Method for preparing cyclohexanone by converting acetone and 1, 3-propylene glycol

Abstract

The invention relates to a method for preparing cyclohexanone by conversion of acetone and 1, 3-propylene glycol, and belongs to the technical field of chemical engineering. The method comprises the following steps: catalyzing a dialkylation reaction of acetone and 1, 3-propylene glycol by virtue of a supported nickel or palladium catalyst and a potassium phosphate cocatalyst, and removing water from acetone and 1, 3-propylene glycol which are equal in molar weight, so as to obtain cyclohexanone. The method contributes to the production of bulk chemicals and fine chemicals by a fermentation method, and makes a contribution to the strategic goal of low-carbon development.

Description

Technical Field

[0001] The invention belongs to the field of chemical engineering technology and relates to a catalytic conversion technology for chemicals, in particular to a method for preparing cyclohexanone by converting acetone obtained by a fermentation method and 1,3-propylene glycol. Background Art

[0002] Cyclohexanone is mainly used in industry to produce monomers for nylon 6,6 and nylon 6, but its initial raw material is benzene from fossil resources. The process of cyclohexane oxidation of benzene to a mixture of cyclohexanol and cyclohexanone involves high temperature, high pressure and a large amount of flammable substances, which will produce a large amount of secondary oxidation products, reducing the yield and selectivity of the products. About half of the cyclohexanone produced worldwide is converted to adipic acid as one of the two monomers for nylon 6,6 through nitric acid oxidation of KA oil (a mixture of cyclohexanone and cyclohexanol). The other half of cyclohexanone is converted to cyclohexanone oxime, which is then rearranged into caprolactam under the action of sulfuric acid catalyst to become the monomer of nylon 6.

[0003] Microorganisms are considered to be powerful hosts for biomass production of biofuels and chemicals. Microbial fermentation can produce a variety of chemicals, including C2-C6 carboxylic acids, dicarboxylic acids, fruit acids, amino acids, alcohols, diols and diamines (Biotechnol. Bioeng. 2012, 109, 2437–2459). However, the number of chemicals that can be produced by microorganisms is very limited, so there is an urgent need to expand existing fermentation products through chemical technology.

[0004] Both acetone and 1,3-propylene glycol can be obtained by fermentation. Therefore, through the double alkylation reaction of acetone and an equimolar amount of 1,3-propylene glycol, a green production process for cyclohexanone can be developed to achieve the conversion of biomass resources. The catalyst for the alkylation reaction of monohydric alcohols and acetone is a bifunctional catalyst. The transition metal in the catalyst is a dehydrogenation / hydrogenation active component, while the base accelerates the formation of CC bonds through the aldol condensation of alcohol-derived aldehyde intermediates with acetone (Chem. Eng. J. 2017, 313, 1486–1493). The present invention applies this catalytic strategy to the synthesis of cyclohexanone, which will help to produce bulk chemicals and fine chemicals using biomass fermentation, and contribute to the strategic goal of achieving low-carbon development. The production of acetone and 1,3-propylene glycol using biomass fermentation can further develop monomers of nylon 6,6 and nylon 6 through the route of the present invention. Summary of the invention

[0005] The present invention aims at the fact that cyclohexanone is mainly produced industrially using traditional petrochemical product benzene as raw material, and the production process consumes a lot of energy and causes serious pollution. The present invention provides a method for obtaining cyclohexanone, an intermediate of a high molecular monomer, from the fermentation product by using the directed catalysis of the fermentation product of bio-based 1,3-propanediol and bio-butanol.

[0006] In view of the problems that acetone, a by-product of biobutanol fermentation, cannot be efficiently utilized and the energy consumption of 1,3-propylene glycol separation is high, the present invention develops an alkylation reaction based on acetone and 1,3-propylene glycol, couples the separation process of 1,3-propylene glycol, reduces energy consumption, and obtains cyclohexanone, an intermediate of a high molecular monomer, from the fermentation product, providing renewable raw materials for the preparation of biomass-based nylon 66 and nylon 6. The key technology for preparing cyclohexanone by selective alkylation of acetone and 1,3-propylene glycol is developed, and the separation process is coupled to achieve energy conservation and emission reduction, providing technical support for my country to achieve carbon peak in 2030 and carbon neutrality in 2060.

[0007] To achieve the above purpose, the present invention adopts the following four technical solutions:

[0008] 1. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, comprising the following steps:

[0009] The nickel salt is dissolved in anhydrous ethanol, and the solution is recorded as solution a; hydrotalcite is added to solution a, and the obtained suspension is recorded as slurry b; the beaker containing the slurry is placed on a magnetic stirrer to stir the slurry, so that the ethanol is completely evaporated to obtain a solid; the solid in the beaker is ground into fine powder; the fine powder is placed in a tubular furnace, and reduced in H2 (5% inAr) at 300-600°C for 1-12 hours to prepare a catalyst Ni / MgAlO;

[0010] Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; Ni / MgAlO equivalent to 0.1-10wt% of system d is added to system d; the reactor is purged with N2 for 1-3 times, and then 0.1-1MPa MPa of N2 is injected; the reactor is then reacted at 150-250°C and a rotation speed of 600-1000rpm for 0.1-24 hours to obtain a reaction liquid containing cyclohexanone; after the reaction is completed, the reactor is immediately taken out and immersed in cold water for cooling until the temperature drops to room temperature; the reactor is opened, and the product is quantified by gas chromatography (GC-FID).

[0011] 2. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, comprising the following steps:

[0012] The nickel salt is dissolved in anhydrous ethanol, and the solution is recorded as solution a; hydrotalcite is added to solution a, and the obtained suspension is recorded as slurry b; the beaker containing the slurry is placed on a magnetic stirrer to stir the slurry, so that the ethanol is completely evaporated to obtain a solid; the solid in the beaker is ground into fine powder; the fine powder is placed in a tubular furnace, and reduced in H2 (5% inAr) at 300-600°C for 1-12 hours to prepare a catalyst Ni / MgAlO;

[0013] Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; Ni / MgAlO equivalent to 0.1-10wt% of system d is added to system d; K3PO4 equivalent to 0.1-10wt% of system d is added to system d; the reactor is purged with N2 for 1-3 times, and then 0.1-1MPaMPa of N2 is injected; the reactor is then reacted at 150-250°C and a rotation speed of 600-1000rpm for 0.1-24 hours to obtain a reaction solution containing cyclohexanone; after the reaction is completed, the reactor is immediately taken out and immersed in cold water for cooling until the temperature drops to room temperature; the reactor is opened, and the product is quantified by gas chromatography (GC-FID).

[0014] 3. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, comprising the following steps:

[0015] Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; commercial Pd / C (5% loading amount) equivalent to 0.1-10wt% of system d is added to system d; K3PO4 equivalent to 0.1-200wt% of system d is added to system d; the reactor is purged with N2 for 1-3 times, and then 0.1-1MPa MPa of N2 is injected; the reactor is then reacted at 150-250°C and a rotation speed of 600-1000rpm for 0.1-24 hours to obtain a reaction solution containing cyclohexanone; after the reaction is completed, the reactor is immediately taken out and immersed in cold water for cooling until the temperature drops to room temperature; the reactor is opened and the product is quantified by gas chromatography (GC-FID).

[0016] 4. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, comprising the following steps:

[0017] Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; commercial Pd / C (5% loading amount) equivalent to 0.1-10wt% of system d is added to system d; K3PO4 equivalent to 0.1-200wt% of system d is added to system d; the reactor is purged with H2 for 1-3 times, and then 0.1-1MPa MPa of H2 is injected; the reactor is then reacted at 150-250°C and a rotation speed of 600-1000rpm for 0.1-24 hours to obtain a reaction solution containing cyclohexanone; after the reaction is completed, the reactor is immediately taken out and immersed in cold water for cooling until the temperature drops to room temperature; the reactor is opened, and the product is quantified by gas chromatography (GC-FID).

[0018] The present invention adopts the above technical solution, which has the following advantages:

[0019] (1) In view of the problem of high energy consumption and serious pollution in the industrial production of cyclohexanone using petrochemical product benzene as raw material, a catalytic upgrading pathway for bio-based 1,3-propylene glycol and acetone, a byproduct of bio-butanol fermentation, was proposed, providing a new way to high-value utilization of biomass. We developed a new catalytic conversion method that converts 1,3-propylene glycol and acetone into cyclohexanone by selectively dehydrogenating and hydrogenating the raw materials and intermediates on a supported metal catalyst and promoting CC bond coupling with an alkaline co-catalyst.

[0020] (2) The types of chemicals produced by biomass microbial fermentation are very limited, so there is an urgent need to expand the existing fermentation products through chemical technology. By coupling two fermentation products into other chemicals, it not only provides another way for the high-value utilization of acetone, but also expands the application field of 1,3-propylene glycol, deeply explores the potential of fermentation to produce chemicals from biomass, and expands the downstream products of fermentation products. BRIEF DESCRIPTION OF THE DRAWINGS

[0021] Figure 1 : Yield of cyclohexanone prepared by conversion of 1,3-propylene glycol and acetone using different catalysts. DETAILED DESCRIPTION

[0022] The present invention is described in detail below by way of examples.

[0023] Example 1

[0024] First, acetone and 1,3-propylene glycol were mixed in a reactor with a total mass of 10 g and a molar ratio of acetone to 1,3-propylene glycol of 1:1. 17 mL of water was added, followed by 17 g of K3PO4﹒3H2O, followed by 0.1 g of commercial Pd / C (5% loading). The reactor was purged with N2 three times, and then 1 MPa of N2 was injected. The reaction was carried out at 250°C for 0.5 hours to obtain a reaction solution containing cyclohexanone. After the reaction was completed, the reactor was immediately taken out and immersed in cold water to cool until the temperature dropped to room temperature. The reactor was opened and the product was quantified by gas chromatography (GC-FID).

[0025] Example 2

[0026] 1) The specific steps of preparing a hydrotalcite-supported nickel catalyst by an impregnation method are as follows: weigh 0.42 g of Ni(CH3COO)2﹒4H2O and dissolve it in 40 mL of ethanol solvent, then add 1.90 g of hydrotalcite to the above Ni(CH3COO)2 ethanol solution to obtain a slurry; place a beaker containing the above slurry on a magnetic stirrer to stir the slurry to completely evaporate the ethanol to obtain a solid; grind the solid in the beaker into a fine powder; put the above fine powder into a tubular furnace and reduce it in H2 (5% inAr) at 600°C for 6 hours to prepare a catalyst Ni / MgAlO.

[0027] 2) First, 5 g of acetone and 1,3-propylene glycol were mixed in a reactor in a molar ratio of 1:1. 15 mL of water was added, and then 0.2 g of Ni / MgAlO was added. The reactor was purged with N2 three times, and then 0.4 MPa of N2 was injected. The reaction was carried out at 220 ° C for 6 hours to obtain a reaction solution containing cyclohexanone. After the reaction was completed, the reactor was immediately taken out and immersed in cold water to cool until the temperature dropped to room temperature. The reactor was opened and the product was quantified by gas chromatography (GC-FID).

[0028] Example 3

[0029] First, acetone and 1,3-propylene glycol were mixed in a reactor with a total mass of 10 g and a molar ratio of acetone to 1,3-propylene glycol of 1:1. 17 mL of water was added, followed by 17 g of K3PO4﹒3H2O, followed by 0.1 g of commercial Pd / C (5% loading). The reactor was purged with N2 three times, and then 1 MPa of H2 was injected. The reaction solution containing cyclohexanone was obtained by reacting at 250°C for 0.5 hours. After the reaction was completed, the reactor was immediately taken out and immersed in cold water to cool until the temperature dropped to room temperature. The reactor was opened and the product was quantified by gas chromatography (GC-FID).

[0030] Example 4

[0031] 1) The specific steps of preparing a hydrotalcite-supported nickel catalyst by an impregnation method are as follows: weigh 0.42 g of Ni(CH3COO)2﹒4H2O and dissolve it in 40 mL of ethanol solvent, then add 1.90 g of hydrotalcite to the above Ni(CH3COO)2 ethanol solution to obtain a slurry; place a beaker containing the above slurry on a magnetic stirrer to stir the slurry to completely evaporate the ethanol to obtain a solid; grind the solid in the beaker into a fine powder; put the above fine powder into a tubular furnace and reduce it in H2 (5% inAr) at 600°C for 6 hours to prepare a catalyst Ni / MgAlO.

[0032] 2) First, 5 g of acetone and 1,3-propylene glycol were mixed in a reactor in a molar ratio of 1:1. 15 mL of water was added, followed by 0.2 g of Ni / MgAlO and 0.1 g of K3PO4﹒3H2O. The reactor was purged with N2 three times, and then 0.4 MPa of N2 was injected. The reaction was carried out at 220°C for 6 hours to obtain a reaction solution containing cyclohexanone. After the reaction was completed, the reactor was immediately taken out and immersed in cold water to cool until the temperature dropped to room temperature. The reactor was opened and the product was quantified by gas chromatography (GC-FID).

Claims

1. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, characterized in that: The following steps are involved: 1) dissolving a metal nickel salt in an anhydrous organic solvent, the solution being referred to as solution a; adding hydrotalcite to solution a, the resulting suspension being referred to as slurry b; placing a beaker containing the slurry on a magnetic stirrer to stir the slurry, so that the organic solvent is completely evaporated to obtain a solid; grinding the solid in the beaker into a fine powder; placing the fine powder in a tubular furnace, and reducing it in H2 (5% inAr) at 300-600° C. for 1-12 hours to prepare a catalyst Ni / MgAlO; 2) Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; Ni / MgAlO equivalent to 0.1-10wt% of system d is added to system d; the reactor is purged with N2 for 1-3 times, and then 0.1-1MPa MPa of N2 is injected; the reactor is then reacted at 150-250°C and 600-1000rpm for 0.1-24 hours to obtain a reaction solution containing cyclohexanone.

2. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, characterized in that: The following steps are involved: The nickel salt is dissolved in an anhydrous organic solvent, and the solution is recorded as solution a; hydrotalcite is added to solution a, and the obtained suspension is recorded as slurry b; the beaker containing the slurry is placed on a magnetic stirrer to stir the slurry, so that the organic solvent is completely evaporated to obtain a solid; the solid in the beaker is ground into fine powder; the fine powder is placed in a tubular furnace, and reduced in H2 (5% inAr) at 300-600°C for 1-12 hours to prepare a catalyst Ni / MgAlO; Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; Ni / MgAlO equivalent to 0.1-10wt% of system d is added to system d; K3PO4 equivalent to 0.1-10wt% of system d is added to system d; the reactor is purged with N2 for 1-3 times, and then 0.1-1MPaMPa of N2 is injected; the reactor is then reacted at 150-250°C and a rotation speed of 600-1000rpm for 0.1-24 hours to obtain a reaction solution containing cyclohexanone.

3. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, characterized in that: The following steps are involved: Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; commercial Pd / C (1-10wt% loading amount) equivalent to 0.1-10wt% of system d is added to system d; K3PO4 equivalent to 0.1-200wt% of system d is added to system d; the reactor is purged with N2 for 1-3 times, and then 0.1-1MPaMPa of N2 is injected; the reactor is then reacted at 150-250°C and a rotation speed of 600-1000rpm for 0.1-24 hours to obtain a reaction solution containing cyclohexanone.

4. A method for preparing cyclohexanone by converting acetone and 1,3-propylene glycol, characterized in that: The following steps are involved: Acetone and 1,3-propylene glycol are mixed in a reactor to obtain solution c; water equivalent to 10-200wt% of solution c is added to solution c to obtain system d; commercial Pd / C (1-10wt% loading amount) equivalent to 0.1-10wt% of system d is added to system d; K3PO4 equivalent to 0.1-200wt% of system d is added to system d; the reactor is purged with H2 for 1-3 times, and then 0.1-1MPaMPa of H2 is injected; the reactor is then reacted at 150-250°C and a rotation speed of 600-1000rpm for 0.1-24 hours to obtain a reaction solution containing cyclohexanone.

5. The method according to claims 1 to 4, characterized in that The molar ratio of the acetone to 1,3-propylene glycol is 1:5 to 5:

1.

6. The method according to claims 1-2, characterized in that: The organic solvent is one or more of methanol, ethanol, propanol, acetone, and butanol, and the metal nickel salt is one or more of nickel acetate, nickel chloride, nickel nitrate, and nickel acetylacetonate.

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