ·6H ₂ O and (NH ₄ )H ₂ W ₁₂ O ₄₀ ·xH ₂ O in water to obtain a mixed solution, and the Al ₂ O ₃ carrier When it is added into the mixed solution and heated for crystallization, a eutectic will be produced at this time, which will cause a synergistic effect between the metal units and further improve the catalytic efficiency. In the present invention, the ammonium metatungstate can not only support the auxiliary agent but also interact with the carrier to further improve the pore structure of the carrier.

Further, the specific operation of the impregnation method is: dissolving RuCl ₃ ·xH ₂ O in water, adding the metal-modified carrier, heating and stirring to make the ruthenium loaded uniformly.

Further, the Al ₂ O ₃ carrier is prepared by modifying after mixing pseudo-boehmite, citric acid, turnip powder, methyl cellulose and water.

Further, the BET specific surface area of the Al ₂ O ₃ support is 228.29m ² /g, the pore volume is 0.61mL/g, and the pore diameter is 8.27nm.

Further, the content of Ru in RuCl ₃ ·xH ₂ O is 37.0%.

Further, the W content in (NH ₄ )H ₂ W ₁₂ O ₄₀ ·xH ₂ O is 74.6%.

Further, the hydrogenation catalyst has a BET specific surface area of 190-210 m ² /g, a pore volume of 0.5-0.6 mL/g, and a pore diameter of 7.5-8.5 nm after the hydrogenation catalyst is calcined.

Further, the catalyst of the present invention is prepared according to the following steps:

S1. Weigh a certain amount of dry-treated Al ₂ O ₃ carrier through a 40-mesh sieve for later use, and then weigh different masses of Ni(NO ₃ ) ₂ .6H ₂ O (Ni content 20.2%) and (NH ₄ ) according to different preparation ratios H ₂ W ₁₂ O ₄₀ .xH ₂ O (W content 74.6%) was put in a beaker, and an appropriate amount of deionized water was added to stir to dissolve, and then the dry treated Al ₂ O ₃ carrier was slowly added at one time and stirred evenly, and NH ₄ HCO ₃ The aqueous solution adjusts Ph to 7-8;

S2. The suspension obtained in step S1 is placed in a water bath at 60° C. to 80° C., heated and stirred to crystallize for 1 to 2 hours;

S3. Filtrating, washing and drying the solid powder obtained in step S2, and roasting at 400-600° C. for 2-4 hours;

S4. Weigh a certain amount of RuCl ₃ .xH ₂ O (Ru content 37.0%) in a beaker in proportion, add an appropriate amount of deionized water to dissolve completely, add the product roasted in step S3 to fully stir and place it in a water bath to stir The active components are evenly loaded, and after the surface moisture is completely evaporated, put it into an oven for drying treatment;

S5. Calcining the solid powder obtained in step S4 at 200-400° C. for 2-4 hours, and reducing to 200-300° C. for 2-3 hours in a hydrogen atmosphere after tablet molding to obtain the desired prepared catalyst.

The second object of the present invention is to provide an application method of a hydrogenation catalyst, which has the same technical effect, reduces economic demands, and is beneficial to industrialization.

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

The application method of the hydrogenation catalyst provided by the invention is to use the hydrogenation catalyst in the hydrogenation process of tetramethyl pyromellitic acid.

Further, the benzene ring hydrogenation process of tetramethyl pyromellitic acid is carried out in a fixed-bed reactor, and the process conditions are: temperature 150-180°C, pressure 3.5-5.5MPa, liquid space velocity 0.18-0.28h ^-1 .

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

The present invention adopts ruthenium and aluminum oxide respectively in the selection of the active component and the carrier, plus nickel and tungsten as additives, the synergistic effect between several metal elements makes the dispersion of the active component be improved, and the addition of nickel makes the benzene ring add The selectivity of the hydrogen process has increased, and WO _x has stronger acidity. Compared with Ru/Al ₂ O ₃ , Ru-Ni/Al ₂ O ₃ can provide more acid sites and WO _x The π bond has a strong affinity, so it is beneficial to the hydrogenation of the benzene ring, which improves the yield and conversion rate. And choosing ruthenium as the active component, compared with multi-component noble metal catalysts such as ruthenium, rhodium, and palladium, reduces the economic demand and is conducive to industrialization.

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 ruthenium-based hydrogenation catalyst proposed according to the present invention, its specific implementation, characteristics and effects, are described in detail The description is as follows.

Example 1

Preparation of hydrogenation catalyst:

S1. Weigh 19.7g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 0.50g and (NH ₄ )H ₂ W ₁₂ O ₄₀ .xH ₂ O 0.13g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 400°C for 4h, then weigh 0.27g of RuCl ₃ ·xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 200° C. for 3 h, and reducing it under hydrogen atmosphere for 3 h at 200° C. to obtain a catalyst after tablet molding.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 0.5%, the content of tungsten is 0.5%, and the rest is carrier aluminum oxide.

Example 2

Preparation of hydrogenation catalyst:

S1. Weigh 19.7g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 0.50g and (NH ₄ )H ₂ W ₁₂ O ₄₀ .xH ₂ O 0.13g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 500°C for 3h, then weigh 0.27g of RuCl ₃ xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 300°C for 3 hours, and reducing it under hydrogen atmosphere at 250°C for 3 hours after tablet molding, to obtain a catalyst;

The mass content of the active component ruthenium is 0.5%, the content of nickel is 0.5%, the content of tungsten is 0.5%, and the rest is carrier aluminum oxide.

Example 3

Preparation of hydrogenation catalyst:

S1. Weigh 19.7g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 0.50g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.13g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h, filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then bake at 600°C for 2h;

S3. Then weigh 0.27g of RuCl ₃ ·xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, add the roasted product into it and fully stir and impregnate;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 400° C. for 2 hours, and reducing it under a hydrogen atmosphere for 2 hours at 300° C. to obtain a catalyst after tablet molding.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 0.5%, the content of tungsten is 0.5%, and the rest is carrier aluminum oxide.

Example 4

Preparation of hydrogenation catalyst:

S1. Weigh 19.3g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 1.49g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.40g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 400°C for 4h, then weigh 0.27g of RuCl ₃ ·xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 200° C. for 3 h, and reducing it under hydrogen atmosphere for 3 h at 200° C. to obtain a catalyst after tablet molding.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 1.5%, the content of tungsten is 1.5%, and the rest is carrier aluminum oxide.

Example 5

Preparation of hydrogenation catalyst:

S1. Weigh 19.3g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 1.49g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.40g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 500°C for 3h, then weigh 0.27g of RuCl ₃ xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 300° C. for 3 hours, and reducing it under hydrogen atmosphere at 250° C. for 3 hours after tableting to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 1.5%, the content of tungsten is 1.5%, and the rest is carrier aluminum oxide.

Example 6

Preparation of hydrogenation catalyst:

S1. Weigh 19.3g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 1.49g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.40g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 600°C for 2h, then weigh 0.27g of RuCl ₃ ·xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 400° C. for 2 hours, and reducing it under a hydrogen atmosphere for 2 hours at 300° C. to obtain a catalyst after tablet molding.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 1.5%, the content of tungsten is 1.5%, and the rest is carrier aluminum oxide.

Example 7

Preparation of hydrogenation catalyst:

S1. Weigh 18.9g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 2.48g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.67g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 400°C for 4h, then weigh 0.27g of RuCl ₃ .xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 200° C. for 3 h, and reducing it under hydrogen atmosphere for 3 h at 200° C. to obtain a catalyst after tablet molding.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 2.5%, the content of tungsten is 2.5%, and the rest is carrier aluminum oxide.

Example 8

Preparation of hydrogenation catalyst:

S1. Weigh 18.9g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 2.48g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.67g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 500°C for 3h, then weigh 0.27g of RuCl ₃ xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 300° C. for 3 hours, and reducing it under hydrogen atmosphere at 250° C. for 3 hours after tableting to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 2.5%, the content of tungsten is 2.5%, and the rest is carrier aluminum oxide.

Example 9

Preparation of hydrogenation catalyst:

S1. Weigh 18.9g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 2.48g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.67g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 600°C for 2h, then weigh 0.27g of RuCl ₃ ·xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S4. Then heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 400° C. for 2 hours, and reducing it under a hydrogen atmosphere for 2 hours at 300° C. to obtain a catalyst after tablet molding.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 2.5%, the content of tungsten is 2.5%, and the rest is carrier aluminum oxide.

performance analysis

The characterization and analysis of the hydrogenation catalysts of Examples 1-9 are shown in Tables 1-3.

The pore structure of the hydrogenation catalyst of table 1. embodiment 1～9

Example <![CDATA[Specific surface area m²/g]]> <![CDATA[pore volume cm³/g]]> Aperture nm 1 199.77 0.58 8.44 2 201.34 0.59 8.44 3 203.04 0.59 8.34 4 194.62 0.59 8.37 5 196.43 0.59 8.39 6 203.67 0.59 8.33 7 193.41 0.57 8.30 8 194.85 0.57 8.28 9 196.25 0.58 8.28 <![CDATA[Carrier Al₂O₃]]> 228.29 0.61 8.27

Table 2. Embodiment 1～9 catalyst composition and preparation

Example Composition (except carrier) one stage roasting Second stage roasting reduction 1 0.5Ru%, 0.5Ni%, 0.5%W 400℃, 4h 200℃, 3h 200℃, 3h 2 0.5Ru%, 0.5Ni%, 0.5%W 500℃, 3h 300℃, 3h 250℃, 3h 3 0.5Ru%, 0.5Ni%, 0.5%W 600℃, 2h 400℃, 2h 300℃, 2h 4 0.5Ru%, 1.5Ni%, 1.5%W 400℃, 4h 200℃, 3h 200℃, 3h 5 0.5Ru%, 1.5Ni%, 1.5%W 500℃, 3h 300℃, 3h 250℃, 3h 6 0.5Ru%, 1.5Ni%, 1.5%W 600℃, 2h 400℃, 2h 300℃, 2h 7 0.5Ru%, 2.5Ni%, 2.5%W 400℃, 4h 200℃, 3h 200℃, 3h 8 0.5Ru%, 2.5Ni%, 2.5%W 500℃, 3h 300℃, 3h 250℃, 3h 9 0.5Ru%, 2.5Ni%, 2.5%W 600℃, 2h 400℃, 2h 300℃, 2h

44.8 g of tetramethyl pyromellitic acid was dissolved in 500 mL of 1,4-dioxane, and a solution with a mass fraction of 8% was used as a raw material for hydrogenation reaction. Next, the catalyst is loaded into the single-tube fixed-bed reactor, and the temperature is programmed to rise and reduced in a hydrogen atmosphere. After the reduction is completed, the raw material is transported into the reactor through a metering pump. Reaction conditions: temperature 160°C, pressure 4.5MPa, liquid space velocity 0.28h ^-1 , volume ratio of hydrogen to oil 696:1, after the reaction is stable, samples are taken for chromatographic analysis. The hydrogenation performance evaluation of the catalysts of Examples 1-9 is shown in Table 3 below.

Table 3. Catalyst hydrogenation activity evaluation

Example Conversion rate/% selectivity/% 1 99.1 97.2 2 99.6 98.8 3 99.3 98.8 4 99.9 99.1 5 99.9 99.1 6 99.9 99.4 7 99.1 98.1 8 99.2 98.3 9 99.2 98.4

Comparative Example 1

S1. Weigh 19.3g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 1.49g and (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.40g into a 150mL beaker and add 50mL Stir to dissolve in deionized water;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven dry at 75°C for 6h, and then roast at 500°C for 3h, then weigh 0.27g of RuCl ₃ xH ₂ O into a 100mL beaker, add 15mL of deionized water to dissolve completely, and roast the obtained product Add to it and stir well for impregnation;

S3. Heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S4. Calcining the obtained solid powder at 300° C. for 3 hours, and reducing it at 250° C. for 3 hours in a hydrogen atmosphere after tableting to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 1.5%, the content of tungsten is 1.5%, and the rest is carrier aluminum oxide.

Comparative Example 2

S1. Weigh 19.3g alumina carrier for later use, then weigh Ni(NO ₃ ) ₂ 6H ₂ O 1.49g, (NH ₄ )H ₂ W ₁₂ O ₄₀ xH ₂ O 0.40g, RuCl ₃ .xH ₂ O Put 0.27g in a 150mL beaker and add 50mL deionized water to stir and dissolve;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven-dry at 75°C for 6 hours, and then bake at 300°C for 3 hours. After the firing is completed, tablet molding is performed and reduced at 250°C for 3 hours in a hydrogen atmosphere to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, the content of nickel is 1.5%, the content of tungsten is 1.5%, and the rest is carrier aluminum oxide.

Comparative Example 3

First weigh 19.6g of alumina carrier for later use, then weigh 1.49g of Ni(NO ₃ ) ₂ .6H ₂ O into a 150mL beaker, add 18mL of deionized water and stir to dissolve, then place in a 70°C water bath and add the dried The Al ₂ O ₃ carrier was stirred evenly, and after the surface moisture was completely evaporated, it was placed in an oven at 75°C for 6 hours of drying treatment, and the obtained solid powder was roasted at 500°C for 3 hours, and then weighed RuCl ₃ .xH ₂ O 0.27g into a 150mL beaker, Add 18mL of deionized water to dissolve completely, add the roasted solid powder and stir evenly, then heat and stir in a 70°C water bath to make the loading of active components more uniform, and after the surface water has completely evaporated, put it in a 75°C oven to dry for 6 hours. The obtained solid powder was calcined at 300°C for 3 hours, and after the calcining was completed, it was compressed into tablets and reduced at 250°C for 3 hours in a hydrogen atmosphere to obtain a catalyst. The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, and the rest is carrier aluminum oxide.

Comparative Example 3

S1. Weigh 19.6g of alumina carrier for later use, then weigh 1.49g of Ni(NO ₃ ) ₂ 6H ₂ O into a 150mL beaker and add 18mL of deionized water to stir and dissolve;

S2. Place in a 70°C water bath, add the dried Al ₂ O ₃ carrier and stir evenly. After the surface moisture has completely evaporated, put it into a 75°C oven for drying treatment for 6 hours;

S3. Roast the obtained solid powder at 500°C for 3 hours, then weigh 0.27 g of RuCl ₃ xH ₂ O into a 150 mL beaker, add 18 mL of deionized water to dissolve completely, add the roasted solid powder and stir evenly;

S4. Heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it in a 75°C oven to dry for 6 hours;

S5. Calcining the obtained solid powder at 300° C. for 3 hours, and then pressing it into tablets and reducing it at 250° C. for 3 hours in a hydrogen atmosphere to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, and the rest is carrier aluminum oxide.

Comparative Example 4

S1. Weigh 19.3g of alumina carrier for later use, then weigh 1.49g of Ni(NO ₃ ) ₂ 6H ₂ O and 0.27g of RuCl ₃ xH ₂ O into a 150mL beaker and add 18mL of deionized water to stir and dissolve;

S2. Place in a 70°C water bath, add the dried Al ₂ O ₃ carrier and stir evenly. After the surface moisture is completely evaporated, put it in a 75°C oven for 6 hours, then bake at 300°C for 3 hours;

S3. After the calcination is completed, reduce at 250° C. for 3 hours under a hydrogen atmosphere to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, and the rest is carrier aluminum oxide.

Comparative Example 5

S1. Weigh 19.3g alumina carrier for later use, then weigh (NH ₄ )H ₂ W ₁₂ O ₄₀ .xH ₂ O 0.40g, RuCl ₃ xH ₂ O 0.27g in a 150mL beaker and add 50mL deionized water to stir dissolve;

S2. Slowly add the dried Al ₂ O ₃ carrier at one time and stir evenly, then adjust the Ph of the suspension to 7-8 with 10% NH ₄ HCO ₃ aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize 1h;

S3. Filter and wash the obtained solid powder overnight, oven-dry at 75°C for 6 hours, and then bake at 300°C for 3 hours. After the firing is completed, tablet molding is performed and reduced at 250°C for 3 hours in a hydrogen atmosphere to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, the content of tungsten is 1.5%, and the rest is carrier aluminum oxide.

Comparative Example 6

S1. Weigh 19.9g of alumina carrier for later use, then weigh 0.27g of RuCl ₃ ·xH ₂ O into a 150mL beaker, add 18mL of deionized water to dissolve completely, then add dry treated Al ₂ O ₃ carrier and stir;

S2. Heat and stir in a 70°C water bath to make the loading of active components more uniform. After the surface moisture is completely evaporated, put it into a 75°C oven for drying treatment for 6 hours;

S3. Calcining the obtained solid powder at 300° C. for 3 hours, and then pressing it into tablets and reducing it at 250° C. for 3 hours in a hydrogen atmosphere to obtain a catalyst.

The mass content of the active component ruthenium is 0.5%, and the rest is carrier alumina.

Hydrogenation activity comparison test

44.8 g of tetramethyl pyromellitic acid was dissolved in 500 mL of 1,4-dioxane, and a solution with a mass fraction of 8% was used as a raw material for hydrogenation reaction. Next, the catalyst is loaded into the single-tube fixed-bed reactor, and the temperature is programmed to rise and reduced in a hydrogen atmosphere. After the reduction is completed, the raw material is transported into the reactor through a metering pump. Reaction conditions: temperature 160°C, pressure 4.5MPa, liquid space velocity 0.28h ^-1 , volume ratio of hydrogen to oil 696:1, after the reaction is stable, samples are taken for chromatographic analysis. The pore structure analysis and hydrogenation performance evaluation of the catalysts under different loadings, calcination conditions and preparation methods are compared as follows.

Table 4. Comparative examples 1～6 catalyst pore structure analysis

catalyst <![CDATA[Specific surface area m²/g]]> <![CDATA[pore volume cm³/g]]> Aperture nm C1 194.62 0.59 8.39 C2 179.25 0.56 8.11 C3 203.67 0.60 8.33 C4 199.62 0.59 8.21 C5 201.43 0.59 8.25 C6 211.41 0.60 8.30 <![CDATA[Carrier Al₂O₃]]> 228.29 0.61 8.27

Table 5. Catalyst composition and preparation of comparative examples 1 to 6

Table 6. Comparative examples 1～6 Catalyst hydrogenation activity evaluation

catalyst Conversion rate/% selectivity/% C1 99.9 99.1 C2 88.2 90.2 C3 99.7 96.2 C4 89.9 90.9 C5 95.4 90.2 C6 99.9 93.7

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. A process for preparing the dual-assistant Ru-series hydrocatalyst features use of Ni (NO) ₃ ) ₂ ·6H ₂ O and (NH) ₄ )H ₂ W ₁₂ O ₄₀ ·xH ₂ Precipitation deposition of O on Al ₂ O ₃ Modifying the carrier and then roasting to obtain a metal modified carrier; loading ruthenium by using a metal modified carrier through an impregnation method, roasting, and reducing by using hydrogen to obtain the hydrogenation catalyst;

wherein, the mass fraction of ruthenium is 0.45-0.55%, the mass fraction of Ni is 0.5-2.5%, the mass fraction of W is 0.5-2.5%, and the rest is alumina carrier.

2. The preparation method of the ruthenium-based double-promoter hydrogenation catalyst according to claim 1, wherein the precipitation deposition method comprises the following specific operations: mixing Ni (NO) ₃ ) ₂ ·6H ₂ O and (NH) ₄ )H ₂ W ₁₂ O ₄₀ ·xH ₂ Dissolving O in water to obtain mixed solution, and dissolving Al in the mixed solution ₂ O ₃ And adding the carrier into the mixed solution for heating crystallization.

3. The preparation method of ruthenium dual-promoter hydrogenation catalyst according to claim 1 or 2, wherein the impregnation method comprises the following specific operations: adding RuCl ₃ ·xH ₂ Dissolving O in water, adding the metal modified carrier, heating and stirring to make the load of ruthenium uniform.

4. The method for preparing the ruthenium-based double-promoter hydrogenation catalyst as claimed in claim 1, wherein the Al is ₂ O ₃ The carrier is prepared by mixing and modifying pseudo-boehmite, citric acid, sesbania powder, methyl cellulose and water.

5. The method of claim 1, wherein the Al is added in the hydrogenation catalyst ₂ O ₃ The BET specific surface area of the carrier is 220.00 to 230.00m ² (iv)/g, pore volume 0.55 to 0.65mLg, the pore diameter is 8.1 to 8.3nm.

6. The method for preparing ruthenium dual promoter hydrogenation catalyst as claimed in claim 1, wherein the RuCl is added ₃ ·xH ₂ The content of Ru in O is 35.0-37.0%.

7. The method for preparing a ruthenium-based double promoter hydrogenation catalyst as claimed in claim 1, wherein the (NH) ₄ )H ₂ W ₁₂ O ₄₀ ·xH ₂ The W content in O was 74.6%.

8. The preparation method of a ruthenium double-promoter hydrogenation catalyst as claimed in claim 1, wherein the BET specific surface area of the calcined hydrogenation catalyst is 190 to 210m ² The pore volume is 0.5 to 0.6mL/g, and the pore diameter is 7.5 to 8.5nm.

9. The application method of the hydrogenation catalyst obtained by the preparation method according to any one of claims 1 to 8, wherein the hydrogenation catalyst is used in a hydrogenation process of tetramethyl pyromellitate.

10. The application method of the hydrogenation catalyst according to claim 9, wherein the process conditions of the hydrogenation process are as follows: the temperature is 150 to 180 ℃, the pressure is 3.5 to 5.5MPa, and the liquid air speed is 0.18 to 0.28h ^-1 。