Preparation method and application method of ruthenium-based 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 ruthenium-based hydrogenation catalyst. The technical key points are as follows: Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 ·xH2O are used to modify the Al2O3 support by the precipitation deposition method and then calcined to obtain a metal-modified support; then, ruthenium is loaded on the metal-modified support by the impregnation method and then calcined, 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 remaining components are the alumina support. In the present invention, ruthenium and alumina are respectively used for the selection of the active component and the support, and together with the auxiliaries nickel and tungsten, the synergistic effect among several metal elements improves the dispersion degree of the active component.

Description

Technical Field

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

[0002] Ruthenium-based catalysts are widely used in the field of benzene ring hydrogenation. 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 produce a synergistic effect to promote the catalytic efficiency, and are often used in the fields of petrochemical industry, pharmaceutical synthesis, etc. With the booming development of new materials, the requirements for catalytic processes are gradually increasing, and the performance requirements for catalysts are also constantly improving.

[0003] In the existing benzene ring hydrogenation process, the selected catalysts are divided into two types: ruthenium carbon and ruthenium and other noble metal composite catalysts. Among them, the total yield of the ruthenium carbon catalyst is relatively low, only 63%; while although the total yield of the ruthenium and other noble metal composite catalysts can exceed 70%, the dosage of noble metals is large, the catalyst cost is high, and the reaction temperature is relatively high, which is likely to cause the cleavage of ester groups and affect the product purity.

[0004] In view of the above defects of the existing benzene ring hydrogenation catalytic reaction, based on the rich experience and professional knowledge in this field for many years, the inventor cooperates with theoretical analysis, conducts research and innovation, and develops a preparation method and an application method of a ruthenium-based hydrogenation catalyst. Summary of the Invention

[0005] The purpose of the present invention is to provide a preparation method and an application method of a ruthenium-based hydrogenation catalyst. Ruthenium and alumina are respectively used, together with additives nickel and tungsten, and the synergistic effect among several metal elements improves the dispersion degree of the active components.

[0006] Based on the reaction kinetic principle of the catalyst in the hydrogenation of the benzene ring, hydrogen spillover will occur 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. The spilled hydrogen acts on the aromatic hydrocarbon molecules at the acidic sites. Since WOx has strong acidity and WO x 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 / Al2O3 and Ru-Ni / Al2O3, it can provide more acidic sites, which is beneficial to the progress of the reaction. The addition of nickel can produce a metal synergistic effect with ruthenium, reduce the reduction temperature of NiOx, and the nickel-based additive can promote the further complete hydrogenation of the intermediate cyclohexene substances in the benzene ring that are not fully hydrogenated, improving the hydrogenation selectivity. The combination between free RuO2 and the additive oxide weakens the interaction force between RuO2 and the carrier Al2O3, and the weakening of the interaction force can improve the dispersion degree of the metal.

[0007] The above technical object of the present invention is achieved by the following technical solutions:

[0008] A preparation method of a ruthenium-based dual-promoter hydrogenation catalyst provided by the present invention uses Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 ·xH2O to modify the Al2O3 support by the precipitation-deposition method and then calcine it to obtain a metal-modified support; then, the ruthenium is loaded on the metal-modified support by the impregnation method and then calcined, and the hydrogenation catalyst is obtained after hydrogen reduction;

[0009] Among them, 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 of the components are alumina supports.

[0010] In the present invention, two loadings and two calcinations are adopted and the promoter is loaded before the active component because for the catalyst obtained by one-time loading and calcination, when the promoter and the active component are added simultaneously, the promoter will occupy the active sites or cover the active component to a certain extent, thus affecting the catalyst activity. Two loadings and calcinations can effectively avoid such situations, and through the control of temperature in the two calcinations, the catalyst can have appropriate texture properties and mechanical strength.

[0011] In the catalyst provided by the present invention, the addition of the promoter increases the overall acidity of the catalyst, increases the activity of the catalyst for the reaction, makes the reaction temperature conditions milder, and avoids the phenomenon of increased by-products caused by the breakage of the ester bond during the hydrogenation process due to temperature factors. Under the same conditions, compared with Ru / Al2O3, Ru-Ni / Al2O3 and Ru-W / Al2O3 catalysts, the catalytic effect of the dual-promoter is better, and the effect of the staged calcination of the promoter and the active component is also better than that of one-time loading.

[0012] Further, the specific operation of the precipitation-deposition method is as follows: Dissolve Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 ·xH2O in water to obtain a mixed solution, add the Al2O3 support to the mixed solution and heat for crystallization. At this time, eutectics will be generated, enabling a synergistic effect between metal units and further improving the catalytic efficiency. In the present invention, ammonium metatungstate can not only load the promoter but also act with the support to further improve the pore structure of the support.

[0013] Further, the specific operation of the impregnation method is as follows: Dissolve RuCl3·xH2O in water, add the metal-modified support, and heat and stir to make the loading of ruthenium uniform.

[0014] Further, the Al2O3 support is obtained by modifying a mixture of pseudoboehmite, citric acid, carboxymethyl cellulose, methyl cellulose and water.

[0015] Further, the BET specific surface area of the Al2O3 support is 228.29 m 2 / g, the pore volume is 0.61 mL / g, and the pore diameter is 8.27 nm.

[0016] Further, the content of Ru in RuCl3·xH2O is 37.0%.

[0017] Further, the content of W in (NH4)H2W 12 O 40 ·xH2O is 74.6%.

[0018] Further, the BET specific surface area of the hydrogenation catalyst after calcination is 190 - 210 m 2 / g, the pore volume is 0.5 - 0.6 mL / g, and the pore diameter is 7.5 - 8.5 nm.

[0019] Further, the catalyst of the present invention is prepared according to the following steps:

[0020] S1. Weigh a certain amount of dried 40 - mesh Al2O3 support for standby, and then weigh different masses of Ni(NO3)2·6H2O (Ni content 20.2%) and (NH4)H2W 12 O 40 .xH2O (W content 74.6%) into a beaker, add an appropriate amount of deionized water and stir to dissolve. Then slowly add the dried Al2O3 support all at once and stir evenly, and adjust the pH to 7 - 8 with an NH4HCO3 aqueous solution;

[0021] S2. Place the suspension obtained in step S1 in a water bath and heat and stir for crystallization at 60°C - 80°C for 1 - 2 h;

[0022] S3. Filter, wash, and dry the solid powder obtained in step S2, and then calcine it at 400 - 600°C for 2 - 4 h;

[0023] S4. Weigh a certain amount of RuCl3·xH2O (Ru content 37.0%) into a beaker according to the proportion. After completely dissolving it with an appropriate amount of deionized water, add the product obtained by calcination in step S3 into it, stir well, and place it in a water bath to stir to make the active components uniformly loaded. After the surface moisture is completely evaporated, put it into an oven for drying treatment;

[0024] S5. Calcinate the solid powder obtained in step S4 at 200 - 400°C for 2 - 4 h, press it into tablets, and then reduce it at 200 - 300°C in a hydrogen atmosphere for 2 - 3 h to obtain the required catalyst.

[0025] The second object of the present invention is to provide a method for applying a hydrogenation catalyst, which has the same technical effects, reduces the economic requirements, and is conducive to industrialization.

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

[0027] The method for applying the hydrogenation catalyst provided by the present invention is to use the hydrogenation catalyst in the hydrogenation process of tetramethyl pyromellitate.

[0028] Further, the benzene ring hydrogenation process of tetramethyl pyromellitate is carried out in a fixed bed reactor, and the process conditions are: temperature 150-180 °C, pressure 3.5-5.5 MPa, liquid hourly space velocity 0.18-0.28 h -1 .

[0029] In summary, the present invention has the following beneficial effects:

[0030] In the present invention, ruthenium and alumina are respectively used in the selection of the active ingredient and the carrier, together with the promoters nickel and tungsten. The synergistic effect between several metal elements improves the dispersion degree of the active component. The addition of nickel increases the selectivity of the benzene ring hydrogenation process. WO x has strong acidity. Compared with Ru / Al2O3, Ru-Ni / Al2O3 can provide more acid sites and WO x has a strong affinity for the π bond in the benzene ring. Therefore, it is beneficial to the hydrogenation of the benzene ring, improving the yield and conversion rate. And ruthenium is selected as the active component, which reduces the economic requirements compared with multi-component noble metal catalysts such as ruthenium, rhodium, and palladium, and is conducive to industrialization. Specific embodiments

[0031] To further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, a preparation method and an application method of a ruthenium-based hydrogenation catalyst according to the present invention are described in detail below in terms of their specific embodiments, features and effects.

[0032] Example 1

[0033] Preparation of hydrogenation catalyst:

[0034] S1. Weigh 19.7 g of alumina carrier for standby, then weigh 0.50 g of Ni(NO3)2·6H2O and 0.13 g of (NH4)H2W 12 O 40 .xH2O into a 150 mL beaker and add 50 mL of deionized water to stir and dissolve;

[0035] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the suspension Ph to 7-8 with 10% NH4HCO3 aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize for 1 hour;

[0036] S3, after the solid powder is left overnight, it is filtered and washed, dried in an oven at 75°C for 6 hours, and then calcined at 400°C for 4 hours, then 0.27 g of RuCl3·xH2O is weighed into a 100 mL beaker, 15 mL of deionized water is added to dissolve it completely, and then the calcined product is added thereto and stirred thoroughly for impregnation;

[0037] S4, then place it in a 70°C water bath and heat and stir to make the active component loading more uniform, and after the surface water is completely evaporated, place it in a 75°C oven and dry it for 6 hours;

[0038] S5. The obtained solid powder is calcined at 200° C. for 3 h, pressed into tablets, and then reduced at 200° C. for 3 h in a hydrogen atmosphere to obtain a catalyst.

[0039] The mass content of the active component ruthenium is 0.5%, the mass content of nickel is 0.5%, the mass content of tungsten is 0.5%, and the remaining component is carrier aluminum oxide.

[0040] Example 2

[0041] Preparation of hydrogenation catalyst:

[0042] S1. Weigh 19.7g of alumina carrier for use, then weigh 0.50g of Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 .xH2O 0.13g in a 150mL beaker and add 50mL deionized water and stir to dissolve;

[0043] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the suspension Ph to 7-8 with 10% NH4HCO3 aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize for 1 hour;

[0044] S3, after the solid powder is left overnight, it is filtered and washed, dried in an oven at 75°C for 6 hours, and then calcined at 500°C for 3 hours, then 0.27 g of RuCl3·xH2O is weighed into a 100 mL beaker, 15 mL of deionized water is added to dissolve it completely, and then the calcined product is added thereto and stirred thoroughly for impregnation;

[0045] S4, then place it in a 70°C water bath and heat and stir to make the active component loading more uniform, and after the surface water is completely evaporated, place it in a 75°C oven and dry it for 6 hours;

[0046] S5. Bake the obtained solid powder at 300 °C for 3 h, press it into tablets, and then reduce it at 250 °C for 3 h under a hydrogen atmosphere to obtain the catalyst.

[0047] The mass content of the active component ruthenium is 0.5%, the nickel content is 0.5%, the tungsten content is 0.5%, and the remaining component is the carrier alumina.

[0048] Example 3

[0049] Preparation of the hydrogenation catalyst:

[0050] S1. Weigh 19.7 g of the alumina carrier for standby, and then weigh 0.50 g of Ni(NO3)2·6H2O and 0.13 g of (NH4)H2W 12 O 40 ·xH2O into a 150 mL beaker, add 50 mL of deionized water, and stir to dissolve.

[0051] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly. Then adjust the pH of the suspension to 7 - 8 with 10% NH4HCO3 aqueous solution. Place the suspension in a 70 °C water bath and stir and heat for crystallization for 1 h. Filter and wash the obtained solid powder overnight, dry it in an oven at 75 °C for 6 h, and then bake it at 600 °C for 2 h.

[0052] S3. Then weigh 0.27 g of RuCl3·xH2O into a 100 mL beaker. After completely dissolving it with 15 mL of deionized water, add the product obtained by baking into it and stir well for impregnation.

[0053] S4. Then place it in a 70 °C water bath and heat and stir to make the loading of the active component more uniform. After the surface moisture is completely evaporated, put it in an oven at 75 °C and dry for 6 h.

[0054] S5. Bake the obtained solid powder at 400 °C for 2 h, press it into tablets, and then reduce it at 300 °C for 2 h under a hydrogen atmosphere to obtain the catalyst.

[0055] The mass content of the active component ruthenium is 0.5%, the nickel content is 0.5%, the tungsten content is 0.5%, and the remaining component is the carrier alumina.

[0056] Example 4

[0057] Preparation of the hydrogenation catalyst:

[0058] S1. Weigh 19.3 g of the alumina carrier for standby, and then weigh 1.49 g of Ni(NO3)2·6H2O and 0.40 g of (NH4)H2W 12 O 40 ·xH2O into a 150 mL beaker, add 50 mL of deionized water, and stir to dissolve.

[0059] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the suspension Ph to 7-8 with 10% NH4HCO3 aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize for 1 hour;

[0060] S3, after the solid powder is left overnight, it is filtered and washed, dried in an oven at 75°C for 6 hours, and then calcined at 400°C for 4 hours, then 0.27 g of RuCl3·xH2O is weighed into a 100 mL beaker, 15 mL of deionized water is added to dissolve it completely, and then the calcined product is added thereto and stirred thoroughly for impregnation;

[0061] S4, then place it in a 70°C water bath and heat and stir to make the active component loading more uniform, and after the surface water is completely evaporated, place it in a 75°C oven and dry it for 6 hours;

[0062] S5. The obtained solid powder is calcined at 200° C. for 3 h, pressed into tablets, and then reduced at 200° C. for 3 h in a hydrogen atmosphere to obtain a catalyst.

[0063] 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 remaining components are carrier aluminum oxide.

[0064] Example 5

[0065] Preparation of hydrogenation catalyst:

[0066] S1. Weigh 19.3g of alumina carrier for use, then weigh 1.49g of Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 · xH2O 0.40g in a 150mL beaker and add 50mL deionized water and stir to dissolve;

[0067] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the suspension Ph to 7-8 with 10% NH4HCO3 aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize for 1 hour;

[0068] S3, after the solid powder is left overnight, it is filtered and washed, dried in an oven at 75°C for 6 hours, and then calcined at 500°C for 3 hours, then 0.27 g of RuCl3·xH2O is weighed into a 100 mL beaker, 15 mL of deionized water is added to dissolve it completely, and then the calcined product is added thereto and stirred thoroughly for impregnation;

[0069] S4, then place it in a 70°C water bath and heat and stir to make the active component loading more uniform, and after the surface water is completely evaporated, place it in a 75°C oven and dry it for 6 hours;

[0070] S5. Calcinate the obtained solid powder at 300 °C for 3 h, press it into tablets, and then reduce it at 250 °C for 3 h under a hydrogen atmosphere to obtain the catalyst.

[0071] The mass content of its active component ruthenium is 0.5%, the nickel content is 1.5%, the tungsten content is 1.5%, and the remaining component is the carrier alumina.

[0072] Example 6

[0073] Preparation of the hydrogenation catalyst:

[0074] S1. Weigh 19.3 g of alumina carrier for standby, then weigh 1.49 g of Ni(NO3)2·6H2O and 0.40 g of (NH4)H2W 12 O 40 ·xH2O into a 150 mL beaker, add 50 mL of deionized water, and stir to dissolve.

[0075] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the pH of the suspension to 7 - 8 with 10% NH4HCO3 aqueous solution, and place the suspension in a 70 °C water bath and stir and heat for crystallization for 1 h.

[0076] S3. Filter and wash the obtained solid powder overnight, dry it in an oven at 75 °C for 6 h, then calcine it at 600 °C for 2 h. Then weigh 0.27 g of RuCl3·xH2O into a 100 mL beaker, add 15 mL of deionized water to dissolve completely, and then add the calcined product into it and stir thoroughly for impregnation.

[0077] S4. Then place it in a 70 °C water bath and heat and stir to make the loading of the active component more uniform. After the surface moisture is completely evaporated, put it in an oven at 75 °C and dry for 6 h.

[0078] S5. Calcinate the obtained solid powder at 400 °C for 2 h, press it into tablets, and then reduce it at 300 °C for 2 h under a hydrogen atmosphere to obtain the catalyst.

[0079] The mass content of its active component ruthenium is 0.5%, the nickel content is 1.5%, the tungsten content is 1.5%, and the remaining component is the carrier alumina.

[0080] Example 7

[0081] Preparation of the hydrogenation catalyst:

[0082] S1. Weigh 18.9 g of alumina carrier for standby, then weigh 2.48 g of Ni(NO3)2·6H2O and 0.67 g of (NH4)H2W 12 O 40 ·xH2O into a 150 mL beaker, add 50 mL of deionized water, and stir to dissolve.

[0083] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the suspension Ph to 7-8 with 10% NH4HCO3 aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize for 1 hour;

[0084] S3, after the solid powder is left overnight, it is filtered and washed, dried in an oven at 75°C for 6 hours, and then calcined at 400°C for 4 hours, then 0.27 g of RuCl3.xH2O is weighed into a 100 mL beaker, 15 mL of deionized water is added to dissolve it completely, and then the calcined product is added thereto and stirred thoroughly for impregnation;

[0085] S4, then place it in a 70°C water bath and heat and stir to make the active component loading more uniform, and after the surface water is completely evaporated, place it in a 75°C oven and dry it for 6 hours;

[0086] S5. The obtained solid powder is calcined at 200° C. for 3 h, pressed into tablets, and then reduced at 200° C. for 3 h in a hydrogen atmosphere to obtain a catalyst.

[0087] 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 remaining components are carrier aluminum oxide.

[0088] Example 8

[0089] Preparation of hydrogenation catalyst:

[0090] S1. Weigh 18.9g of alumina carrier for use, then weigh 2.48g of Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 · xH2O 0.67g in a 150mL beaker and add 50mL deionized water and stir to dissolve;

[0091] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the suspension Ph to 7-8 with 10% NH4HCO3 aqueous solution, place the suspension in a 70°C water bath, stir and heat to crystallize for 1 hour;

[0092] S3, after the solid powder is left overnight, it is filtered and washed, dried in an oven at 75°C for 6 hours, and then calcined at 500°C for 3 hours, then 0.27 g of RuCl3·xH2O is weighed into a 100 mL beaker, 15 mL of deionized water is added to dissolve it completely, and then the calcined product is added thereto and stirred thoroughly for impregnation;

[0093] S4, then place it in a 70°C water bath and heat and stir to make the active component loading more uniform, and after the surface water is completely evaporated, place it in a 75°C oven and dry it for 6 hours;

[0094] S5. The obtained solid powder was calcined at 300 °C for 3 h, pressed into tablets, and then reduced at 250 °C for 3 h under a hydrogen atmosphere to obtain the catalyst.

[0095] The mass content of the active component ruthenium was 0.5%, the nickel content was 2.5%, the tungsten content was 2.5%, and the remaining component was the carrier alumina.

[0096] Example 9

[0097] Preparation of the hydrogenation catalyst:

[0098] S1. Weigh 18.9 g of alumina carrier for standby, and then weigh 2.48 g of Ni(NO3)2·6H2O and 0.67 g of (NH4)H2W 12 O 40 ·xH2O into a 150 mL beaker, add 50 mL of deionized water, and stir to dissolve.

[0099] S2. Slowly add the dried Al2O3 carrier all at once and stir evenly, then adjust the pH of the suspension to 7 - 8 with 10% NH4HCO3 aqueous solution, and place the suspension in a 70 °C water bath and stir and heat for crystallization for 1 h.

[0100] S3. After leaving the obtained solid powder overnight, filter and wash it, dry it in an oven at 75 °C for 6 h, then calcine it at 600 °C for 2 h. Then weigh 0.27 g of RuCl3·xH2O into a 100 mL beaker, add 15 mL of deionized water to dissolve completely, and then add the calcined product to it and stir well for impregnation.

[0101] S4. Then place it in a 70 °C water bath and heat and stir to make the loading of the active component more uniform. After the surface moisture is completely evaporated, put it in an oven at 75 °C and dry for 6 h.

[0102] S5. The obtained solid powder was calcined at 400 °C for 2 h, pressed into tablets, and then reduced at 300 °C for 2 h under a hydrogen atmosphere to obtain the catalyst.

[0103] The mass content of the active component ruthenium was 0.5%, the nickel content was 2.5%, the tungsten content was 2.5%, and the remaining component was the carrier alumina.

[0104] Performance analysis

[0105] The characterization analysis of the hydrogenation catalysts in Examples 1 - 9 is shown in Tables 1 - 3.

[0106] Table 1. Pore structure of the hydrogenation catalysts in Examples 1 - 9

[0107] Example <![CDATA[Specific surface area m 2 / g]]> <![CDATA[Pore volume cm 3 / g]]> Pore diameter 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[Support Al2O3]]> 228.29 0.61 8.27

[0108] Table 2. Catalyst composition and preparation in Examples 1 - 9

[0109] Example Composition (except carrier) First-stage calcination Second-stage calcination 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

[0110] Dissolve 44.8 g of tetramethyl pyromellitate in 500 mL of 1,4-dioxane to prepare a solution with a mass fraction of 8% as the raw material for the hydrogenation reaction. Then, load the catalyst into a single-tube fixed-bed reactor, set the temperature to rise programatically and reduce it in a hydrogen atmosphere. After the reduction is completed, transport the raw material to the reactor through a metering pump. Reaction conditions: temperature 160 °C, pressure 4.5 MPa, liquid hourly space velocity 0.28 h -1 , hydrogen-oil volume ratio 696:1. After the reaction stabilizes, take samples for chromatographic analysis. The hydrogenation performance of the catalysts in Examples 1-9 is evaluated as shown in Table 3 below.

[0111] Table 3. Evaluation of Catalyst Hydrogenation Activity

[0112] 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

[0113] Comparative Example 1

[0114] S1. Weigh 19.3 g of alumina support for standby. Then, weigh 1.49 g of Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 ·xH2O 0.40 g into a 150 mL beaker and add 50 mL of deionized water to stir and dissolve.

[0115] S2. Slowly add the dried Al2O3 support all at once and stir evenly. Then, adjust the pH of the suspension to 7-8 with 10% aqueous NH4HCO3 solution, and place the suspension in a 70 °C water bath and stir and heat for crystallization for 1 h.

[0116] S3. Filter and wash the obtained solid powder overnight, dry it in an oven at 75 °C for 6 h, then calcine it at 500 °C for 3 h. Then, weigh 0.27 g of RuCl3·xH2O into a 100 mL beaker, add 15 mL of deionized water to dissolve completely, and then add the calcined product to it and stir well for impregnation.

[0117] S3. Place it in a 70 °C water bath and heat and stir to make the active component loading more uniform. After the surface moisture is completely evaporated, put it in an oven at 75 °C and dry for 6 h.

[0118] S4. Calcinate the obtained solid powder at 300 °C for 3 h, press it into tablets, and then reduce it at 250 °C for 3 h in a hydrogen atmosphere to obtain the catalyst.

[0119] The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, the tungsten content is 1.5%, and the remaining components are the carrier alumina.

[0120] Comparative Example 2

[0121] S1. Weigh 19.3 g of alumina support for standby. Then weigh 1.49 g of Ni(NO3)2·6H2O and 0.40 g of (NH4)H2W 12 O 40 ·xH2O and 0.27 g of RuCl3.xH2O into a 150 mL beaker, and add 50 mL of deionized water to stir and dissolve them;

[0122] S2. Slowly add the dried alumina support all at once and stir evenly. Then adjust the pH of the suspension to 7 - 8 with 10% NH4HCO3 aqueous solution. Place the suspension in a 70°C water bath and stir and heat for crystallization for 1 h;

[0123] S3. Filter and wash the obtained solid powder after leaving it overnight, dry it in an oven at 75°C for 6 h, then calcine it at 300°C for 3 h. After the calcination is completed, press it into tablets and reduce it at 250°C for 3 h in a hydrogen atmosphere to obtain the catalyst.

[0124] The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, the tungsten content is 1.5%, and the remaining component is the support alumina.

[0125] Comparative Example 3

[0126] First, weigh 19.6 g of alumina support for standby. Then weigh 1.49 g of Ni(NO3)2.6H2O into a 150 mL beaker, add 18 mL of deionized water to stir and dissolve it. Then place it in a 70°C water bath, add the dried alumina support and stir evenly. After the surface moisture has completely evaporated, put it in an oven at 75°C for drying treatment for 6 h. Calcinate the obtained solid powder at 500°C for 3 h. Then weigh 0.27 g of RuCl3.xH2O into a 150 mL beaker, add 18 mL of deionized water to dissolve it completely, add the calcined solid powder and stir evenly. Then place it in a 70°C water bath and heat and stir to make the active component loading more uniform. After the surface moisture has completely evaporated, put it in an oven at 75°C for drying for 6 h. Calcinate the obtained solid powder at 300°C for 3 h. After the calcination is completed, press it into tablets and reduce it at 250°C for 3 h in a hydrogen atmosphere to obtain the catalyst. The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, and the remaining component is the support alumina.

[0127] Comparative Example 3

[0128] S1. Weigh 19.6 g of alumina support for standby. Then weigh 1.49 g of Ni(NO3)2·6H2O into a 150 mL beaker and add 18 mL of deionized water to stir and dissolve it;

[0129] S2. Place the dried Al2O3 support in a 70 °C water bath, stir evenly, and after the surface moisture has completely evaporated, place it in a 75 °C oven for drying for 6 h;

[0130] S3. Calcinate the obtained solid powder at 500 °C for 3 h. Then, weigh 0.27 g of RuCl3·xH2O into a 150 mL beaker, add 18 mL of deionized water to dissolve it completely, and then add the calcined solid powder and stir evenly;

[0131] S4. Place it in a 70 °C water bath, heat and stir to make the loading of the active component more uniform. After the surface moisture has completely evaporated, place it in a 75 °C oven for drying for 6 h;

[0132] S5. Calcinate the obtained solid powder at 300 °C for 3 h. After the calcination, press it into tablets and reduce it at 250 °C for 3 h under a hydrogen atmosphere to obtain the catalyst.

[0133] The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, and the remaining components are the carrier alumina.

[0134] Comparative Example 4

[0135] S1. Weigh 19.3 g of alumina support for standby. Then, weigh 1.49 g of Ni(NO3)2·6H2O and 0.27 g of RuCl3·xH2O into a 150 mL beaker, and add 18 mL of deionized water and stir to dissolve;

[0136] S2. Place it in a 70 °C water bath, add the dried Al2O3 support and stir evenly. After the surface moisture has completely evaporated, place it in a 75 °C oven for drying for 6 h and then calcinate it at 300 °C for 3 h;

[0137] S3. After the calcination, reduce it at 250 °C for 3 h under a hydrogen atmosphere to obtain the catalyst.

[0138] The mass content of the active component ruthenium is 0.5%, the nickel content is 1.5%, and the remaining components are the carrier alumina.

[0139] Comparative Example 5

[0140] S1. Weigh 19.3 g of alumina support for standby. Then, weigh (NH4)H2W 12 O 40 .xH2O 0.40 g and 0.27 g of RuCl3·xH2O into a 150 mL beaker, and add 50 mL of deionized water and stir to dissolve;

[0141] S2. Slowly add the dried Al2O3 support all at once and stir evenly. Then, adjust the pH of the suspension to 7 - 8 with 10% NH4HCO3 aqueous solution. Place the suspension in a 70 °C water bath and stir and heat for crystallization for 1 h;

[0142] S3. Filter and wash the obtained solid powder after overnight, dry it in an oven at 75 °C for 6 h, then calcine it at 300 °C for 3 h. After the calcination is completed, press it into tablets and reduce it at 250 °C for 3 h in a hydrogen atmosphere to obtain the catalyst.

[0143] The mass content of the active component ruthenium is 0.5%, the content of tungsten is 1.5%, and the remaining components are the carrier alumina.

[0144] Comparative Example 6

[0145] S1. Weigh 19.9 g of alumina carrier for standby. Then weigh 0.27 g of RuCl3·xH2O into a 150 mL beaker, add 18 mL of deionized water to dissolve it completely, and then add the dried Al2O3 carrier and stir.

[0146] S2. Place it in a water bath at 70 °C and heat with stirring to make the loading of the active component more uniform. After the surface moisture has completely evaporated, put it in an oven at 75 °C for drying treatment for 6 h.

[0147] S3. Calcinate the obtained solid powder at 300 °C for 3 h. After the calcination is completed, press it into tablets and reduce it at 250 °C for 3 h in a hydrogen atmosphere to obtain the catalyst.

[0148] The mass content of the active component ruthenium is 0.5%, and the remaining components are the carrier alumina.

[0149] Hydrogenation activity comparative test

[0150] Take 44.8 g of tetramethyl pyromellitate and dissolve it in 500 mL of 1,4-dioxane to prepare a solution with a mass fraction of 8% as the raw material for the hydrogenation reaction. Then load the catalyst into a single-tube fixed-bed reactor, set the programmed temperature rise and reduce it in a hydrogen atmosphere. After the reduction is completed, pump the raw material into the reactor through a metering pump. Reaction conditions: temperature 160 °C, pressure 4.5 MPa, liquid hourly space velocity 0.28 h -1 , the hydrogen-oil volume ratio is 696:1. After the reaction is stable, take samples for chromatographic analysis. The pore structure analysis and the evaluation of the hydrogenation performance of the catalyst under different loading, calcination conditions and preparation methods are compared as follows.

[0151] Table 4. Pore structure analysis of the catalysts in Comparative Examples 1 - 6

[0152] Catalyst <![CDATA[Specific surface area m 2 / g]]> <![CDATA[Pore volume cm 3 / g]]> Pore diameter 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[Support Al2O3]]> 228.29 0.61 8.27

[0153] Table 5. Catalyst composition and preparation in Comparative Examples 1 - 6

[0154]

[0155] Table 6. Hydrogenation activity evaluation of the catalysts in Comparative Examples 1 - 6

[0156] 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

[0157] As described above, it is only the 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 the preferred embodiment, it is not intended to limit the present invention. Any person skilled in the art, within 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, as long as it does not depart from the content of the technical solution of the present invention, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A preparation method of a ruthenium-based double-promoter hydrogenation catalyst, characterized in that, Using Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 ·xH2O, the Al2O3 support is modified by precipitation deposition method and then calcined to obtain a metal-modified support; then, ruthenium is loaded on the metal-modified support by impregnation method and then calcined, and the hydrogenation catalyst is obtained after hydrogen reduction; Among them, 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 remaining component is an alumina support; The BET specific surface area of the hydrogenation catalyst after calcination is 190-210 m 2 / g, the pore volume is 0.5-0.6 mL / g, and the pore diameter is 7.5-8.5 nm; the hydrogenation catalyst is used in the hydrogenation process of tetramethyl pyromellitate, and the process conditions of the hydrogenation process are: temperature 150-180 °C, pressure 3.5-5.5 MPa, liquid hourly space velocity 0.18-0.28 h -1 .

2. The preparation method of a ruthenium-based double-promoter hydrogenation catalyst according to claim 1, characterized in that, The specific operation of the precipitation deposition method is as follows: Dissolve Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 ·xH2O in water to obtain a mixed solution, and add the Al2O3 support to the mixed solution and heat it for crystallization.

3. The preparation method of a ruthenium-based double-promoter hydrogenation catalyst according to claim 1 or 2, characterized in that, The specific operation of the impregnation method is as follows: Dissolve RuCl3·xH2O in water, add a metal-modified support, and heat and stir to make the ruthenium loading uniform.

4. The preparation method of a ruthenium-based double-promoter hydrogenation catalyst according to claim 1, characterized in that, The Al2O3 support is prepared by modifying a mixture of pseudo-boehmite, citric acid, carboxymethyl cellulose, and water.

5. The preparation method of a ruthenium-based double-promoter hydrogenation catalyst according to claim 1, characterized in that, The BET specific surface area of the Al2O3 support is 220.00 - 230.00 m 2 / g, the pore volume is 0.55 - 0.65 mL / g, and the pore diameter is 8.1 - 8.3 nm.

6. The preparation method of a ruthenium-based double-promoter hydrogenation catalyst according to claim 3, characterized in that, The content of Ru in RuCl3·xH2O is 35.0 - 37.0%.

7. The preparation method of a ruthenium-based double-promoter hydrogenation catalyst according to claim 1, characterized in that, The (NH4)H2W 12 O 40 ·xH2O contains 74.6% of W by weight.

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