A niobium phytate-supported nano-metal catalyst system for hydrogenation of levulinic acid and esters

Abstract

The invention relates to a niobium phytate-loaded nano-metal catalyst system used for hydrogenation of levulinic acid to prepare gamma-valerolactone, which belongs to the field of chemical industry applications. The catalytic system is composed of niobium phytate and supported nanometer metals, and is suitable for catalyzing the hydrogenation of levulinic acid and esters to prepare γ-valerolactone. The catalytic system is suitable for levulinic acid, methyl levulinate, ethyl levulinate and isopropyl levulinate. In this catalytic system, the amount of nanometer metal is 0.2mol%-10mol% of the levulinic acid or ester used, and the reaction temperature is 25-150°C. 2 The pressure is 0.1-8MPa, and the reaction time is 0.5-24 hours. Compared with traditional methods, the catalytic system has mild reaction conditions, high activity and selectivity, cheap and easy-to-obtain carrier niobium phytate, good biocompatibility, and can be recycled by simple centrifugation, which has strong industrial application value.

Description

technical field

[0001] The invention relates to the application field of chemical industry, in particular to a niobium phytate-supported nano-metal catalytic system for preparing gamma-valerolactone through selective hydrogenation of levulinic acid. Background technique

[0002] With the depletion of fossil resources such as coal, oil, and natural gas, it has become an urgent problem for human beings to find alternative energy sources for fossil energy. Biomass resources are the only renewable organic carbon resources on the earth. They have the advantages of abundant reserves and wide sources, and can be used to replace fossil resources to produce chemicals and functional materials. Therefore, the conversion and utilization of biomass has become the frontier hot spot of current scientific research. Among many biomass-based chemicals, γ-valerolactone has attracted extensive research interest, including its synthesis and application. Generally, γ-valerolactone can be prepar...

Examples

Embodiment 1

[0015] 5 millimoles of levulinic acid and a catalyst (the amount of the nanometer metal catalyst is 5 mol% of the levulinic acid) were added into a 15 milliliter autoclave. After airtight vacuum degassing, filled with H 2 to 3MPa, and then reacted in a heating furnace at 60°C for 8 hours. After cooling and degassing, using n-dodecane as an internal standard, the yield of γ-valerolactone was detected by gas chromatography. When using Ru / niobium phytate, Pd / niobium phytate, Pt / niobium phytate, Au / niobium phytate as the catalyst and without catalyst, the yield of γ-valerolactone is shown in the table below.

[0016] catalyst Yield(%) Ru / niobium phytate 99 Pd / niobium phytate 12 Pt / niobium phytate 49 Au / niobium phytate 3 no catalyst 0

Embodiment 2

[0018] Add 5 mmol of levulinic acid and the catalyst Ru / niobium phytate into a 15 ml autoclave. After airtight vacuum degassing, filled with H 2 to 3MPa, and then reacted in a heating furnace at 60°C for 8 hours. After cooling and degassing, using n-dodecane as an internal standard, the yield of γ-valerolactone was detected by gas chromatography. When the amount of Ru is 0.2 mol%, 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 5 mol%, and 10 mol%, respectively, the yield of γ-valerolactone is shown in the table below.

[0019]

Embodiment 3

[0021] 5 mmol of levulinic acid and Ru / niobium phytate (5 mol%) were added into a 15 ml autoclave. After airtight vacuum degassing, filled with H 2 to 3MPa, and then reacted in furnaces at different temperatures for 8 hours. After cooling and degassing, using n-dodecane as an internal standard, the yield of γ-valerolactone was detected by gas chromatography. When the reaction temperature is 25°C, 40°C, 50°C, 60°C, 70°C, 80°C, the yield of γ-valerolactone is shown in the table below.

[0022] Reaction temperature (°C) Yield(%) 25 42 40 63 50 89 60 99 70 99 80 99

technical field

[0001] The invention relates to the application field of chemical industry, in particular to a niobium phytate-supported nano-metal catalytic system for preparing gamma-valerolactone through selective hydrogenation of levulinic acid. Background technique

[0002] With the depletion of fossil resources such as coal, oil, and natural gas, it has become an urgent problem for human beings to find alternative energy sources for fossil energy. Biomass resources are the only renewable organic carbon resources on the earth. They have the advantages of abundant reserves and wide sources, and can be used to replace fossil resources to produce chemicals and functional materials. Therefore, the conversion and utilization of biomass has become the frontier hot spot of current scientific research. Among many biomass-based chemicals, γ-valerolactone has attracted extensive research interest, including its synthesis and application. Generally, γ-valerolactone can be prepar...

Examples

Embodiment 1

[0015] 5 millimoles of levulinic acid and a catalyst (the amount of the nanometer metal catalyst is 5 mol% of the levulinic acid) were added into a 15 milliliter autoclave. After airtight vacuum degassing, filled with H 2 to 3MPa, and then reacted in a heating furnace at 60°C for 8 hours. After cooling and degassing, using n-dodecane as an internal standard, the yield of γ-valerolactone was detected by gas chromatography. When using Ru / niobium phytate, Pd / niobium phytate, Pt / niobium phytate, Au / niobium phytate as the catalyst and without catalyst, the yield of γ-valerolactone is shown in the table below.

[0016] catalyst Yield(%) Ru / niobium phytate 99 Pd / niobium phytate 12 Pt / niobium phytate 49 Au / niobium phytate 3 no catalyst 0

Embodiment 2

[0018] Add 5 mmol of levulinic acid and the catalyst Ru / niobium phytate into a 15 ml autoclave. After airtight vacuum degassing, filled with H 2 to 3MPa, and then reacted in a heating furnace at 60°C for 8 hours. After cooling and degassing, using n-dodecane as an internal standard, the yield of γ-valerolactone was detected by gas chromatography. When the amount of Ru is 0.2 mol%, 0.5 mol%, 1 mol%, 2 mol%, 3 mol%, 5 mol%, and 10 mol%, respectively, the yield of γ-valerolactone is shown in the table below.

[0019]

Embodiment 3

[0021] 5 mmol of levulinic acid and Ru / niobium phytate (5 mol%) were added into a 15 ml autoclave. After airtight vacuum degassing, filled with H 2 to 3MPa, and then reacted in furnaces at different temperatures for 8 hours. After cooling and degassing, using n-dodecane as an internal standard, the yield of γ-valerolactone was detected by gas chromatography. When the reaction temperature is 25°C, 40°C, 50°C, 60°C, 70°C, 80°C, the yield of γ-valerolactone is shown in the table below.

[0022] Reaction temperature (°C) Yield(%) 25 42 40 63 50 89 60 99 70 99 80 99

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