CN113968783A - Method for preparing short-carbon-chain dicarboxylic acid ester derivative - Google Patents

Method for preparing short-carbon-chain dicarboxylic acid ester derivative Download PDF

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CN113968783A
CN113968783A CN202010708401.8A CN202010708401A CN113968783A CN 113968783 A CN113968783 A CN 113968783A CN 202010708401 A CN202010708401 A CN 202010708401A CN 113968783 A CN113968783 A CN 113968783A
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catalyst
acid
supported
reaction
dicarboxylic acid
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CN113968783B (en
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孙乾辉
郑路凡
陈公哲
杜泽学
宗保宁
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Sinopec Research Institute of Petroleum Processing
China Petroleum and Chemical Corp
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China Petroleum and Chemical Corp
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Abstract

The invention discloses a method for preparing a short carbon chain dicarboxylic acid ester derivative with 3-6 carbon atoms, which comprises the following steps: in the presence of an alcohol compound and a hydrodeoxygenation catalyst, reacting short-carbon-chain dicarboxylic acid with alpha-oxygen-containing substituent with hydrogen and alcohol molecules to obtain the short-carbon-chain dicarboxylic acid ester derivative; wherein the hydrodeoxygenation catalyst is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst. The method is green and environment-friendly, and the yield of the short carbon chain dicarboxylic acid ester derivative is high.

Description

Method for preparing short-carbon-chain dicarboxylic acid ester derivative
Technical Field
The invention relates to a method for preparing a short carbon chain dicarboxylic acid ester derivative with 3-6 carbon atoms.
Background
The short carbon chain dicarboxylic acid ester derivatives with 3-6 carbon atoms are a chemical with very important value. For example, ester derivatives of adipic acid, such as dimethyl adipate, and the like, are useful as synthetic intermediates, raw materials for medicines, perfumes, as plasticizers, and high-boiling solvents. The adipic acid ester derivative can be used for preparing adipic acid after hydrolysis, and can also be used as a raw material for producing 1, 6-hexanediol by hydrogenation. The ester derivative of glutaric acid, such as dimethyl glutarate, is an environment-friendly high-boiling point solvent, has the characteristics of good dissolving power, low volatility, easy flowing, high safety, no toxicity, photochemical stability and the like, is widely used for automobile coatings, color steel plate coatings, can coatings, enameled wires and household appliance coatings, is also an important intermediate of fine chemicals, and is used for preparing polyester resin, adhesives, synthetic fibers, membrane materials and the like. Ester derivatives of succinic acid, such as dimethyl succinate, can be used for synthesizing light stabilizers, high-grade coatings, bactericides and medical intermediates. Dimethyl succinate can be oxidized into fumarate, and p-light benzoates and butenedioates are superior to organic acids and salts thereof in mildew resistance of foods. Dimethyl succinate is also an important medical upstream product, has high additional value and can be widely applied to the production process of various medical drugs.
At present, the production of the short carbon chain dicarboxylic acid ester derivatives is mainly obtained by esterification reaction of corresponding dicarboxylic acid and alcohol compounds, and the production of the dicarboxylic acid compounds mostly depends on non-renewable fossil resources, so that the problems of large pollution, environmental friendliness and the like in the production process are solved. In recent years, with the development of biomass conversion technology, new raw materials and methods are provided for the production of existing important chemicals.
The short carbon chain dicarboxylic acid with the alpha-oxygen-containing substituent is a common intermediate product or metabolite in the biomass conversion and utilization process, for example, the alpha-ketoglutaric acid is an important metabolic intermediate product in the tricarboxylic acid cycle of the microorganism, participates in the synthesis of amino acid, protein and vitamin in the organism and regulates and controls multiple energy metabolism, is an important nutrient substance, and has wide application prospects in various fields. In addition, alpha-ketoglutaric acid is also widely used in the field of chemical organic synthesis because of its special chemical properties. The alpha-ketoglutaric acid product can be safely and greenly obtained by a microbial fermentation method (food and fermentation industry, 2018, 44 (12): 150-. 2, 3-dihydroxy succinic acid is used as antioxidant synergist, retarder, tanning agent, chelating agent and medicine. Widely used in the industries of medicine, food, leather, textile and the like (synthetic chemistry, 2016,24(3): 266-. The 2-hydroxysuccinic acid is widely applied to the food and medicine industries (technical report of food science, 2019,37(2): 1-9).
Therefore, the synthesis of the short-carbon-chain dicarboxylic acid ester derivative from the short-carbon-chain dicarboxylic acid with the alpha-oxygen-containing substituent group has important contribution to reducing the dependence on petroleum-based products and further improving the application value of biomass raw materials, and has very important economic significance to the development and utilization of the whole biomass.
Disclosure of Invention
The invention provides a method for preparing a short-carbon-chain dicarboxylic acid ester derivative, which is characterized in that short-carbon-chain dicarboxylic acid with alpha-oxygen substituent is efficiently converted into a target product, namely the short-carbon-chain dicarboxylic acid ester derivative in an alcohol compound in one step, and the method is simple in process, green, environment-friendly and high in efficiency.
A method for preparing a short carbon chain dicarboxylic acid ester derivative comprises the following steps:
in the presence of an alcohol compound and a hydrodeoxygenation catalyst, reacting short-carbon-chain dicarboxylic acid containing 3-6 carbon atoms and alpha-oxygen-containing substituent with hydrogen and the alcohol compound to obtain the short-carbon-chain dicarboxylic acid ester derivative containing 3-6 carbon atoms;
wherein the hydrodeoxygenation catalyst is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst.
The alcohol compound is selected from C1-C6 saturated aliphatic alcohol or alicyclic alcohol, and is preferably methanol, ethanol or n-propanol.
The chemical structural formula of the short carbon chain dicarboxylic acid with the alpha-oxygen-containing substituent is as follows:
Figure BDA0002595568900000021
wherein R is1、R2And R3Is hydroxyl or carbonyl, n1 ranges from 0 to 3, and n2 ranges from 0 to 2. The oxygen-containing substituent is hydroxyl or carbonyl.
The short carbon chain dicarboxylic acid having an alpha-oxygen-containing substituent is preferably alpha-ketoglutaric acid, 2-hydroxyglutaric acid, 2-hydroxysuccinic acid, and 2, 3-dihydroxybutanedioic acid.
The chemical structural formula of the short carbon chain dicarboxylic acid ester derivative is as follows:
Figure BDA0002595568900000022
wherein R is4Is C1-C6 saturated straight chain or branched chain alkyl or saturated naphthenic base, and the value range of n3 is 1-4.
The short-carbon chain dicarboxylic acid ester derivative can be malonate, succinate, glutarate or adipate, and preferably succinate and glutarate.
The reaction has the following reaction formula:
Figure BDA0002595568900000031
wherein R is1、R2And R3Is hydroxy or carbonyl, R4Is C1-C6 saturated straight chain or branched chain alkyl or saturated naphthenic base, n1 is in the range of 0-3, n2 is in the range of 0-2, and n3 is in the range of 1-4.
For example, in the presence of methanol and a hydrodeoxygenation catalyst, alpha-ketoglutaric acid reacts with hydrogen and methanol according to the formula:
Figure BDA0002595568900000032
for example, the reaction of 2-hydroxyglutaric acid with hydrogen and methanol in the presence of methanol and a hydrodeoxygenation catalyst is represented by the formula:
Figure BDA0002595568900000033
for example, the reaction of 2-hydroxysuccinic acid with hydrogen and methanol in the presence of methanol and a hydrodeoxygenation catalyst is represented by the formula:
Figure BDA0002595568900000034
for example, the reaction of 2, 3-dihydroxybutanedioic acid with hydrogen and methanol in the presence of methanol and a hydrodeoxygenation catalyst is represented by the formula:
Figure BDA0002595568900000035
in the solution formed by the short carbon chain dicarboxylic acid with the alpha-oxygen-containing substituent and alcohol, the mass percentage of the short carbon chain dicarboxylic acid with the alpha-oxygen-containing substituent is 1-60%, preferably 2-45%, and more preferably 5-30%.
The supported metal catalyst comprises a carrier and a metal loaded on the carrier, wherein the metal is selected from one or more of VIII and IB group metals, and is preferably Co, Ni, Ru, Pd or Pt. The carrier is one or more of activated carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon-aluminum oxide or molecular sieve. The loading amount of the metal is 0.5-45%, preferably 1-35%, based on the total mass of the carrier.
When the metal is a noble metal, the loading is 1-5%, and when the metal is a non-noble metal, the loading is 5-25%.
The supported metal oxide catalyst comprises a carrier and a metal oxide supported on the carrier, wherein the metal oxide is selected from MoO3、WO3Or ReO3One or more of (a). The carrier is one or more of activated carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon-aluminum oxide or molecular sieve. The loading amount of the metal oxide is 1-60%, preferably 2-40%, and more preferably 5-25% based on the total mass of the carrier.
The supported heteropolyacid catalyst comprises a support and a heteropolyacid supported on the support, wherein the metal atom in the heteropolyacid is selected from one or more of W, Mo, Re, V, Nb and Ta, and the hetero atom in the heteropolyacid is selected from one or more of Si or P, preferably one or more of tungstenic heteropolyacid, molybdenitic heteropolyacid or rhenium-containing heteropolyacid, and more preferably phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid and phosphotrhenic acid. The carrier is one or more of activated carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon-aluminum oxide or molecular sieve. The loading amount of the heteropoly acid is 1-60%, preferably 2-40%, and more preferably 5-25% based on the total mass of the carrier.
In the hydrodeoxygenation catalyst, (mass of supported metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) 1: 0.1 to 100, preferably 1:0.2 to 10, more preferably 1:0.5 to 5.
According to one embodiment of the invention, the process conditions are as follows:
in the hydrodeoxygenation catalyst, the molar ratio of the metal in the supported metal catalyst to the short carbon chain dicarboxylic acid having an alpha-oxygen containing substituent may be 1: 1 to 1000, preferably 1:5 to 500, more preferably 1:5 to 250.
The reaction is carried out at a pressure of 1MPa to 10MPa, preferably 2MPa to 6 MPa.
The reaction temperature is 150 ℃ to 250 ℃, preferably 160 ℃ to 240 ℃, and more preferably 180 ℃ to 220 ℃.
The reaction time may be 1 to 40 hours, preferably 5 to 30 hours, and more preferably 10 to 20 hours.
The hydrodeoxygenation catalyst used in the process of the invention is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst or at least one supported heteropolyacid catalyst, and can be formulated by simple mechanical mixing.
The supported metal catalyst can be prepared according to the existing method, such as an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method or a vacuum impregnation method. During the specific preparation, after metal deposition, the solid powder is placed in an oven at 100-140 ℃ for drying for about 6-24 hours, the obtained supported catalyst precursor is calcined in the air at 300-800 ℃ for a period of time, and then the calcination is carried out in a reducing atmosphere (such as H)2Or H2And N2Mixed atmosphere) at a temperature of 200-500 ℃ for about 6-24 hours to obtain the supported metal catalyst.
The supported metal oxide catalyst or the supported heteropolyacid catalyst can be prepared according to the existing method, such as an isochoric impregnation method, an incipient wetness impregnation method, an ion exchange method, a deposition-precipitation method or a vacuum impregnation method; during the preparation, after the deposition of the metal oxide precursor or the heteropoly acid precursor, the solid powder is placed in an oven at 100-140 ℃ for drying for about 6-24 hours, and the obtained supported catalyst precursor is calcined in the air at 300-800 ℃ for about 6-24 hours to obtain the supported metal oxide catalyst or the supported heteropoly acid catalyst.
The supported metal oxide catalyst or the supported heteropolyacid catalyst and the supported metal catalyst can be uniformly ground according to a certain proportion before reaction and then added into a reaction system, and can also be respectively added into the reaction system according to a certain proportion.
When the method is used for preparing the short carbon chain dicarboxylic acid ester derivative, the preparation can be carried out in a reaction kettle, after the reaction is finished, the reaction kettle is taken out, cooled to room temperature, the pressure of the reaction kettle is relieved, after a kettle cover is opened, a liquid-solid mixture is taken out for suction filtration and separation, the obtained liquid is analyzed by liquid chromatography, and the conversion rate and the product yield are calculated. The method of the invention can also adopt other conventional reactors, such as fixed bed reactors and the like.
The method for preparing the short-carbon-chain dicarboxylic acid ester derivative uses the short-carbon-chain dicarboxylic acid containing the alpha-oxygen substituent, which is a common intermediate product or metabolite in the biomass conversion and utilization process, as a raw material, uses the alcohol compound, does not introduce other miscellaneous elements except a used heterogeneous catalyst, and has higher yield of the short-carbon-chain dicarboxylic acid ester derivative, so that the method not only further reduces the production cost, but also is more environment-friendly.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Wherein the sources of the tartronic acid, the 2-malic acid, the 2, 3-dicarboxylic acid, the 2-hydroxyglutaric acid, the alpha-ketoglutaric acid and the 2-hydroxyadipic acid are Beijing YinuoKa science and technology Co.
Preparation example 1
Hydrogenation catalyst 10% Ni/Al2O3The preparation of (1):
1mol/L of Ni (NO3)21.7mL of hydrochloric acid solution and 3.0mL of deionized water are mixed and stirred uniformly, and then SiO is added2Adding 0.9g of carrier into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and drying in an oven at 110 ℃ for 12 hours to obtain a catalyst precursor. The loading amount of Ni was 10% (mass%). Putting the precursor prepared in the step into a quartz tube, firstly calcining for 4H at 500 ℃ in the air, and then calcining for 20% H2+N2Reducing for 3h at the temperature of 500 ℃ to obtain the load type 10 percent Ni/Al2O3A catalyst.
Preparation of 20% Co/SiO according to the above method2，5％Pd/TiO2And 1% Pt/C catalyst.
Preparation example 2
Supported metal oxide catalyst 10% MoO3/TiO2The preparation of (1):
0.2g of ammonium molybdate is mixed with 5.0mL of water, the mixture is stirred evenly, and then TiO is added2Adding 1.00g of carrier into the mixed solution, stirring and soaking for 10 hours at room temperature, evaporating to remove water, and drying in an oven at 110 ℃ for 12 hours to obtain a catalyst precursor. MoO3The supporting amount of (B) is 10 mass%. Putting the precursor prepared in the step into a quartz tube, and calcining the precursor in the air at 500 ℃ for 3 hours to obtain 10% MoO3/TiO2。
The supported metal oxide catalyst is prepared according to the method, and 5 percent of ReO is loaded respectively3C and 20% WO3/ZrO2. Different supported metal oxide catalysts are prepared by selecting precursors corresponding to supported components, for example, the supported component is ReO3When the precursor is ammonium perrhenate, the precursor can be selected; the load component is WO3When the precursor is ammonium metatungstate, ammonium metatungstate can be selected as the precursor.
Preparation example 3
Preparation of the supported heteropolyacid catalyst:
the preparation method of different supported heteropolyacid catalysts is similar to that of supported metal oxides, and the precursors corresponding to the supported components are selected to prepare the supported heteropolyacid catalysts according to the examples, if the supported components are tungstic heteropolyacids such as phosphotungstic acid, silicotungstic acid and the like, the corresponding tungstic heteropolyacids such as phosphotungstic acid, silicotungstic acid and the like can be selected as the precursors; when the load component is a molybdenum-containing heteropoly acid, the corresponding molybdenum-containing heteropoly acid, such as phosphomolybdic acid, silicomolybdic acid and the like, can be selected as a precursor.
The supported heteropolyacid catalyst is prepared according to the method, and 20 percent of PWO is loaded respectivelyx/SiO2，10％SiMoOx/ZrO2And 5% PReOx/C。
EXAMPLE 1 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 10% Ni/Al was added2O3Catalyst, 0.2g 10% MoO3/TiO2The catalyst and 10g of methanol are added, 2MPa hydrogen is filled in the reaction kettle to replace residual air in the reaction kettle after the reaction kettle is closed, after the reaction is repeated for three times, 2MPa hydrogen is filled in the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 180 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 2 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, add0.5g of 2-hydroxysuccinic acid, 0.2g of 10% Ni/Al2O3Catalyst, 0.2g 10% MoO3/TiO2The catalyst and 10g of methanol are added, after the reaction kettle is closed, 2MPa hydrogen is filled to replace residual air in the reaction kettle, after the reaction is repeated for three times, 2MPa hydrogen is filled into the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 200 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 3 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 10% Ni/Al was added2O3Catalyst, 0.2g 10% MoO3/TiO2The catalyst and 10g of methanol are added, after the reaction kettle is closed, 2MPa hydrogen is filled to replace residual air in the reaction kettle, after the reaction is repeated for three times, 2MPa hydrogen is filled into the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 220 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 4 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 10% Ni/Al was added2O3Catalyst, 0.2g10％MoO3/TiO2The catalyst and 10g of methanol are added, after the reaction kettle is closed, 6MPa hydrogen is filled to replace residual air in the reaction kettle, after the reaction is repeated for three times, 4MPa hydrogen is filled into the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 180 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 5 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 20% Co/SiO2+20％WO3/ZrO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.1g of 20% Co/SiO2Catalyst, 0.4g 20% WO3/ZrO2The catalyst and 10g of methanol are added, 2MPa hydrogen is filled in the reaction kettle to replace residual air in the reaction kettle after the reaction kettle is closed, after the reaction is repeated for three times, 2MPa hydrogen is filled in the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 180 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 6 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 5% Pd/TiO2+5％ReO3The catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.05g of 5% Pd/TiO was added2Catalyst, 0.5g 5% ReO3The reaction kettle is sealed, 2MPa hydrogen is filled to replace residual air in the reaction kettle, and the reaction is repeated for three times2MPa of hydrogen is filled into the kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 180 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 7 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 1% Pt/C + 20% PWOx/SiO2As a hydrodeoxygenation catalyst.
In a 50mL autoclave, 1g of 2-hydroxysuccinic acid, 0.1g of 1% Pt/C catalyst, 0.2g of 20% PWOx/SiO2The catalyst and 10g of methanol are added, 2MPa hydrogen is filled in the reaction kettle to replace residual air in the reaction kettle after the reaction kettle is closed, after the reaction is repeated for three times, 2MPa hydrogen is filled in the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 180 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 8 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 5% Pd/TiO2+10％SiMoOx/ZrO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 2g of 2-hydroxysuccinic acid, 0.05g of 5% Pd/TiO was added2Catalyst, 0.2g 10% SiMoOx/ZrO2The catalyst and 10g of methanol are added, after the reaction kettle is closed, 2MPa hydrogen is filled to replace residual air in the reaction kettle, after the reaction is repeated for three times, 2MPa hydrogen is filled into the reaction kettle, the reaction kettle is placed on a heating furnace to be heated to the reaction temperature of 200 ℃, and the reaction is carried out for 20 hours under the rotation speed of 700rpm by stirring. After the reaction is finished, taking out the reaction kettle from the heating furnace, and coolingCooling to room temperature, reducing the pressure in the kettle to normal pressure, opening the kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using liquid chromatography, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 9 preparation of dimethyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 3g of 2-hydroxysuccinic acid, 0.1g of 1% Pt/C catalyst, 0.5g of 5% PReOxAnd C, catalyst and 10g of methanol, filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
Example 10 preparation of diethyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 10% Ni/Al was added2O3Catalyst, 0.2g 10% MoO3/TiO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. After the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, and obtaining liquidAnalysis was performed by liquid chromatography and conversion and product yield were calculated. The reaction results are shown in Table 1.
EXAMPLE 11 preparation of dipropyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 10% Ni/Al was added2O3Catalyst, 0.2g 10% MoO3/TiO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. The reaction results are shown in Table 1.
EXAMPLE 12 preparation of di-n-butyl succinate from 2-Hydroxysuccinic acid
With 10% Ni/Al2O3+10％MoO3/TiO2The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.
In a 50mL autoclave, 0.5g of 2-hydroxysuccinic acid, 0.2g of 10% Ni/Al was added2O3Catalyst, 0.2g 10% MoO3/TiO2And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is closed, repeating the steps for three times, filling 2MPa hydrogen into the reaction kettle, placing the reaction kettle on a heating furnace, heating to the reaction temperature of 200 ℃, and stirring and reacting for 20 hours at the rotating speed of 700 rpm. And after the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, reducing the pressure in the kettle to normal pressure, opening a kettle cover, taking out the liquid-solid mixture, performing suction filtration and separation, analyzing the obtained liquid by using a liquid chromatogram, and calculating the conversion rate and the product yield. Reaction ofThe results are shown in Table 1.
Example 13 preparation of dimethyl succinate from 2, 3-Dihydroxysuccinic acid
The reaction was carried out in accordance with the procedure of example 2, except that 2-hydroxysuccinic acid in the reaction raw material was changed to 2, 3-dihydroxybutanedioic acid of the same quality. The reaction results are shown in Table 1.
EXAMPLE 14 preparation of dimethyl glutarate from alpha-ketoglutarate
The reaction was carried out in accordance with the procedure of example 2, except that 2-hydroxysuccinic acid in the reaction raw material was changed to α -ketoglutaric acid of the same mass. The reaction results are shown in Table 1.
EXAMPLE 15 preparation of dimethyl glutarate from 2-Hydroxyglutaric acid
The reaction was carried out in accordance with the procedure of example 2, except that 2-hydroxysuccinic acid in the reaction raw material was changed to 2-hydroxyglutaric acid of the same mass. The reaction results are shown in Table 1.
EXAMPLE 16 preparation of dimethyl malonate from Hydroxymalonic acid
The reaction was carried out in accordance with the procedure of example 2, except that 2-hydroxysuccinic acid in the reaction raw material was changed to hydroxymalonic acid of the same mass. The reaction results are shown in Table 1.
EXAMPLE 17 preparation of dimethyl adipate from 2-Hydroxyadipic acid
The reaction was carried out in accordance with the procedure of example 2, except that 2-hydroxysuccinic acid in the reaction raw material was changed to 2-hydroxyadipic acid of the same mass. The reaction results are shown in Table 1.
Comparative example 1
The reaction was carried out according to the procedure of example 2, except that only 10% Ni/Al was added2O3Catalyst without addition of 10% MoO3/TiO2A catalyst. The reaction results are shown in Table 1.
Comparative example 2
The reaction was carried out according to the procedure of example 2, except that only 10% MoO was added3/TiO2Catalyst without addition of 10% Ni/Al2O3A catalyst. Inverse directionThe results are shown in Table 1.
Comparative example 3
The reaction was carried out according to the procedure of example 2, except that "0.2 g of 10% MoO" was added3/TiO2Catalyst "replacement by" 0.2g MoO3Catalyst ". The reaction results are shown in Table 1.
Comparative example 4
The procedure of preparation 1 was followed at 10% MoO3/TiO2Further loading 10% Ni component on the catalyst to obtain 10% Ni/10% MoO3/TiO2Co-supported catalyst
The reaction was carried out according to the procedure of example 2, except that "0.2 g 10% Ni/Al" was added2O3Catalyst, 0.2g 10% MoO3/TiO2Catalyst "replacement" 0.2g 10% Ni/10% MoO3/TiO2Co-supported catalyst ". The reaction results are shown in Table 1.
The data in table 1 show that the method for preparing the short-carbon-chain dicarboxylic acid ester derivatives provided by the invention can well realize the conversion from the short-carbon-chain dicarboxylic acid with the alpha-oxygen-containing substituent to the short-carbon-chain dicarboxylic acid ester derivatives which are important chemical raw materials in an organic solvent. Starting from 2-hydroxysuccinic acid, the yield of dimethyl succinate of up to 87% can be obtained. Starting from 2, 3-dihydroxysuccinic acid, the yield of dimethyl succinate of up to 81% can be obtained. Starting from alpha-ketoglutaric acid, the yield of dimethyl glutarate can be up to 85%. Starting from 2-hydroxyglutaric acid, yields of dimethyl glutarate of up to 83% are obtained. Starting from tartronic acid, a yield of dimethyl malonate of up to 83% can be obtained. Starting from 2-hydroxyadipic acid, yields of up to 81% of dimethyl adipate can be achieved.
As can be seen from comparative examples 1 and 2, neither supported metal catalyst nor supported metal oxide catalyst alone can yield succinate derivative products. As can be seen from comparative examples 3 and 4, neither the combination of the supported metal catalyst and the metal oxide nor the catalyst supported by the metal and the metal oxide can achieve the yield level of the succinate derivative of the catalyst system of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
TABLE 1 reaction conditions, conversion and yield of examples and comparative examples
Figure BDA0002595568900000121
Figure BDA0002595568900000131

Claims (15)

1. A method for preparing a short carbon chain dicarboxylic acid ester derivative comprises the following steps:
in the presence of an alcohol compound and a hydrodeoxygenation catalyst, reacting short-carbon-chain dicarboxylic acid containing 3-6 carbon atoms and alpha-oxygen-containing substituent with hydrogen and the alcohol compound to obtain a short-carbon-chain dicarboxylic acid ester derivative containing 3-6 carbon atoms;
wherein the hydrodeoxygenation catalyst is a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and/or at least one supported heteropolyacid catalyst.
2. The process according to claim 1, wherein the alcohol compound is selected from the group consisting of C1-C6 saturated aliphatic or alicyclic alcohols, preferably methanol, ethanol or n-propanol.
3. The method of claim 1, wherein the short carbon chain dicarboxylic acid having an alpha-oxygen containing substituent has the chemical formula:
Figure FDA0002595568890000011
wherein R is1、R2And R3Is hydroxyl or carbonyl, n1 ranges from 0 to 3, and n2 ranges from 0 to 2.
4. The method according to claim 3, wherein the short carbon chain dicarboxylic acid having an alpha-oxygen containing substituent is preferably alpha-ketoglutaric acid, 2-hydroxyglutaric acid, 2-hydroxysuccinic acid and 2, 3-dihydroxysuccinic acid.
5. The method according to claim 1, wherein the short carbon chain dicarboxylic acid ester derivative has a chemical formula:
Figure FDA0002595568890000012
wherein R is4Is C1-C6 saturated straight chain or branched chain alkyl or saturated naphthenic base, and the value range of n3 is 1-4.
6. The method according to claim 1, wherein the solution of the short carbon chain dicarboxylic acid with alpha-oxygen substituent and the alcohol contains 1 to 60% by weight of the short carbon chain dicarboxylic acid with alpha-oxygen substituent, preferably 2 to 45% by weight of the solution, and more preferably 5 to 30% by weight of the solution.
7. The process according to claim 1, wherein the supported metal catalyst comprises a support and a metal selected from one or more of group VIII and IB metals, preferably Co, Ni, Ru, Pd or Pt, supported on the support; the loading amount of the metal is 0.5-45%, preferably 1-35%, based on the total mass of the carrier.
8. The method according to claim 7, wherein when the metal is a noble metal, the loading amount is 1-5%; when the metal is a non-noble metal, the loading capacity is 5-25%.
9. The process according to claim 1, wherein the supported metal oxide catalyst comprises a carrier and a metal oxide selected from MoO supported on the carrier3、WO3Or ReO3One or more of; the loading amount of the metal oxide is 1-60%, preferably 2-40%, and more preferably 5-25% based on the total mass of the carrier.
10. A process according to claim 1, wherein the supported heteropolyacid catalyst comprises a support and a heteropolyacid supported on the support, the heteropolyacid having metal atoms selected from one or more of W, Mo, Re, V, Nb and Ta and heteroatoms selected from one or more of Si or P, preferably one or more of a tungstenic heteropolyacid, a molybdenic heteropolyacid or a rhenium-containing heteropolyacid, more preferably a phosphotungstic acid, a silicotungstic acid, a phosphomolybdic acid, a silicomolybdic acid and a phosphotrhenic acid; the loading amount of the heteropoly acid is 1-60%, preferably 2-40%, and more preferably 5-25% based on the total mass of the carrier.
11. The process of any one of claims 7, 9 or 10, wherein the support is one or more of activated carbon, silica, alumina, zirconia, titania, silica alumina or a molecular sieve.
12. The process according to claim 1, wherein in the hydrodeoxygenation catalyst (mass of supported metal catalyst): (mass of supported metal oxide catalyst and/or supported heteropolyacid catalyst) 1: 0.1 to 100, preferably 1:0.2 to 10, more preferably 1:0.5 to 5.
13. The process of claim 1, wherein the molar ratio of metal in the supported metal catalyst in the hydrodeoxygenation catalyst to the short carbon chain dicarboxylic acid having alpha-oxygen containing substituents is from 1: 1 to 1000, preferably 1:5 to 500, more preferably 1:5 to 250.
14. The process according to claim 1, wherein the reaction is carried out at a pressure of 1 to 10MPa, preferably 2 to 6 MPa.
15. The process according to claim 1, wherein the reaction temperature is 150 ℃ to 250 ℃, preferably 160 ℃ to 240 ℃, more preferably 180 ℃ to 220 ℃.
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