Preparation method of high-activity bisphenol A hydrogenation catalyst
By introducing fourth-period transition metal salts into ruthenium-based catalysts to form "island" structures, the problem of ruthenium agglomeration is solved, the metal utilization and catalytic activity of the catalyst are improved, the cost is reduced, and the stability of the catalyst is enhanced.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- PETROCHINA CO LTD
- Filing Date
- 2024-11-08
- Publication Date
- 2026-05-12
AI Technical Summary
Existing precious metal catalysts tend to agglomerate in the hydrogenation reaction of bisphenol A, resulting in low metal utilization, affecting catalytic activity and stability. Furthermore, traditional modification methods are either costly or environmentally unfriendly.
Fourth-period transition metal salts are used as protective agents and auxiliaries to interact with ruthenium, forming "island" structures to avoid aggregation. Through heat treatment and reduction, highly active bisphenol A hydrogenation catalysts are formed, improving the dispersibility and utilization of ruthenium.
It improves the metal utilization rate and catalytic activity of the catalyst, reduces the cost of precious metals, and enhances the stability and reaction conversion rate of the catalyst.
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Abstract
Description
Technical Field
[0001] This invention belongs to the field of chemical monomer hydrogenation catalysts, specifically relating to a method for preparing a highly active bisphenol A hydrogenation catalyst. Background Technology
[0002] Hydrogenated bisphenol A, the hydrogenation product of bisphenol A, can replace it in the production of polymer materials such as polycarbonate and epoxy resin. In the presence of a catalyst, the two benzene rings of bisphenol A are continuously hydrogenated to obtain hydrogenated bisphenol A. Noble metal supported catalysts such as ruthenium are commonly used for this reaction. As industrial requirements for catalytic processes and product quality continue to increase, the performance requirements for catalysts are also constantly being updated.
[0003] Precious metals increase the cost of catalysts due to their scarcity and high value. Furthermore, because of their high surface energy, precious metal atoms tend to agglomerate on catalysts, forming large metal clusters that reduce metal utilization and thus severely affect catalyst activity.
[0004] In existing technologies, catalysts can be modified to meet their application requirements, including optimizing the metal active sites, modifying and improving the support materials, and introducing new functional components. Therefore, modifying ruthenium-based catalysts to maintain higher reactivity at lower loading levels is of significant importance and practical application value.
[0005] Chinese patent CN202111345207.9 describes a process where a zinc-aluminum hydrotalcite dispersion is mixed with a ruthenium source solution and an alkaline solution, followed by crystallization. The resulting precursor is then reduced in a reducing gas atmosphere to obtain a Ru-Zn hydrogenation catalyst. In the catalytic hydrogenation alkylation of benzene to cyclohexylbenzene, the benzene conversion rate can reach 76.65%, and the selectivity for cyclohexylbenzene can reach 80.39%. However, the ruthenium hydroxide precipitate formed under alkaline conditions tends to form large metal clusters without protection, and the metal particles are deposited on the support through physical forces. These forces are relatively weak and detrimental to the catalyst's stability.
[0006] Chinese patent CN201710760364.3 describes a method involving adding an organic modifier to an alcoholic solution of Ru and Ni metal precursors, adjusting the pH with NaOH, and then reacting with a hydrogen peroxide-lithium aluminum hydride-ethanol solution at a specific temperature to obtain a ruthenium / nickel alloy nanocatalyst. This nanocatalyst exhibits high activity and stability in the catalytic hydrogenation of 1-nitroanthraquinone to 1-aminoanthraquinone. However, this method uses NaOH as a pH adjuster, which generates alkaline waste liquid and is environmentally unfriendly.
[0007] Chinese patent CN201310080626.3 describes the preparation of ruthenium and palladium metal solutions, which were then impregnated onto an alumina support and subsequently calcined to obtain a supported ruthenium-palladium bimetallic hydrogenation catalyst. This catalyst was applied to the selective hydrogenation of dimethyl terephthalate to dimethyl 1,4-cyclohexanedicarboxylate, exhibiting good activity and a high CHDM yield. However, the catalyst's metal components, being both ruthenium and palladium, are not only expensive but also prone to agglomeration due to the lack of pre-calcination protection.
[0008] Chinese patent CN202211652631.2, which combines Ni(NO3)2·6H2O and (NH4)H2W 12 O 40 A hydrogenation catalyst consisting of three metals was obtained by adding xH2O solution to NH4HCO3 solution to deposit it on an Al2O3 support, followed by calcination, impregnation with ruthenium metal, and then calcination and reduction. This catalyst was then applied to the catalytic hydrogenation of tetramethyl pyromellitic acid. However, in this method, the nickel and tungsten salts form stable oxides after calcination, which are difficult to interact with the ruthenium salts that have been impregnated twice. Furthermore, the two-stage calcination process consumes a significant amount of energy. Summary of the Invention
[0009] The purpose of this invention is to provide a method for preparing a highly active bisphenol A hydrogenation catalyst, which improves the metal utilization rate of Ru and contributes to the catalytic activity of the catalyst.
[0010] To achieve the above objectives, the present invention provides a method for preparing a highly active bisphenol A hydrogenation catalyst, the method comprising the following steps:
[0011] Step 1: Weigh the transition metal salt of the fourth period of the periodic table, add it to a mixed solvent of alcohol and deionized water, stir well, and prepare a homogeneous solution.
[0012] Step 2: Weigh the ruthenium-containing compound, add the accelerator, and add deionized water to prepare a homogeneous solution;
[0013] Step 3: Mix the solutions from Step 1 and Step 2 thoroughly and allow them to react to obtain the reaction solution;
[0014] Step 4: Weigh the alumina and add the reaction solution from Step 3 into the alumina to complete the impregnation process;
[0015] Step 5: Heat-treat the sample obtained in Step 4 to obtain the hydrogenation catalyst precursor;
[0016] Step 6: Reduce the hydrogenation catalyst precursor obtained in Step 5 to obtain a reduced highly active bisphenol A hydrogenation catalyst.
[0017] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the transition metal salt of the fourth period of the periodic table is an iron salt and / or a zinc salt.
[0018] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the iron salt is one or more of ferric nitrate, ferric monosodium ethylenediaminetetraacetic acid salt hydrate, ferric ammonium oxalate, ferrous fumarate, and ferric acetylacetone.
[0019] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the zinc salt is one or more of zinc nitrate, zinc diethyldithiocarbamate, zinc acetate, and zinc N-ethyl-N-phenyldithiocarbamate.
[0020] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the alcohol includes methanol and / or ethanol.
[0021] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the alcohol accounts for 25wt%-80wt% of the total solvent in the mixed solvent of alcohol and deionized water.
[0022] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention includes a ruthenium-containing compound comprising one or two of ruthenium nitrite and ruthenium trichloride.
[0023] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the ruthenium accounts for 0.1 wt%-0.3 wt% of the highly active bisphenol A hydrogenation catalyst.
[0024] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the promoter is one or more of isopropanol, n-butanol, sorbitol, and glucose.
[0025] The preparation method of the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the molar amount of the promoter added ranges from 0.0020 to 0.0056 mol.
[0026] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention, wherein the content of the transition metal salt in the fourth period of the periodic table is such that the molar ratio of metal element M to ruthenium element Ru is 5-20.
[0027] In the preparation method of the highly active bisphenol A hydrogenation catalyst of the present invention, in step 3, the reaction temperature is 25-60℃ and the time is 2-8h; preferably, magnetic stirring or mechanical stirring is used during the reaction.
[0028] In the preparation method of the highly active bisphenol A hydrogenation catalyst of the present invention, in step 4, the drying temperature is 20-100℃ and the time is 4-24h; the present invention does not particularly limit the impregnation method in step 4, including but not limited to impregnation methods such as equal volume impregnation and multiple volume impregnation. Preferably, the impregnation is carried out under ultrasonic conditions for 10-30min.
[0029] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention involves a heat treatment temperature of 150-350°C for 2-6 hours, under an atmosphere of air or N2.
[0030] The method for preparing the highly active bisphenol A hydrogenation catalyst of the present invention involves reduction being carried out under an H2 atmosphere at a temperature of 150-300°C for 1-6 hours.
[0031] This invention aims to provide a method for preparing a highly active ruthenium-based hydrogenation catalyst for the reaction process of BPA to HBPA. The preparation method utilizes a fourth-period transition metal salt as a protective agent and promoter. Through interaction with metallic ruthenium, the catalyst surrounds the ruthenium, isolating it like an "island." This "island effect" effectively avoids or reduces the migration and aggregation of metallic ruthenium. Simultaneously, the transition metal's ability to dissociate H2 also contributes to the hydrogenation effect.
[0032] In the continuous hydrogenation production of HBPA, ruthenium-based supported catalysts are commonly used. However, without protection of the ruthenium particles, they easily agglomerate, forming large metal clusters. This reduces the effective utilization of the metal and negatively impacts the catalyst's activity and reaction conversion. This invention introduces a promoter and a fourth-period transition metal salt into the ruthenium salt solution during the conventional impregnation method. This interaction enriches the Ru atoms with transition metal, isolating them like "islands." Furthermore, the M-Ru structure formed after heat treatment has a higher Thyman temperature than single ruthenium metal, raising the temperature threshold for Ru atom migration and broadening the applicable reaction temperature range. Simultaneously, the fourth-period transition metal oxide also dissociates H2, providing a hydrogen-rich environment during the reaction and enhancing the catalyst's hydrogenation activity. Additionally, the Lewis acid sites introduced by the transition metal facilitate reactant adsorption, further improving the catalytic effect.
[0033] The method for preparing a highly active bisphenol A hydrogenation catalyst provided by this invention uses a fourth-period transition metal salt as a protectant and promoter to interact with Ru, promoting its dispersion in the form of "islands" and reducing its aggregation by forming a bimetallic structure. This improves the metal utilization of Ru and contributes to the catalytic activity of the catalyst. Detailed Implementation
[0034] The following provides a detailed description of the embodiments of the present invention: These embodiments are implemented based on the technical solution of the present invention, and provide detailed implementation methods and processes. However, the scope of protection of the present invention is not limited to the following embodiments. Experimental methods in the following embodiments that do not specify specific conditions are generally performed under conventional conditions.
[0035] Example 1
[0036] Weigh 2.40 g of ferric nitrate nonahydrate, add it to a mixed solvent of 8 g ethanol and 7 g deionized water, and stir to form a homogeneous solution. Weigh 0.34 g of isopropanol, add it to 15 g of deionized water and stir until homogeneous. Add 0.080 g of ruthenium trichloride hydrate to form a homogeneous solution. Mix the two solutions and react them at a constant temperature of 35 °C for 6 hours with magnetic stirring.
[0037] Weigh 10g of alumina, add it to the mixture, and sonicate for 10min. Dry at 20℃ for 24h, then treat in a muffle furnace at 150℃ in air for 6h. Reduce at 300℃ in hydrogen atmosphere for 2h to obtain reduced Ru catalyst cal-1.
[0038] Example 2
[0039] Weigh 0.268 g of zinc diethyldithiocarbamate, add it to a mixed solvent of 2.5 g methanol and 5 g deionized water, and stir to form a homogeneous solution. Weigh 0.36 g of sorbitol, add it to 15 g of deionized water and stir until homogeneous. Add 1.0 mL of ruthenium nitrite nitrate solution to form a homogeneous solution. Mix the two solutions and react them at a constant temperature of 60 °C for 2 h using magnetic stirring.
[0040] Weigh 10g of alumina, add it to the mixed solution, and sonicate for 20min. Dry at 100℃ for 4h, then treat in a muffle furnace at 300℃ for 3h under N2 atmosphere. Reduce at 150℃ for 4h under hydrogen atmosphere to obtain reduced Ru catalyst cal-2.
[0041] Example 3
[0042] Weigh out 0.168 g of ferrous fumarate and 0.147 g of zinc nitrate, add them to a mixed solvent of 2.5 g of ethanol and 7.5 g of deionized water, and stir to form a homogeneous solution. Weigh out 0.11 g of n-butanol and 0.27 g of glucose, add 5 g of deionized water and stir until homogeneous, then add 0.0267 g of ruthenium trichloride hydrate to form a homogeneous solution. Mix the two solutions and react them at a constant temperature of 40 °C for 7 h using magnetic stirring.
[0043] Weigh 10g of alumina, add it to the mixture, and sonicate for 30min. Dry at 30℃ for 12h, then treat in a muffle furnace at 350℃ for 2h under N2 atmosphere. Reduce at 200℃ for 1h under hydrogen atmosphere to obtain reduced Ru catalyst cal-3.
[0044] Example 4
[0045] Weigh out 0.524 g of ferric acetylacetone and 0.88 g of zinc nitrate, add them to a mixed solvent of 8 g of ethanol and 2 g of deionized water, and stir to form a homogeneous solution. Weigh out 0.296 g of n-butanol, add 5 g of deionized water and stir until homogeneous, then add 0.080 g of ruthenium trichloride hydrate to form a homogeneous solution. Mix the two solutions and react them at a constant temperature of 25 °C for 8 hours with magnetic stirring.
[0046] Weigh 10g of alumina, add it to the mixture, and sonicate for 30min. Dry at 50℃ for 8h, then treat in a muffle furnace at 200℃ for 2h under air atmosphere. Reduce at 200℃ for 6h under hydrogen atmosphere to obtain the reduced Ru catalyst cal-4.
[0047] Comparative Example 1
[0048] Weigh 0.34 g of isopropanol, add 15 g of deionized water and stir until homogeneous. Add 0.080 g of hydrated ruthenium trichloride to form a homogeneous solution. React at a constant temperature of 35 °C for 6 h using magnetic stirring.
[0049] Weigh 10g of alumina, add it to the mixture, and sonicate for 10min. Dry at 20℃ for 24h, then treat in a muffle furnace at 150℃ in air for 6h. Reduce at 300℃ in hydrogen atmosphere for 2h to obtain reduced Ru catalyst d-1.
[0050] Comparative Example 2
[0051] The ruthenium catalyst prepared in Comparative Example 2 was prepared according to the method described in CN202211652631.2, by weighing 0.50 g of Ni(NO3)2·6H2O and 0.13 g of (NH4)H2W. 12 O 40 ·xH2O was dissolved in 50 mL of deionized water in a beaker by stirring. 19.7 g of alumina was added and stirred until homogeneous. The pH was adjusted to 7-8 using a 10% NH4HCO3 aqueous solution, and then heated in a 70°C water bath with stirring for 1 h. The solid powder was left overnight, filtered, washed, and dried in a 75°C oven for 6 h, followed by calcination in a muffle furnace at 400°C for 4 h to obtain support DS-1. 0.27 g of hydrated ruthenium trichloride was weighed and dissolved in 15 mL of deionized water. Support DS-1 was added, and the mixture was stirred thoroughly to complete the impregnation. The mixture was heated in a 70°C water bath with stirring until the surface moisture was completely evaporated, and then dried in a 75°C oven for 6 h. The powder sample was then calcined in a muffle furnace at 200°C for 3 h, pressed into tablets, and reduced at 200°C for 3 h under a hydrogen atmosphere to obtain reduced Ru catalyst d-2.
[0052] Table 1. Static chemisorption of CO by the highly active bisphenol A hydrogenation catalysts obtained in the embodiments and comparative examples of the present invention.
[0053]
[0054] Table 2. Activity of the highly active bisphenol A hydrogenation catalysts obtained in the embodiments and comparative examples of the present invention.
[0055]
[0056] The static chemisorption and catalytic activities of CO on the ruthenium catalysts obtained in Examples 1-4 and Comparative Examples 1 and 2 are shown in Tables 1 and 2. The data in the tables show that the preparation method of the present invention significantly improves the dispersion of the ruthenium catalyst, and the crystal size also shows a clear change in grain size. Meanwhile, the catalytic activity data in Table 2 demonstrate that the preparation method of the present invention, through the interaction between transition metal salts and Ru, improves Ru dispersion while also exhibiting a hydrogenation effect, thus achieving a high catalytic hydrogenation effect with a relatively low Ru loading. In contrast, the Ru dispersion in Comparative Example 1 is relatively low, resulting in poor catalyst activity. Comparative Example 2, utilizing Ni and W metal-modified supports, does not inherently possess the ability to improve Ru dispersion; its catalytic effect originates from the superposition of the hydrogenation capabilities of Ru and Ni / W. Although it exhibits high activity, its cost is higher than that of the examples of the present invention.
[0057] Of course, the present invention may have other various embodiments. Without departing from the spirit and essence of the present invention, those skilled in the art can make various corresponding changes and modifications according to the present invention, but these corresponding changes and modifications should all fall within the protection scope of the claims of the present invention.
Claims
1. A method for preparing a highly active bisphenol A hydrogenation catalyst, characterized in that, Includes the following steps: Step 1: Weigh the transition metal salt of the fourth period of the periodic table, add it to a mixed solvent of alcohol and deionized water, stir well, and prepare a homogeneous solution. Step 2: Weigh the ruthenium-containing compound, add the accelerator, and add deionized water to prepare a homogeneous solution; Step 3: Mix the solutions from Step 1 and Step 2 thoroughly and allow them to react to obtain the reaction solution; Step 4: Weigh the alumina and add the reaction solution from Step 3 into the alumina to complete the impregnation process; Step 5: Heat-treat the sample obtained in Step 4 to obtain the hydrogenation catalyst precursor; Step 6: Reduce the hydrogenation catalyst precursor obtained in Step 5 to obtain a reduced highly active bisphenol A hydrogenation catalyst.
2. The preparation method according to claim 1, characterized in that, The transition metal salts in the fourth period of the periodic table are iron salts and / or zinc salts.
3. The preparation method according to claim 2, characterized in that, The iron salt is one or more of ferric nitrate, ferric monosodium ethylenediaminetetraacetate salt hydrate, ferric ammonium oxalate, ferrous fumarate, and ferric acetylacetone; the zinc salt is one or more of zinc nitrate, zinc diethyldithiocarbamate, zinc acetate, and zinc N-ethyl-N-phenyldithiocarbamate.
4. The preparation method according to claim 1, characterized in that, The alcohol includes methanol and / or ethanol; the alcohol accounts for 25 wt% to 80 wt% of the total solvent in the mixed solvent of the alcohol and deionized water.
5. The preparation method according to claim 1, characterized in that, The ruthenium-containing compound includes one or two of ruthenium nitrite and ruthenium trichloride; the proportion of ruthenium in the highly active bisphenol A hydrogenation catalyst is 0.1 wt% to 0.3 wt%.
6. The preparation method according to claim 1, characterized in that, The accelerator is one or more of isopropanol, n-butanol, sorbitol, and glucose; the molar amount of the accelerator added ranges from 0.0020 to 0.0056 mol.
7. The preparation method according to claim 1, characterized in that, The content of the transition metal salt in the fourth period of the periodic table is such that the molar ratio of metal element M to ruthenium element Ru is 5-20.
8. The preparation method according to claim 1, characterized in that, In step 3, the reaction temperature is 25-60℃ and the time is 2-8 hours; In step 4, the drying temperature is 20-100℃ and the time is 4-24h, and the impregnation is carried out under ultrasonic conditions for 10-30min.
9. The preparation method according to claim 1, characterized in that, The heat treatment temperature is 150-350℃, the time is 2-6 hours, and the atmosphere is air or N2.
10. The preparation method according to claim 1, characterized in that, The reduction is carried out in an H2 atmosphere at a temperature of 150-300℃ for 1-6 hours.