A heterogeneous catalytic reaction system for the reduction of substituted acrolein in alcohol solvents

Abstract

A heterogeneous catalytic reaction for the reduction of substituted acrolein in an alcoholic solvent comprises: 3-(2-furyl)acrolein as a reaction substrate, a linear alcohol as a solvent, high-purity nitrogen as a protective gas, a solid high-entropy catalyst, heating and stirring, and filtering to obtain 3-(2-furyl)propanol; the mass ratio of the solid high-entropy catalyst to the substrate 3-(2-furyl)acrolein is 0.1 to 0.3:1. The present invention has the following beneficial effects: efficient and highly selective conversion of 3-(2-furyl)acrolein is achieved through the catalytic reaction; the raw materials used are inexpensive and readily available; the reaction process is highly safe; and the catalyst is easily recyclable. Compared with traditional precious metal catalysts, the present invention has the advantages of good economic efficiency, simple preparation method, and strong sustainability.

Description

Technical Field

[0001] The invention relates to the field of chemical industry, and in particular to a heterogeneous catalytic reaction system for reducing substituted acrolein in an alcohol solvent. Background Art

[0002] Furfural, as a biomass platform compound, has a unique molecular structure that allows it to undergo various chemical reactions to produce a range of biomass derivatives. Its downstream products cover multiple industries, including pharmaceuticals, coatings, and resins. Currently, the oxidation-condensation reaction of furfural and fatty alcohols is also an effective way to extend carbon chains, generating longer hydrocarbon chains and high-value liquid fuels. Among them, furfural and n-propanol undergo an aldol condensation reaction under alkaline conditions. The condensation product contains 8 carbon atoms and can serve as a high-value-added chemical intermediate and a precursor to liquid fuels. The generated longer hydrocarbon chains can be further reduced to higher-saturation, high-value liquid fuels, showing broad development prospects.

[0003] In addition, in previous similar studies, precious metals were often used as catalysts, which have high costs and have limited industrial applications.

[0004] Therefore, we designed and developed a new highly active catalyst to achieve efficient utilization of 3-(2-furyl)acrolein. Summary of the Invention

[0005] The main purpose of the present invention is to solve the above problems and provide a multiphase catalytic reaction system for the reduction of substituted acrolein in an alcohol solvent. The reaction equation is as follows: Figure 1 .

[0006] A heterogeneous catalytic reaction for the reduction of substituted acrolein in an alcohol solvent comprises: using 3-(2-furyl)acrolein as a reaction substrate and a straight-chain alcohol as a solvent; introducing high-purity nitrogen as a protective gas; adding a solid high-entropy catalyst; heating and stirring, and filtering to obtain 3-(2-furyl)propanol; and a mass ratio of the solid high-entropy catalyst to the substrate 3-(2-furyl)acrolein of 0.1-0.3:1.

[0007] The preparation method of the solid high-entropy catalyst is to use hydrated nitrate and citric acid to react, the molar ratio of the two is 1:1.2, and add ammonia water to adjust the pH of the solution to neutral.

[0008] The hydrated nitrate used is copper nitrate trihydrate, cobalt nitrate hexahydrate, aluminum nitrate nonahydrate, nickel nitrate hexahydrate or iron nitrate nonahydrate.

[0009] The nickel nitrate hexahydrate or the iron nitrate nonahydrate is replaced by metal cerium or zirconium hydrated nitrate.

[0010] The reaction temperature is 100-220° C., the reaction time is 1-3 h, and the stirring rate is 0-450 rpm / min.

[0011] The linear alcohol solvent used preferably comprises short-chain alcohols of different carbon numbers.

[0012] The linear alcohol solvent used is preferably n-propanol, methanol, isopropanol, ethanol, n-butanol, n-pentanol, n-hexanol or n-octanol.

[0013] The reaction protection gas is nitrogen, argon or helium.

[0014] The beneficial effects of the present invention are: efficient and highly selective conversion of 3-(2-furyl)acrolein is achieved through a catalytic reaction, the raw materials used are cheap and readily available, the reaction process is highly safe, and the catalyst is easily recyclable; compared with traditional precious metal catalysts, it has the advantages of good economy, simple preparation method, and strong sustainability. BRIEF DESCRIPTION OF THE DRAWINGS

[0015] Figure 1 This is the reaction equation for the heterogeneous catalytic reaction of the present invention for the reduction of substituted acrolein in an alcohol solvent. DETAILED DESCRIPTION

[0016] In order to make the technical problems, technical solutions and beneficial effects to be solved by the present invention clearer and more understandable, the present invention is further described in detail below with examples.

[0017] The specific operation mode of the present invention is as follows:

[0018] A certain amount of 3-(2-furyl)propenal was weighed as the reaction substrate, and isopropanol was used as the solvent. A solid high-entropy catalyst was added, and the system was de-aired and filled with nitrogen at a certain pressure. The system was heated and stirred to induce a catalytic reduction of 3-(2-furyl)propenal. After the reaction, the high-entropy catalyst was separated from the solution using a syringe and a filter membrane, and the product was analyzed by gas chromatography. Example 1

[0019] Add 2 mmol of copper nitrate trihydrate Cu(NO3)2•3H2O, cobalt nitrate hexahydrate Co(NO3)2•6H2O, aluminum nitrate nonahydrate Al(NO3)3•9H2O, cerium nitrate hexahydrate Ce(NO3)2•6H2O, and nickel nitrate hexahydrate Ni(NO3)2•6H2O to 100 ml of deionized water and stir thoroughly for 20 min until they are fully dissolved. Add 12 mmol of citric acid and stir for 20 min until the solution is fully mixed. Adjust the pH of the solution to neutral with ammonia water (NH3•H2O), heat and stir at 85°C for 4 h until the solution becomes gel-like, transfer it to a vacuum drying oven at 80°C and dry overnight. After drying, transfer it to a crucible and self-propagate in a muffle furnace at 500°C for 4 h. Grind to obtain a high entropy catalyst. 0.025 g of the above catalyst, 0.1 g of 3-(2-furyl)propenal, and 20 ml of isopropanol were added to a high-pressure hydrogenation autoclave, which was sealed and filled with 1 MPa of nitrogen. The autoclave was heated and stirred at 200°C for 1 hour. After filtering the reaction solution, gas chromatography-mass spectrometry (GC-MS) analysis revealed a conversion of greater than 99.9% for 3-(2-furyl)propenal, and a selectivity of 95.16% for 3-(2-furyl)propanol. Example 2

[0020] Add 2 mmol of copper nitrate trihydrate Cu(NO3)2•3H2O, cobalt nitrate hexahydrate Co(NO3)2•6H2O, aluminum nitrate nonahydrate Al(NO3)3•9H2O, zirconium nitrate pentahydrate Zr(NO3)4•5H2O, and nickel nitrate hexahydrate Ni(NO3)2•6H2O to 100 ml of deionized water and stir thoroughly for 20 min until they are fully dissolved. Add 12 mmol of citric acid and stir for 20 min until the solution is fully mixed. Adjust the pH of the solution to neutral with ammonia water (NH3•H2O), heat and stir at 85°C for 4 h until the solution becomes gel-like, transfer it to a vacuum drying oven at 80°C and dry overnight. After drying, transfer it to a crucible and self-propagate in a muffle furnace at 500°C for 4 h. Grind to obtain a high entropy catalyst. 0.025 g of the above catalyst, 0.1 g of 3-(2-furyl)propenal, and 20 ml of isopropanol were added to a high-pressure hydrogenation autoclave, which was sealed and filled with 1 MPa of nitrogen. The autoclave was heated and stirred at 200°C for 1 hour. After filtering the reaction solution, gas chromatography-mass spectrometry (GC-MS) analysis revealed an 82.32% conversion of 3-(2-furyl)propenal and a 20.91% selectivity for 3-(2-furyl)propanol. Example 3

[0021] Add 2 mmol of copper nitrate trihydrate Cu(NO3)2•3H2O, cobalt nitrate hexahydrate Co(NO3)2•6H2O, aluminum nitrate nonahydrate Al(NO3)3•9H2O, cerium nitrate hexahydrate Ce(NO3)2•6H2O, and zirconium nitrate pentahydrate Zr(NO3)4•5H2O to 100 ml of deionized water and stir thoroughly for 20 min until they are fully dissolved. Add 12 mmol of citric acid and stir for 20 min until the solution is fully mixed. Adjust the pH of the solution to neutral with ammonia water (NH3•H2O), heat and stir at 85°C for 4 h until the solution becomes gel-like, transfer it to a vacuum drying oven at 80°C and dry overnight. After drying, transfer it to a crucible and self-propagate in a muffle furnace at 500°C for 4 h. Grind to obtain a high entropy catalyst. 0.025 g of the above catalyst, 0.1 g of 3-(2-furyl)propenal, and 20 ml of isopropanol were added to a high-pressure hydrogenation autoclave. The autoclave was sealed, filled with 1 MPa of nitrogen, and heated with stirring at 200°C for 1 hour. After filtering the reaction solution, gas chromatography-mass spectrometry (GC-MS) analysis revealed a 91.85% conversion of 3-(2-furyl)propenal and a 58.92% selectivity for 3-(2-furyl)propanol. Example 4

[0022] Add 2 mmol of copper nitrate trihydrate Cu(NO3)2•3H2O, cobalt nitrate hexahydrate Co(NO3)2•6H2O, aluminum nitrate nonahydrate Al(NO3)3•9H2O, nickel nitrate hexahydrate Ni(NO3)2•6H2O, and iron nitrate nonahydrate Fe(NO3)3•9H2O to 100 ml of deionized water and stir thoroughly for 20 min until they are fully dissolved. Add 12 mmol of citric acid and stir for 20 min until the solution is fully mixed. Adjust the pH of the solution to neutral with ammonia water (NH3•H2O), heat and stir at 85°C for 4 h until the solution becomes gel-like, transfer it to a vacuum drying oven at 80°C and dry overnight. After drying, transfer it to a crucible and self-propagate in a muffle furnace at 500°C for 4 h. Grind to obtain a high entropy catalyst. 0.025 g of the above catalyst, 0.1 g of 3-(2-furyl)propenal, and 20 ml of isopropanol were added to a high-pressure hydrogenation autoclave, which was sealed and filled with 1 MPa of nitrogen. The reaction mixture was heated and stirred at 200°C for 1 hour. After filtration, gas chromatography analysis revealed a conversion of 3-(2-furyl)propenal exceeding 99.9%, with a selectivity for 3-(2-furyl)propanol reaching 92.99%. Example 5

[0023] Add 2 mmol of copper nitrate trihydrate Cu(NO3)2•3H2O, cobalt nitrate hexahydrate Co(NO3)2•6H2O, aluminum nitrate nonahydrate Al(NO3)3•9H2O, cerium nitrate hexahydrate Ce(NO3)2•6H2O, and iron nitrate nonahydrate Fe(NO3)3•9H2O to 100 ml of deionized water and stir thoroughly for 20 min until they are fully dissolved. Add 12 mmol of citric acid and stir for 20 min until the solution is fully mixed. Adjust the pH of the solution to neutral with ammonia water (NH3•H2O), heat and stir at 85°C for 4 h until the solution becomes gel-like, transfer it to a vacuum drying oven at 80°C and dry overnight. After drying, transfer it to a crucible and self-propagate in a muffle furnace at 500°C for 4 h. Grind to obtain a high entropy catalyst. 0.025 g of the above catalyst, 0.1 g of 3-(2-furyl)propenal, and 20 ml of isopropanol were added to a high-pressure hydrogenation autoclave, which was sealed and filled with 1 MPa of nitrogen. The autoclave was heated and stirred at 200°C for 1 hour. After filtering the reaction solution, gas chromatography-mass spectrometry (GC-MS) analysis revealed a 92.08% conversion of 3-(2-furyl)propenal and a 62.52% selectivity for 3-(2-furyl)propanol. Example 6

[0024] Add 2 mmol of copper nitrate trihydrate Cu(NO3)2•3H2O, cobalt nitrate hexahydrate Co(NO3)2•6H2O, aluminum nitrate nonahydrate Al(NO3)3•9H2O, zirconium nitrate pentahydrate Zr(NO3)4•5H2O, and iron nitrate nonahydrate Fe(NO3)3•9H2O to 100 ml of deionized water and stir thoroughly for 20 min until they are fully dissolved. Add 12 mmol of citric acid and stir for 20 min until the solution is fully mixed. Adjust the pH of the solution to neutral with ammonia water (NH3•H2O), heat and stir at 85°C for 4 h until the solution becomes gel-like, transfer it to a vacuum drying oven at 80°C and dry overnight. After drying, transfer it to a crucible and self-propagate in a muffle furnace at 500°C for 4 h. Grind to obtain a high entropy catalyst. 0.025 g of the above catalyst, 0.1 g of 3-(2-furyl)propenal, and 20 ml of isopropanol were added to a high-pressure hydrogenation autoclave, which was sealed and filled with 1 MPa of nitrogen. The autoclave was heated and stirred at 200°C for 1 hour. After filtering the reaction solution, gas chromatography-mass spectrometry (GC-MS) analysis revealed a 3-(2-furyl)propenal conversion of 86.53% and a 3-(2-furyl)propanol selectivity of 39.87%. Example 7

[0025] 0.025 g of the catalyst from Example 4, 0.1 g of 3-(2-furyl)propenal, and 20 ml of ethanol were added to a high-pressure hydrogenation autoclave. The autoclave was sealed, filled with 1 MPa of nitrogen, and heated with stirring at 200°C for 1 hour. After filtering the reaction solution, gas chromatography-mass spectrometry (GC-MS) analysis revealed a conversion of greater than 99.9% for 3-(2-furyl)propanol, with a selectivity of 86.22%. Example 8

[0026] 0.025 g of the catalyst from Example 4, 0.1 g of 3-(2-furyl)propenal, and 20 ml of n-propanol solvent were added to a high-pressure hydrogenation autoclave. The autoclave was sealed, filled with 1 MPa of nitrogen, and heated with stirring at 200°C for 1 hour. After filtering the reaction solution, gas analysis revealed a conversion of 3-(2-furyl)propenal exceeding 99.9%, and a selectivity for 3-(2-furyl)propanol of 32.91%. Example 9

[0027] 0.025 g of the catalyst from Example 4, 0.1 g of 3-(2-furyl)propenal, and 20 ml of n-butanol solvent were added to a high-pressure hydrogenation autoclave. The autoclave was sealed, filled with 1 MPa of nitrogen, and heated with stirring at 200°C for 1 hour. After filtering the reaction solution, gas chromatography-mass spectrometry (GC-MS) analysis revealed a 52.61% conversion of 3-(2-furyl)propenal and a 7.09% selectivity for 3-(2-furyl)propanol.

Claims

1. A heterogeneous catalytic reaction for the reduction of substituted acrolein in an alcohol solvent, characterized by: 3-(2-furyl)propenal is used as a reaction substrate, and isopropanol, ethanol, n-pentanol, n-hexanol, or n-octanol is used as a solvent; high-purity nitrogen, argon, or helium is introduced as a protective gas; a solid high-entropy catalyst is added; the mixture is heated and stirred, and filtered to obtain 3-(2-furyl)propanol; the mass ratio of the solid high-entropy catalyst to the substrate 3-(2-furyl)propenal is 0.1-0.3:1; the reaction temperature is 100-220°C, the reaction time is 1-3 hours, and the stirring rate is 0-450 rpm / min; The preparation method of the high entropy catalyst is: 2 mmol of copper nitrate trihydrate (Cu(NO3)2•3H2O), cobalt nitrate hexahydrate (Co(NO3)2•6H2O), aluminum nitrate nonahydrate (Al(NO3)3•9H2O), cerium nitrate hexahydrate (Ce(NO3)2•6H2O), and nickel nitrate hexahydrate (Ni(NO3)2•6H2O) were added to 100 ml of deionized water and stirred for 20 min until they were fully dissolved. 12 mmol of citric acid was added and stirred for 20 min until the solution was fully mixed. The pH of the solution was adjusted to neutral with aqueous ammonia (NH3•H2O). The solution was heated and stirred at 85°C for 4 h until a gel appeared. The solution was transferred to a vacuum drying oven and dried at 80°C overnight. After drying, the solution was transferred to a crucible and self-propagated in a muffle furnace at 500°C for 4 h. The high entropy catalyst was obtained by grinding. or: Add 2 mmol of copper nitrate trihydrate Cu(NO3)2•3H2O, cobalt nitrate hexahydrate Co(NO3)2•6H2O, aluminum nitrate nonahydrate Al(NO3)3•9H2O, nickel nitrate hexahydrate Ni(NO3)2•6H2O, and iron nitrate nonahydrate Fe(NO3)3•9H2O to 100 ml of deionized water and stir thoroughly for 20 min until they are fully dissolved. Add 12 mmol of citric acid and stir for 20 min until the solution is fully mixed. Adjust the pH of the solution to neutral with ammonia water (NH3•H2O), heat and stir at 85°C for 4 h until the solution becomes gel-like, transfer it to a vacuum drying oven at 80°C and dry overnight. After drying, transfer it to a crucible and self-propagate in a muffle furnace at 500°C for 4 h. Grind to obtain a high entropy catalyst.

2. The heterogeneous catalytic reaction for the reduction of substituted acrolein in an alcohol solvent according to claim 1, characterized in that: The protective gas is high-purity nitrogen.

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