Preparation method of 2, 5-dimethylfuran

Abstract

The invention discloses a preparation method of 2,5-dimethylfuran and relates to 2,5-dimethylfuran. A furan aldehyde compound serving as a substrate is added into an organic solvent to prepare a reaction substrate solution; the reaction substrate solution, anhydrous formic acid and a non-precious-metal catalyst are mixed and put into a reaction kettle, nitrogen gas is used for replacing dischargedair, heating and stirring are conducted for hydrodeoxygenation, and 2,5-dimethylfuran is obtained. The prepared supported non-precious-metal Ni-Cu / SBA-15 serves as a catalyst, formic acid serves as ahydrogen donor, and the furan aldehyde compound is subjected to catalytic transfer hydrogenation to synthesize DMF. The whole process is simple and easy to operate, the cost is low, the reaction system is green, the catalyst is high in activity, the selectivity of DMF is high, the yield is high, and the method has a wide industrial application prospect. Direct use of H2 is avoided, formic acid isused as a hydrogen source, 2,5-dimethylfuran is convenient to store and use, the requirement of a reaction solvent for the hydrogen solubility is reduced, the hydrogenation effect is good, the synthesis method is simple, the method is easy to operate, and energy consumption is low.

Description

technical field

[0001] The invention relates to 2,5-dimethylfuran, in particular to a preparation method of 2,5-dimethylfuran. technical background

[0002] With the increasing consumption of fossil energy, the development of renewable new energy fuels to replace fossil fuels has become a current research hotspot. Among them, biomass energy is considered to be the most ideal substitute for fossil energy due to its wide source, wide distribution, low cost, and as the only renewable energy containing organic carbon. Currently, the biomass-derived chemical 2,5-dimethylfuran (DMF) is the most extensively researched fuel substitute, with many excellent properties similar to gasoline. For example, DMF has high energy density (30MJ / L) and high octane number (119), its boiling point is 92-94°C, its solubility in water is only 0.26wt%, and it can be miscible with gasoline or used alone. Compared with biofuel ethanol, which is easily soluble in water, difficult to preserve, and has ...

Examples

Embodiment 1

[0024] Add 0.18g of 5-formyloxymethylfurfural to 10mL of tetrahydrofuran, then add 400μL of anhydrous formic acid and 0.10g of non-precious metal catalyst A, mix and place in a closed high-pressure reactor, replace with nitrogen 4 to 5 times to exhaust the air, 200 The mixture was heated and stirred at ℃ for 5 hours to carry out hydrodeoxygenation reaction to obtain 2,5-dimethylfuran with a yield of 40.70%.

[0025] Wherein, the mass fraction of nickel and copper accounting for carrier SBA-15 in the non-precious metal catalyst A is 48%, wherein the mass ratio of nickel and copper is 3: 1; the preparation method of catalyst A comprises the following steps: take 0.5g SBA-15, according to The mass fraction of copper and nickel was prepared by preparing nickel nitrate and copper nitrate aqueous solutions, adding them dropwise to molecular sieve SBA-15, mixing them evenly, and impregnating them in equal volumes for 12 hours; drying the impregnated products at 110°C for 10 hours to o...

Embodiment 2

[0027] Add 0.18g of 5-formyloxymethylfurfural to 10mL of tetrahydrofuran, then add 560μL of anhydrous formic acid and 0.10g of non-precious metal catalyst A, mix and place in a closed high-pressure reactor, replace with nitrogen 4 to 5 times to exhaust the air, 220 The mixture was heated and stirred at °C for hydrodeoxygenation reaction for 5 hours to obtain 2,5-dimethylfuran with a yield of 71.04%.

[0028] See Example 1 for the preparation method of non-noble metal catalyst A.

Embodiment 3

[0030] Add 0.18g of 5-formyloxymethylfurfural to 10mL of 1,4-dioxane, then add 400μL of anhydrous formic acid and 0.10g of non-precious metal catalyst A, mix them in a closed autoclave, and replace with nitrogen for 4~ The air was discharged five times, heated and stirred at 220° C. for hydrodeoxygenation reaction for 5 hours to obtain 2,5-dimethylfuran with a yield of 62.73%.

[0031] See Example 1 for the preparation method of non-noble metal catalyst A.

technical field

[0001] The invention relates to 2,5-dimethylfuran, in particular to a preparation method of 2,5-dimethylfuran. technical background

[0002] With the increasing consumption of fossil energy, the development of renewable new energy fuels to replace fossil fuels has become a current research hotspot. Among them, biomass energy is considered to be the most ideal substitute for fossil energy due to its wide source, wide distribution, low cost, and as the only renewable energy containing organic carbon. Currently, the biomass-derived chemical 2,5-dimethylfuran (DMF) is the most extensively researched fuel substitute, with many excellent properties similar to gasoline. For example, DMF has high energy density (30MJ / L) and high octane number (119), its boiling point is 92-94°C, its solubility in water is only 0.26wt%, and it can be miscible with gasoline or used alone. Compared with biofuel ethanol, which is easily soluble in water, difficult to preserve, and has ...

Examples

Embodiment 1

[0024] Add 0.18g of 5-formyloxymethylfurfural to 10mL of tetrahydrofuran, then add 400μL of anhydrous formic acid and 0.10g of non-precious metal catalyst A, mix and place in a closed high-pressure reactor, replace with nitrogen 4 to 5 times to exhaust the air, 200 The mixture was heated and stirred at ℃ for 5 hours to carry out hydrodeoxygenation reaction to obtain 2,5-dimethylfuran with a yield of 40.70%.

[0025] Wherein, the mass fraction of nickel and copper accounting for carrier SBA-15 in the non-precious metal catalyst A is 48%, wherein the mass ratio of nickel and copper is 3: 1; the preparation method of catalyst A comprises the following steps: take 0.5g SBA-15, according to The mass fraction of copper and nickel was prepared by preparing nickel nitrate and copper nitrate aqueous solutions, adding them dropwise to molecular sieve SBA-15, mixing them evenly, and impregnating them in equal volumes for 12 hours; drying the impregnated products at 110°C for 10 hours to o...

Embodiment 2

[0027] Add 0.18g of 5-formyloxymethylfurfural to 10mL of tetrahydrofuran, then add 560μL of anhydrous formic acid and 0.10g of non-precious metal catalyst A, mix and place in a closed high-pressure reactor, replace with nitrogen 4 to 5 times to exhaust the air, 220 The mixture was heated and stirred at °C for hydrodeoxygenation reaction for 5 hours to obtain 2,5-dimethylfuran with a yield of 71.04%.

[0028] See Example 1 for the preparation method of non-noble metal catalyst A.

Embodiment 3

[0030] Add 0.18g of 5-formyloxymethylfurfural to 10mL of 1,4-dioxane, then add 400μL of anhydrous formic acid and 0.10g of non-precious metal catalyst A, mix them in a closed autoclave, and replace with nitrogen for 4~ The air was discharged five times, heated and stirred at 220° C. for hydrodeoxygenation reaction for 5 hours to obtain 2,5-dimethylfuran with a yield of 62.73%.

[0031] See Example 1 for the preparation method of non-noble metal catalyst A.

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