Application of nickel-based organic metal framework catalyst in hydrogenation reaction
The nickel-based organometallic framework catalyst solves the problems of poor selectivity and high cost of existing catalysts in hydrogenation reactions, realizing efficient and low-cost hydrogenation reactions, and is suitable for catalytic applications of a variety of compounds.
Patent Information
- Application Number
- CN202511586327.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-11-01
- Publication Date
- 2026-02-24
AI Technical Summary
Existing catalysts suffer from poor selectivity, high cost, high energy consumption, and high safety risks in hydrogenation reactions. They are particularly ineffective when dealing with high concentrations of unsaturated double bonds and nitro compounds. Furthermore, traditional catalysts require frequent replacement, which increases production costs.
A nickel-based organometallic framework catalyst was prepared by reacting nickel salts with a linker and a solvent to catalyze the hydrogenation of compounds containing unsaturated double bonds and nitro groups at relatively low temperatures and pressures. The catalyst is easy to prepare and the products are easy to separate.
It enables efficient hydrogenation of high-concentration unsaturated double bonds and nitro compounds, reducing production costs, increasing product yield, reducing energy consumption and safety risks, and is applicable to the hydrogenation reaction of a variety of compounds.
Abstract
Description
Technical Field
[0001] This invention belongs to the field of organic catalysis and green hydrogenation technology, specifically relating to the application of a nickel-based organometallic framework catalyst in hydrogenation reactions. Background Technology
[0002] The hydrogenation reaction of unsaturated double bonds (carbon-carbon double bonds, carbon-nitrogen double bonds, carbon-oxygen double bonds) and the hydrogenation and deoxygenation reaction of nitro groups are core unit reactions in the field of organic synthesis. Their products (alkanes, amines, alcohols, etc.) are widely used in key industries such as pharmaceuticals, dyes, and biofuels, and play an irreplaceable role in the upgrading of the chemical industry.
[0003] The products of these two types of reactions cover multiple high-value-added fields: Hydrogenation of carbon-carbon double bonds is a key step in the preparation of fine chemical intermediates and the purification of polymer precursors; hydrogenation of carbon-nitrogen double bonds can synthesize pharmaceutical secondary / tertiary amines and azo precursors for dyes; hydrogenation of carbon-oxygen double bonds is a major route for alcohol preparation, such as tetrahydrofurfuryl alcohol, which is a key precursor for the synthesis of high-value-added chemicals such as γ-valerate and 1,5-pentanediol, and has development potential in the fields of bio-based materials and renewable energy. The thermal stability brought about by its hydrogenated structure makes it particularly outstanding in the synthesis of thermosetting resins and high-temperature resistant plastics. Energy&Environmental Science , 2016, 9(4): 1144-1189.); Nitro hydrogenation deoxygenation is the core technology for the synthesis of aromatic amines, and aniline, the hydrogenation product of nitrobenzene, is an important chemical component in industry.
[0004] The efficiency and selectivity of these reactions directly determine the quality and cost of downstream products: the pharmaceutical industry requires amine intermediates to have a purity of ≥99.5% and needs to precisely control hydrogenation byproducts; as a green solvent, the hydrogenation efficiency of tetrahydrofurfuryl alcohol, a product of biomass-based furfural hydrogenation, directly affects the industrialization process of biofuels.
[0005] Traditional hydrogenation reactions typically involve low substrate concentrations (<10 wt%), resulting in 40%-60% of total energy consumption being spent on product separation, purification, and crystallization. This leads to low energy utilization and high costs, contradicting the national strategy of carbon neutrality and the trend of green chemical development. Existing catalysts are mostly "single-substrate specific": Pd / C exhibits excellent activity for hydrogenating carbon-carbon double bonds, but nitro hydrogenation easily generates azo byproducts; Raney nickel can catalyze nitro hydrogenation but cannot selectively hydrogenate the carbon-oxygen double bond in furfural, easily generating 2-methylfuran; commercial transition metal catalysts exhibit selective deoxygenation (<90%) for high-concentration nitrobenzene hydrogenation, a characteristic that necessitates frequent catalyst replacements in industrial production, with annual replacement costs exceeding one million yuan per production line. Hydrogenation of substrates containing multiple unsaturated groups faces selectivity challenges: when Raney nickel catalyzes furfural hydrogenation, the furfuryl alcohol yield is below 85%; when Pd / C catalyzes cinnamaldehyde hydrogenation, the yield of the target product, cinnamyl alcohol, is less than 70%. Meanwhile, non-precious metal catalysts require harsh reaction conditions. For example, Raney nickel catalysts for hydrogenation of nitrobenzene require 160-180℃ and 4-5MPa, while Raney nickel catalysts for hydrogenation of furfuryl alcohol require 180-200℃ and 5-6MPa. This not only leads to a surge in energy consumption (energy consumption increases by 8%-10% for every 10℃ increase), but also poses safety risks such as equipment leakage. Summary of the Invention
[0006] To address the problems existing in the prior art, this invention provides a nickel-based organometallic framework catalyst and its application in the hydrogenation reaction of compounds containing unsaturated double bonds or nitro compounds. The catalyst of this invention can be used not only for the hydrogenation of compounds containing unsaturated double bonds (carbon-carbon double bonds, carbon-nitrogen double bonds, carbon-oxygen double bonds) but also for the hydrogenation of nitro compounds. Moreover, the catalyst is inexpensive, easy to prepare, the product is easy to separate, the product yield is high, and the production cost is low, thus having extremely high practical application value.
[0007] This invention achieves its objective through the following steps: 1. Mix nickel salt, binder and solvent, and react in a sealed container at 80-150℃. Separate the solid and liquid products of the reaction. Wash and dry the solid to obtain a nickel-based organometallic framework. Pyrolyze the nickel-based organometallic framework under an inert atmosphere at 400-700℃ to obtain a nickel-based organometallic framework catalyst. The binder is selected from terephthalic acid, trimesic acid, 2-methylimidazolium, basic lignin, 1,10-phenanthroline, citric acid, vitamin C, and glucose; the solvent is prepared by mixing water, anhydrous ethanol, and N,N-dimethylformamide in a volume ratio of 1:1:(5-16). The molar ratio of nickel salt to binder is 1:2-3:2; 2. Under conditions of hydrogen atmosphere, 100-120℃ and in the presence of solvent, nickel-based organometallic framework catalysts catalyze the hydrogenation reaction of compounds containing unsaturated double bonds or nitro compounds to obtain hydrogenation products. The compounds containing unsaturated double bonds are selected from benzaldehyde, syringaldehyde, veratral, 3,4-dihydroxybenzaldehyde, 3-hydroxy4-methylbenzaldehyde, acetophenone, 4-hydroxyacetophenone, styrene, maleic anhydride, furfuryl alcohol, furfural, furfurylimide, and 5-hydroxymethylfurfurylimide; the compounds containing nitro groups are selected from nitrobenzene, p-nitrobenzoic acid, 4-fluoro-nitrobenzene, 4-chloro-2-nitrophenol, p-nitrobenzyl alcohol, m-nitrotoluene, m-iodo-nitrobenzene, 2,5-dimethylnitrobenzene, m-fluoro-nitrobenzene, 1-nitropropane, 3-nitro-o-xylene, m-chloronitrobenzene, p-nitrotoluene, o-nitrotoluene, 2-(4-nitrobenzene)ethanol, 3-bromonitrobenzene, and 3-nitrobenzyl alcohol.
[0008] Advantages and technical effects of the present invention: 1. The catalyst of this invention can be used not only for the hydrogenation of compounds containing unsaturated double bonds (carbon-carbon double bonds, carbon-nitrogen double bonds, carbon-oxygen double bonds), but also for the catalytic hydrogenation and deoxygenation of nitro compounds. 2. This catalyst is inexpensive and easy to prepare, the product is easy to separate, and the product yield is high, making it extremely valuable for practical applications. 3. This catalyst breaks through the concentration limit of industrial hydrogenation. For the hydrogenation (deoxygenation) reaction of the compounds, the concentration exceeds 15 wt%. For compounds such as furfural, furfuryl alcohol, nitrobenzene, acetophenone, and benzaldehyde, solvent-free hydrogenation (deoxygenation) can be achieved, which reduces the energy consumed in the product separation and purification process and greatly reduces its production cost. Detailed Implementation
[0009] The present invention will be further described in detail below with reference to the embodiments, but the scope of protection of the present invention is not limited to the content described. Unless otherwise specified, the reagents and methods used in the embodiments are all conventional reagents and conventional methods. Example 1: Preparation and hydrogenation reaction of nickel-based organometallic framework catalysts 1. 0.02 mol of nickel chloride, 0.015 mol of terephthalic acid, and 54 mL of solvent (prepared by mixing water, anhydrous ethanol, and N,N-dimethylformamide in a volume ratio of 1:1:16) were mixed and reacted in a sealed container at 120 °C. The reaction product was separated into solid and liquid phases. The solid was washed once with water and then three times with ethanol. It was dried at 80 °C to obtain a nickel-based organometallic framework. The nickel-based organometallic framework was pyrolyzed at 400 °C for 3 h under a nitrogen atmosphere to obtain the nickel-based organometallic framework catalyst Ni-NiO2 / C-NiCl2-PTA. 2. Add 2.08g benzaldehyde and 0.1g catalyst Ni-NiO2 / C-NiCl2-PTA to a closed high-pressure reactor and mix evenly. No solvent needs to be added. Purge the air with hydrogen four times and maintain a hydrogen pressure of 3MPa. Heat and stir at 100℃ and 120℃ respectively for 1h to carry out the reduction reaction. The yields of benzyl alcohol are 97.5% and 98.3% respectively. 3. The hydrogenation reaction was catalyzed by Ni-NiO2 / C-NiCl2-PTA catalyst. The conditions and results are shown in the table below. Conditions not marked are the same as in step 2: ; ; .
[0010] Example 2: Preparation and hydrogenation reaction of nickel-based organometallic framework catalysts 1. 0.015 mol of nickel nitrate, 0.015 mol of terephthalic acid, and 54 mL of solvent (prepared by mixing water, anhydrous ethanol, and N,N-dimethylformamide in a volume ratio of 1:1:16) were mixed and reacted in a sealed container at 120 °C. The reaction product was separated into solid and liquid phases. The solid was washed once with water and then three times with ethanol. It was dried at 80 °C to obtain a nickel-based organometallic framework. The nickel-based organometallic framework was pyrolyzed at 400 °C for 3 h under a nitrogen atmosphere to obtain the nickel-based organometallic framework catalyst Ni-NiO2 / C-Ni(NO3)2-PTA. 2. Add 1.7g of furfural and 0.1g of catalyst Ni-NiO2 / C-Ni(NO3)2-PTA to a closed high-pressure reactor and mix thoroughly. No solvent is required. Purge the reactor four times with hydrogen to remove air and maintain a hydrogen pressure of 3MPa. Heat and stir at 100℃ for 2.5h to carry out the reduction reaction. The yield of furfuryl alcohol is 10.7%, the yield of tetrahydrofurfuryl alcohol is 87.8%, and the conversion rate is 100%. 3. The catalyst preparation was the same as above, except that nickel nitrate was replaced with NiOAc2 and NiI2 to prepare catalysts Ni-NiO2 / C-NiOAc2-PTA and Ni-NiO2 / C-NiI2-PTA, which were used for the hydrogenation reaction of furfural (under the same conditions as in Example 2). The catalytic results of catalyst Ni-NiO2 / C-NiOAc2-PTA were: furfuryl alcohol yield 11.1%, tetrahydrofurfuryl alcohol yield 86.7%, and conversion rate 100%; the catalytic results of catalyst Ni-NiO2 / C-NiI2-PTA were: furfuryl alcohol yield 9.4%, tetrahydrofurfuryl alcohol yield 88.1%, and conversion rate 100%.
[0011] Example 3: 1. The catalyst preparation in this embodiment is the same as in Example 1, except that the volume ratio of water, anhydrous ethanol, and N,N-dimethylformamide in the solvent preparation is replaced with 1:1:5; 2. Add 1.8g of nitrobenzene and 0.1g of catalyst to a closed high-pressure reactor and mix evenly. No solvent is required. Purge the air with hydrogen four times and maintain a hydrogen pressure of 3MPa. Heat and stir at 100℃ for 3.5h to carry out the reduction reaction. The yield is 87.8% and the conversion rate is 90%.
[0012] Example 4: The catalyst preparation in this embodiment is the same as in Example 1, except that terephthalic acid is replaced with the linker in the table below. The catalytic reaction conditions not marked are the same as step 2 of Example 1. .
Claims
1. The application of a nickel-based organometallic framework catalyst in hydrogenation reactions, characterized in that: The nickel-based organometallic framework catalyst is prepared by mixing nickel salt, a linker, and a solvent, reacting them in a sealed environment at 80-150°C, separating the solid and liquid products, washing and drying the solid to obtain the nickel-based organometallic framework, and then pyrolyzing the nickel-based organometallic framework at 400-700°C under an inert atmosphere. Nickel-based organometallic framework catalysts catalyze the hydrogenation reaction of compounds containing unsaturated double bonds or nitro compounds under hydrogen atmosphere, 100-120℃, and with or without solvent, to obtain hydrogenation products.
2. The application according to claim 1, characterized in that: The binder is selected from terephthalic acid, pyromellitic acid, 2-methylimidazolium, basic lignin, 1,10-phenanthroline, citric acid, vitamin C, and glucose. The solvent is water, anhydrous ethanol, and N,N-dimethylformamide mixed in a volume ratio of 1:1:(5-16).
3. The application according to claim 1, characterized in that: The molar ratio of nickel salt to binder is 1:2-3:
2.
4. The application according to claim 1, characterized in that: The compounds containing unsaturated double bonds are selected from benzaldehyde, syringaldehyde, veratral, 3,4-dihydroxybenzaldehyde, 3-hydroxy4-methylbenzaldehyde, acetophenone, 4-hydroxyacetophenone, styrene, maleic anhydride, furfuryl alcohol, furfural, furfurylimide, and 5-hydroxymethylfurfurylimide; the compounds containing nitro groups are selected from nitrobenzene, p-nitrobenzoic acid, 4-fluoro-nitrobenzene, 4-chloro-2-nitrophenol, p-nitrobenzyl alcohol, m-nitrotoluene, m-iodo-nitrobenzene, 2,5-dimethylnitrobenzene, m-fluoro-nitrobenzene, 1-nitropropane, 3-nitro-o-xylene, m-chloronitrobenzene, p-nitrotoluene, o-nitrotoluene, 2-(4-nitrobenzene)ethanol, 3-bromonitrobenzene, and 3-nitrobenzyl alcohol.