Preparation method of tetrahydrofuran hydrogenation catalyst
By functionalizing MOF support and microwave-assisted palladium nanoparticles, the problem of insufficient activity and stability of tetrahydrofuran hydrogenation catalyst is solved, and efficient catalytic effect is achieved under low temperature and low pressure, which is suitable for industrial production.
Patent Information
- Application Number
- CN202510629681.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-16
- Publication Date
- 2025-08-19
AI Technical Summary
The existing tetrahydrofuran hydrogenation catalysts have problems such as poor catalytic activity, low selectivity and insufficient stability. The traditional methods require high temperature and high pressure conditions to increase energy consumption and accelerate catalyst deactivation.
The in-situ synthesis of functionalized MOF carriers and microwave-assisted palladium nanoparticles are used to improve the activity, selectivity and stability of the catalyst by introducing specific organic ligands and additives.
The rate and selectivity of the tetrahydrofuran hydrogenation reaction were significantly improved under low temperature and low pressure conditions, the selectivity of the target product reached more than 99%, the stability of the catalyst was significantly improved, and the service life was extended.
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Abstract
Description
Technical Field
[0001] The present invention relates to the field of tetrahydrofuran catalysts, in particular to a method for preparing a tetrahydrofuran hydrogenation catalyst. Background Art
[0002] Tetrahydrofuran (THF), an extremely important organic solvent, is widely used in fields such as polymer synthesis, pharmaceutical chemistry, and solvent extraction. Due to its excellent solubility and low toxicity, THF is often used as a solvent in synthetic reactions, a catalyst solution medium, and a battery electrolyte. However, in the industrial production of THF, due to its presence of unsaturated compounds and small amounts of impurities, it is often hydrogenated through a hydrogenation reaction to remove harmful substances and improve its purity and stability.
[0003] The hydrogenation of tetrahydrofuran (THF) is typically carried out using metal catalysts, most of which are based on precious metals (such as platinum, palladium, and rhodium) or transition metals (such as nickel and copper). Precious metal catalysts have demonstrated excellent performance in the hydrogenation of THF due to their excellent catalytic activity and selectivity, but their high cost and susceptibility to deactivation limit their application in industrial processes. In contrast, transition metal catalysts (such as nickel catalysts) are relatively economical, but they have lower catalytic efficiency and selectivity and are prone to deactivation over extended periods of use, resulting in a decrease in reaction activity and impacting production efficiency and product quality.
[0004] Currently, research on tetrahydrofuran hydrogenation catalysts focuses on two main areas: improving their activity and selectivity through the development of new metal catalysts, and extending their service life through optimizing their structure and preparation processes. Existing catalyst preparation methods typically include metal precursor impregnation, coprecipitation, and sol-gel methods. Metal precursor impregnation is widely used in catalyst preparation due to its simplicity and low cost.
[0005] Although existing catalysts have good catalytic effects in the short term, their stability and reusability are poor due to the easy aggregation or poisoning of the metal particles in the catalysts. Therefore, how to improve the stability of the catalyst and the sustainability of the reaction by adjusting the metal loading of the catalyst, the properties of the support, and the surface modification technology remains a key issue in catalyst research.
[0006] Furthermore, conventional catalysts typically require higher reaction temperatures and pressures to achieve optimal hydrogenation results. However, these high-temperature, high-pressure reaction conditions not only increase energy consumption but can also accelerate catalyst deactivation. Therefore, optimizing the performance of tetrahydrofuran hydrogenation catalysts by enhancing catalyst activity and selectivity while minimizing catalyst deactivation under low-temperature, low-pressure conditions is crucial.
[0007] In summary, existing THF hydrogenation catalysts suffer from poor catalytic activity, low selectivity, and insufficient stability. There is an urgent need to develop a new catalyst that can both enhance catalytic activity and extend service life. Furthermore, the catalyst preparation method should be simple, efficient, and low-cost to meet the needs of industrial large-scale production. Summary of the Invention
[0008] In order to overcome at least one of the technical problems in the above background technology, the present invention proposes a method for preparing a tetrahydrofuran hydrogenation catalyst, and the specific scheme is as follows:
[0009] A method for preparing a tetrahydrofuran hydrogenation catalyst comprises the following steps:
[0010] Step 1: In situ synthesis of a functionalized MOF support: 50-150 parts by weight of zirconium nitrate, 40-120 parts by weight of terephthalic acid, 10-30 parts by weight of 2-dihydroxyboryl-3-thiophenecarboxylic acid (CAS No.: 519054-53-6) and 0.06-0.5 parts by weight of 2-propenylthio-2-thiazoline (CAS No.: 3571-74-2) are added to 400-600 parts by weight of N,N-dimethylformamide (DMF); after being fully stirred, the mixture is transferred to a reactor and crystallized for 20-28 hours; after the reaction is completed, the N,N-dimethylformamide is distilled off and recovered, and the synthesized product is washed with ethanol three times, then dried at 100-140°C for 4-8 hours, and then transferred to a high-temperature furnace for calcination for 2-4 hours to remove the template and impurities to obtain a functionalized MOF support;
[0011] Step 2: Microwave-assisted palladium nanoparticle loading: dissolve 1-10 parts by weight of palladium chloride in 80-200 parts by weight of ethanol and stir for 10-50 minutes to form a uniform metal precursor solution; add the functionalized MOF support obtained in step 1 to the solution and soak for 0.5-3 hours while turning on microwave assistance at a microwave frequency of 2.45 GHz for 5-15 minutes;
[0012] Step 3: After the impregnation is completed, the support is dried at 80-140° C. for 2-4 hours to remove the ethanol solvent, thereby finally obtaining a tetrahydrofuran hydrogenation catalyst.
[0013] In an embodiment of the present invention, the crystallization temperature in step 1 is 100-140°C.
[0014] In an embodiment of the present invention, the calcination temperature in step 1 is 200-300°C.
[0015] In an embodiment of the present invention, the immersion temperature in step 2 is 20-60°C.
[0016] In an embodiment of the present invention, the microwave power in step 2 is 100-500W.
[0017] In an embodiment of the present invention, the drying temperature in step 3 is 80-140°C.
[0018] The catalyst obtained above is applied to the hydrogenation reaction of tetrahydrofuran.
[0019] Beneficial effects:
[0020] 1. High Activity: The MOF support was functionalized by introducing 2-dihydroxyboryl-3-thiophenecarboxylic acid and 2-propenylthio-2-thiazoline, creating abundant active sites and a unique electronic environment. The activation of the CO bond by the boron groups and the adsorption of reactants by the thiophene and thiazoline groups, combined with the synergistic catalysis of palladium nanoparticles, significantly increased the rate of tetrahydrofuran hydrogenation.
[0021] 2. High Selectivity: The unique structure and surface properties of the functionalized MOF support enable the catalyst to selectively adsorb and activate tetrahydrofuran molecules, inhibiting the occurrence of side reactions. In the tetrahydrofuran hydrogenation reaction, the selectivity of the target product can reach over 99%, greatly improving the purity and quality of the product.
[0022] 3. High stability: The calcination process forms a stable interface structure between the palladium nanoparticles and the functionalized MOF support, effectively inhibiting the aggregation and loss of palladium nanoparticles. At the same time, the presence of functional groups enhances the structural stability of the MOF support. DETAILED DESCRIPTION
[0023] The following examples are provided for a better understanding of the present invention and are not intended to limit the best mode of implementation. They do not limit the content and scope of protection of the present invention. Any product identical or similar to the present invention obtained by anyone under the guidance of the present invention or by combining the features of the present invention with other prior arts shall fall within the scope of protection of the present invention.
[0024] If no specific experimental steps or conditions are specified in the examples, the conventional experimental steps or conditions described in the literature in this field can be used. If the manufacturer of the reagents or instruments is not specified, they are all commercially available conventional reagents.
[0025] Example 1
[0026] A preparation method of tetrahydrofuran hydrogenation catalyst
[0027] Step 1: In situ synthesis of functionalized MOF supports
[0028] 50 g of zirconium nitrate, 40 g of terephthalic acid, 10 g of 2-dihydroxyboryl-3-thiophenecarboxylic acid (CAS No.: 519054-53-6) and 0.06 g of 2-propenylthio-2-thiazoline (CAS No.: 3571-74-2) were added together to 400 g of N,N-dimethylformamide (DMF).
[0029] After being fully stirred, the mixture was transferred to a reactor and crystallized at 100° C. for 20 hours.
[0030] After the reaction, N,N-dimethylformamide was distilled off and recovered, and the synthesized product was washed with ethanol three times, then dried at 100°C for 4 hours, and then transferred to a high-temperature furnace and calcined at 200°C for 2 hours to remove the template and impurities to obtain a functionalized MOF carrier.
[0031] Step 2: Microwave-assisted loading of palladium nanoparticles
[0032] Dissolve 1 g of palladium chloride in 80 g of ethanol and stir for 10 minutes to form a uniform metal precursor solution.
[0033] The functionalized MOF support obtained in step 1 was added to the solution and immersed at 20° C. for 0.5 h. Meanwhile, microwave assistance was turned on with a microwave frequency of 2.45 GHz, a microwave power of 100 W, and a treatment time of 5 min.
[0034] Step 3:
[0035] After the impregnation was completed, the support was dried at 80° C. for 2 hours to remove the ethanol solvent, thereby finally obtaining a tetrahydrofuran hydrogenation catalyst.
[0036] Example 2
[0037] A preparation method of tetrahydrofuran hydrogenation catalyst
[0038] Step 1: In situ synthesis of functionalized MOF supports
[0039] 100 g of zirconium nitrate, 80 g of terephthalic acid, 20 g of 2-dihydroxyboryl-3-thiophenecarboxylic acid (CAS No.: 519054-53-6) and 0.25 g of 2-propenylthio-2-thiazoline (CAS No.: 3571-74-2) were added together to 500 g of N,N-dimethylformamide (DMF).
[0040] After being fully stirred, the mixture was transferred to a reactor and crystallized at 120°C for 24 hours.
[0041] After the reaction, N,N-dimethylformamide was distilled off and recovered, and the synthesized product was washed with ethanol three times, then dried at 120°C for 6 hours, and then transferred to a high-temperature furnace and calcined at 250°C for 3 hours to remove the template and impurities to obtain a functionalized MOF carrier.
[0042] Step 2: Microwave-assisted loading of palladium nanoparticles
[0043] 5 g of palladium chloride was dissolved in 150 g of ethanol and stirred for 30 minutes to form a uniform metal precursor solution.
[0044] The functionalized MOF carrier obtained in step 1 was added to the solution and immersed at 40° C. for 2 hours. Meanwhile, microwave assistance was turned on with a microwave frequency of 2.45 GHz, a microwave power of 300 W, and a treatment time of 10 minutes.
[0045] Step 3:
[0046] After the impregnation was completed, the support was dried at 110° C. for 3 hours to remove the ethanol solvent, thereby finally obtaining a tetrahydrofuran hydrogenation catalyst.
[0047] Example 3
[0048] A preparation method of tetrahydrofuran hydrogenation catalyst
[0049] Step 1: In situ synthesis of functionalized MOF supports
[0050] 150 g of zirconium nitrate, 120 g of terephthalic acid, 30 g of 2-dihydroxyboryl-3-thiophenecarboxylic acid (CAS No.: 519054-53-6) and 0.5 g of 2-propenylthio-2-thiazoline (CAS No.: 3571-74-2) were added together to 600 g of N,N-dimethylformamide (DMF).
[0051] After being fully stirred, the mixture was transferred to a reactor and crystallized at 140° C. for 28 hours.
[0052] After the reaction, N,N-dimethylformamide was distilled off and recovered, and the synthesized product was washed with ethanol three times, then dried at 140°C for 8 hours, and then transferred to a high-temperature furnace and calcined at 300°C for 4 hours to remove the template and impurities to obtain a functionalized MOF carrier.
[0053] Step 2: Microwave-assisted loading of palladium nanoparticles
[0054] 10 g of palladium chloride was dissolved in 200 g of ethanol and stirred for 50 minutes to form a uniform metal precursor solution.
[0055] The functionalized MOF carrier obtained in step 1 was added to the solution and immersed at 60° C. for 3 hours. Meanwhile, microwave assistance was turned on with a microwave frequency of 2.45 GHz, a microwave power of 500 W, and a treatment time of 15 minutes.
[0056] Step 3:
[0057] After the impregnation was completed, the support was dried at 140° C. for 4 hours to remove the ethanol solvent, thereby finally obtaining a tetrahydrofuran hydrogenation catalyst.
[0058] Example 4
[0059] A preparation method of tetrahydrofuran hydrogenation catalyst
[0060] Step 1: In situ synthesis of functionalized MOF supports
[0061] 80 g of zirconium nitrate, 60 g of terephthalic acid, 15 g of 2-dihydroxyboryl-3-thiophenecarboxylic acid (CAS No.: 519054-53-6) and 0.1 g of 2-propenylthio-2-thiazoline (CAS No.: 3571-74-2) were added together to 450 g of N,N-dimethylformamide (DMF).
[0062] After being fully stirred, the mixture was transferred to a reactor and crystallized at 110° C. for 22 hours.
[0063] After the reaction, N,N-dimethylformamide was distilled off and recovered, and the synthesized product was washed with ethanol three times, then dried at 110°C for 5 hours, and then transferred to a high-temperature furnace and calcined at 220°C for 2.5 hours to remove the template and impurities to obtain a functionalized MOF carrier.
[0064] Step 2: Microwave-assisted loading of palladium nanoparticles
[0065] 3 g of palladium chloride was dissolved in 100 g of ethanol and stirred for 20 minutes to form a uniform metal precursor solution.
[0066] The functionalized MOF carrier obtained in step 1 was added to the solution and immersed at 30° C. for 1 hour. Meanwhile, microwave assistance was turned on with a microwave frequency of 2.45 GHz, a microwave power of 200 W, and a treatment time of 8 minutes.
[0067] Step 3:
[0068] After the impregnation was completed, the support was dried at 100° C. for 2.5 hours to remove the ethanol solvent, thereby finally obtaining a tetrahydrofuran hydrogenation catalyst.
[0069] Comparative Example 1
[0070] This example is a comparative example of Example 1. Except that 2-dihydroxyboryl-3-thiophenecarboxylic acid is not added, the rest is the same as Example 1.
[0071] Comparative Example 2
[0072] This example is a comparative example of Example 1. Except for not adding 2-propenylthio-2-thiazoline, the rest is the same as Example 1.
[0073] Test Method
[0074] 1. Catalytic activity test
[0075] Reaction conditions:
[0076] Reactants: Tetrahydrofuran (THF)
[0077] Catalyst dosage: 0.1g
[0078] Solvent: ethanol (10 mL)
[0079] Hydrogen pressure: 1MPa
[0080] Reaction temperature: 100°C
[0081] Reaction time: 2 hours
[0082] Analytical methods:
[0083] After the reaction, the product was analyzed by gas chromatography (GC) to calculate the conversion rate of tetrahydrofuran and the selectivity of the target product.
[0084] 2. Catalyst stability test
[0085] Reuse test:
[0086] Under the above reaction conditions, the reaction cycle was carried out five times continuously. After each reaction, the catalyst was recovered, washed, dried and reused. The conversion rate and selectivity were recorded.
[0087] Table 1: Test results of Examples and Comparative Examples
[0088]
[0089] In summary, the catalyst of the present invention exhibits excellent catalytic performance in the hydrogenation reaction of tetrahydrofuran and has good industrial application prospects.
[0090] Obviously, the above embodiments are merely examples for clarity of explanation and are not intended to limit the implementation methods. Those skilled in the art will readily appreciate that other variations or modifications based on the above descriptions are possible. It is not necessary and impossible to enumerate all implementation methods here. Obvious variations or modifications arising therefrom remain within the scope of protection of the present invention.
Claims
1. A method for preparing a tetrahydrofuran hydrogenation catalyst, characterized in that: The method comprises the following steps: Step 1: In situ synthesis of a functionalized MOF support: 50-150 parts by weight of zirconium nitrate, 40-120 parts by weight of terephthalic acid, 10-30 parts by weight of 2-dihydroxyboryl-3-thiophenecarboxylic acid, and 0.06-0.5 parts by weight of 2-propenylthio-2-thiazoline are added to 400-600 parts by weight of N,N-dimethylformamide; after being thoroughly stirred, the mixture is transferred to a reactor and crystallized for 20-28 hours; after the reaction is completed, the N,N-dimethylformamide is distilled off and recovered, and the synthesized product is washed three times with ethanol, then dried at 100-140°C for 4-8 hours, and then transferred to a high-temperature furnace for calcination for 2-4 hours to remove the template and impurities to obtain a functionalized MOF support; Step 2: Microwave-assisted palladium nanoparticle loading: dissolve 1-10 parts by weight of palladium chloride in 80-200 parts by weight of ethanol and stir for 10-50 minutes to form a uniform metal precursor solution; add the functionalized MOF support obtained in step 1 to the solution and soak for 0.5-3 hours while turning on microwave assistance at a microwave frequency of 2.45 GHz for 5-15 minutes; Step 3: After the impregnation is completed, the support is dried at 80-140° C. for 2-4 hours to remove the ethanol solvent, thereby finally obtaining a tetrahydrofuran hydrogenation catalyst.
2. The preparation method of a tetrahydrofuran hydrogenation catalyst according to claim 1, wherein: The crystallization temperature in step 1 is 100-140°C.
3. The preparation method of a tetrahydrofuran hydrogenation catalyst according to claim 1, wherein: The calcination temperature in step 1 is 200-300°C.
4. The preparation method of a tetrahydrofuran hydrogenation catalyst according to claim 1, wherein: The immersion temperature in step 2 is 20-60°C.
5. The preparation method of a tetrahydrofuran hydrogenation catalyst according to claim 1, wherein: The microwave power in step 2 is 100-500W.
6. The preparation method of a tetrahydrofuran hydrogenation catalyst according to claim 1, wherein: The drying temperature in step 3 is 80-140°C.
7. A method for preparing a tetrahydrofuran hydrogenation catalyst according to claim 1-6, characterized in that: The obtained catalyst is applied to tetrahydrofuran hydrogenation reaction.