阅读说明：本技术 一种制备3-羟基丙酸酯类衍生物的方法 (Method for preparing 3-hydroxy propionate derivatives ) 是由 孙乾辉 郑路凡 陈公哲 杜泽学 宗保宁 于 2020-06-24 设计创作，主要内容包括：本发明公开了一种制备3-羟基丙酸酯类衍生物的方法,包括：在醇类化合物和加氢脱氧催化剂的存在下,使甘油酸与氢气和醇类化合物进行反应,得到所述3-羟基丙酸酯类衍生物；其中,所述加氢脱氧催化剂为负载型金属催化剂与至少一种负载型金属氧化物催化剂和/或至少一种负载型杂多酸催化剂的混合物。本发明方法绿色环保,3-羟基丙酸酯类衍生物收率高。(The invention discloses a method for preparing 3-hydroxy propionate derivatives, which comprises the following steps: reacting glyceric acid with hydrogen and an alcohol compound in the presence of an alcohol compound and a hydrodeoxygenation catalyst to obtain the 3-hydroxypropionate 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 3-hydroxy propionate derivatives is high.)

1. A method for preparing a 3-hydroxypropionate derivative, comprising:

reacting glyceric acid with hydrogen and an alcohol compound in the presence of an alcohol compound and a hydrodeoxygenation catalyst to obtain the 3-hydroxypropionate 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.

2. The process according to claim 1, wherein the alcohol compound is selected from the group consisting of C1-C6 aliphatic or alicyclic alcohols, preferably methanol, ethanol or n-propanol.

3. The method according to claim 1, wherein the content of the glyceric acid in the solution of the glyceric acid and the alcohol compound is 0.1 to 60% by mass, preferably 0.5 to 30% by mass, and more preferably 1 to 20% by mass.

4. 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.

5. 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.

6. The process according to claim 5, wherein the supported metal catalyst has a metal loading of 0.5 to 45%, preferably 1 to 35%, based on the total mass of the carrier.

7. The process of claim 6, wherein the metal is a noble metal at a loading of 1 to 5%, and the metal is a non-noble metal at a loading of 5 to 25%.

8. 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 (a).

9. The process according to claim 8, wherein the supported metal oxide catalyst has a metal oxide loading of 1 to 50%, preferably 2 to 40%, more preferably 5 to 30%, 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, molybdenic or rhenium-containing heteropolyacid, more preferably phosphotungstic, silicotungstic, phosphomolybdic, silicomolybdic and phosphotrhenic acid.

11. A process according to claim 10, wherein the supported heteropolyacid catalyst is loaded at a level of from 1% to 50%, preferably from 2% to 40%, more preferably from 5% to 30% based on the total mass of the support.

12. A process according to claim 5, 8 or 10 wherein the support is selected from one or more of activated carbon, silica, alumina, zirconia, titania, silica alumina or molecular sieves.

13. The process of claim 1 wherein the molar ratio of metal in said supported metal catalyst to said glyceric acid is from 1: 1 to 1000, preferably 1:3 to 800, more preferably 1:5 to 500.

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 160 ℃ to 300 ℃, preferably 180 ℃ to 240 ℃, more preferably 180 ℃ to 220 ℃.

Technical Field

The invention relates to a method for preparing ester derivatives, in particular to a method for preparing 3-hydroxypropionate ester derivatives from renewable biomass-based raw materials.

Background

3-hydroxypropionate derivatives, such as methyl 3-hydroxypropionate, are important chemical raw materials and are often used as chemical reagents, pharmaceutical intermediates and material intermediates. The reaction process for synthesizing 1, 3-propanediol (key raw material for producing novel polyester fiber PTT with great development prospect) by using methyl 3-hydroxypropionate avoids the toxicity, instability and other negative factors in the preparation process of another intermediate 3-hydroxypropionaldehyde. Methyl 3-hydroxypropionate is expensive in price, and the synthesis method thereof is less discussed at present, so the research of the synthesis process thereof is highly concerned by the polyester academia (remainder. research of synthesizing methyl 3-hydroxypropionate from ethylene oxide catalyzed by sodium cobalt tetracarbonyl [ D ]. university of Dow. Resulter. 2012.).

The 3-hydroxy propionic acid lipid derivative can be obtained by esterification reaction of 3-hydroxy propionic acid and alcohol molecules. The synthesis process of 3-hydroxy propionic acid includes chemical process and microbial process, and the chemical process includes adding 3-hydroxy propionitrile into sodium hydroxide solution to react at 30 deg.c, adding sulfuric acid and stirring, and extracting with ether to produce 3-hydroxy propionic acid in 28-31% yield. At present, the chemical method uses non-renewable resources, has a plurality of byproducts, is difficult to separate and is easy to cause environmental pollution. The microorganism method is obtained by fermenting engineering Escherichia coli with carbon source such as glycerol and glucose. Although the microbiological method uses renewable resources as raw materials and has low pollution, the method also has the problems of low production efficiency, harsh reaction conditions and the like (the chemical engineering progresses, 2018, 37 (11): 4427-4436). Therefore, the method for green and efficient synthesis of the 3-hydroxypropionate derivatives by the heterogeneous catalysis starts from renewable biomass-based raw materials, and has very important scientific research and application values.

On the other hand, Glyceric acid (CAS: 473-81-4), also known as 2, 3-dihydroxypropionic acid, is an active organic compound containing three functional groups, widely participates in chemical reactions such as polymerization and condensation, and is an important intermediate and multifunctional reagent for chemical synthesis (Anhui agricultural science, 2017, 45 (36): 116-. Glyceric acid can be prepared by oxidizing glycerol which is a main byproduct in the production process of biodiesel and has the characteristics of greenness, renewability, wide sources and the like, and the great development of downstream high-value transformation of glycerol and derivatives thereof has very important significance for the sustainable development of chemical industry in China

CN108329203A discloses a method for preparing 3-hydroxypropionic acid by a two-step method starting from glyceric acid. In the first step of the method, glyceric acid and HI are mixed according to a certain proportion, and an intermediate product, namely 3-iodopropionic acid is obtained under the condition that other catalysts or a certain amount of metal catalysts are not added. And in the second step, reacting the organic phase obtained in the first step with water, and separating and acidifying the organic phase under the condition of adding a basic catalyst to obtain the 3-hydroxypropionic acid. This method has several problems: firstly, hydroiodic acid with extremely strong corrosivity is used in the first step, so that the requirement on the corrosion resistance of the device is enhanced, and the cost and the environmental protection risk of the device are increased; secondly, salts of the 3-hydroxypropionic acid are directly obtained in the second step, and finally, the 3-hydroxypropionic acid product can be obtained through acidification and separation; thirdly, the process flow is long, and complex processes such as extraction and separation of the solvent are involved.

Using ethylene oxide, CO and methanol as raw materials, Co₂(CO)₈The catalyst can also be synthesized into the methyl 3-hydroxypropionate by methyl hydrogen esterification (natural gas chemical industry, 2011, 36 (03): 34-36), the non-renewable petroleum-based ethylene oxide is used as a raw material in the process, the reaction raw materials such as CO, methanol and the like which are flammable, explosive and have high toxicity are involved, and the used cobalt carbonyl and other homogeneous catalysts are difficult to recycle, so that the process has high cost and low environmental friendliness and is not beneficial to the chemical industry in ChinaCan be developed continuously.

Disclosure of Invention

The invention provides a method for preparing 3-hydroxypropionate derivatives, which is used for efficiently converting glyceric acid into a target product, namely the 3-hydroxypropionate derivatives in an alcoholic solution in one step.

The invention provides a method for preparing 3-hydroxy propionate derivatives, which comprises the following steps:

reacting glyceric acid with hydrogen and alcohol in the presence of an alcohol compound neutralization hydrodeoxygenation catalyst to obtain the 3-hydroxypropionate 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, and specifically can be a mixture of a supported metal catalyst and at least one supported metal oxide catalyst, can also be a mixture of a supported metal catalyst and at least one supported heteropolyacid catalyst, and can also be a mixture of a supported metal catalyst and at least one supported metal oxide catalyst and at least one supported heteropolyacid catalyst.

Wherein (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.

The supported metal catalyst comprises a carrier and metal loaded on the carrier, wherein the carrier is selected from one or more of activated carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon aluminum oxide or molecular sieve; the metal is selected from one or more of group VIII and IB metals, preferably Co, Ni, Ru, Pd or Pt. 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 more preferably 1-5%, and when the metal is a non-noble metal, the loading is more preferably 5-25%.

The supported metal oxide catalyst comprises a carrier and a catalyst carrier supported on the carrierThe metal oxide on the carrier takes the total mass of the carrier as a reference, and the loading amount of the metal oxide is 1-50%, preferably 2-40%, and more preferably 5-30%; the carrier is selected from one or more of activated carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon aluminum oxide or molecular sieve; the metal oxide is MoO₃、WO₃Or ReO₃One or more of (a).

The supported heteropolyacid catalyst comprises a carrier and heteropolyacid loaded on the carrier, wherein the loading amount of the heteropolyacid is 1% -50%, preferably 2-40%, and more preferably 5-30% based on the total mass of the carrier; the carrier is one or more of activated carbon, silicon oxide, aluminum oxide, zirconium oxide, titanium oxide, silicon-aluminum oxide or molecular sieve; the metal atom in the heteropoly acid is selected from one or more of W, Mo, Re, V, Nb and Ta, the hetero atom is selected from one or more of Si or P, preferably one or more of tungstenic heteropoly acid, molybdenic heteropoly acid or rhenium heteropoly acid, and more preferably phosphotungstic acid, silicotungstic acid, phosphomolybdic acid, silicomolybdic acid, phosphothrenic acid and the like.

The alcohol compound is selected from one or more of C1-C6 aliphatic alcohol or alicyclic alcohol, and is preferably methanol, ethanol or n-propanol.

In the solution formed by glyceric acid and alcohol compound, the mass percentage content of glyceric acid can be 0.1-60%, preferably 0.5-30%, and more preferably 1-20%.

The molar ratio of the metal in the supported metal catalyst to the glyceric acid in the hydrodeoxygenation catalyst can be 1: 1 to 1000, preferably 1:3 to 800, more preferably 1:5 to 500.

The reaction is carried out at a pressure of 1MPa to 10MPa, preferably 2MPa to 6 MPa.

The temperature of the reaction may be 160 ℃ to 300 ℃, preferably 180 ℃ to 240 ℃, 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 3-hydroxypropionate derivative, the preparation method 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 3-hydroxypropionate derivative provided by the invention is carried out in an alcohol solution, other miscellaneous elements are not introduced except for a used heterogeneous catalyst, and the yield of the 3-hydroxypropionate derivative is higher, 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 glyceric acid is derived from Ikaty technologies, Inc. of Beijing.

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%. The precursor prepared in the above steps is placed in a quartz tube, firstly calcined for 3 hours at 500 ℃ in the air,10% MoO was obtained₃/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 respectively_x/SiO₂， 10％SiMoO_x/ZrO₂And 5% PReO_x/C。

Example 1 preparation of methyl 3-hydroxypropionate from Glycerol

With 10% Ni/Al₂O₃+10％MoO₃/TiO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged₂O₃Catalyst, 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. After the reaction is finished, taking out the reaction kettle from the heating furnace, cooling to room temperature, and putting the kettle intoAnd (3) reducing the pressure to normal pressure, opening a 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 2 preparation of methyl 3-hydroxypropionate from Glycerol

With 10% Ni/Al₂O₃+10％MoO₃/TiO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged₂O₃Catalyst, 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 methyl 3-hydroxypropionate from Glycerol

With 10% Ni/Al₂O₃+10％MoO₃/TiO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged₂O₃Catalyst, 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. 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 using the obtained liquid as a liquid phaseThe chromatography was analyzed and the conversion and product yield were calculated. The reaction results are shown in Table 1.

Example 4 preparation of methyl 3-hydroxypropionate from Glycerol

With 10% Ni/Al₂O₃+10％MoO₃/TiO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged₂O₃Catalyst, 0.2g 10% 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 ethyl 3-hydroxypropionate from Glycerol

With 10% Ni/Al₂O₃+10％MoO₃/TiO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged₂O₃Catalyst, 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 6 preparation of propyl 3-hydroxypropionate from Glycerol

With 10% Ni/Al₂O₃+10％MoO₃/TiO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged₂O₃Catalyst, 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 7 preparation of n-butyl 3-hydroxypropionate from Glycerol

With 10% Ni/Al₂O₃+10％MoO₃/TiO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 10% Ni/Al were charged₂O₃Catalyst, 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 8 preparation of methyl 3-hydroxypropionate from Glycerol

With 20% Co/SiO₂+20％WO₃/ZrO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

Into a 30mL autoclave, 0.5g of glyceric acid and 0.2g of 20% Co/SiO₂Catalyst, 0.1g 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 9 preparation of methyl 3-hydroxypropionate from Glycerol

With 5% Pd/TiO₂+5％ReO₃The catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.

In a 30mL autoclave, 0.5g glyceric acid and 0.05g 5% Pd/TiO were added₂Catalyst, 0.4g 5% ReO₃And C, catalyst and 20g 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 180 ℃, 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 methyl 3-hydroxypropionate from Glycerol

With 1% Pt/C + 20% PWO_x/SiO₂As a hydrodeoxygenation catalyst.

In a 30mL autoclave, 0.2g glyceric acid, 0.1g 1% Pt/C catalyst was addedAgent, 0.5g 20% PWO_x/SiO₂And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is sealed, 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 180 ℃, 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 11 preparation of methyl 3-hydroxypropionate from Glycerol

With 5% Pd/TiO₂+10％SiMoO_x/ZrO₂The catalyst obtained by mechanical mixing was used as a hydrodeoxygenation catalyst.

In a 30mL autoclave, 0.2g glyceric acid and 0.05g 5% Pd/TiO were added₂Catalyst, 0.2g 10% SiMoO_x/ZrO₂And (2) filling 2MPa hydrogen to replace residual air in the reaction kettle after the reaction kettle is sealed, 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 methyl 3-hydroxypropionate from Glycerol

With 1% Pt/C + 5% PReO_xThe catalyst obtained by/C mechanical mixing is used as a hydrodeoxygenation catalyst.

In a 30mL autoclave, 1g of glyceric acid, 0.1g of 1% Pt/C catalyst, 0.2g of 5% PReO were charged_xThe catalyst/C and 10g of methanol are added, 2MPa hydrogen is filled for replacing residual air in the reaction kettle after the reaction kettle is closed, after the reaction is repeated for three times, 2MPa hydrogen is filled into the reaction kettle, and the reaction kettle is placedThe mixture was heated in a heating furnace to a reaction temperature of 180 ℃ and stirred at 700rpm for 20 hours. 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.

Comparative example 1

The reaction was carried out according to the procedure of example 4, 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 4, except that only 10% MoO was added₃/TiO₂Catalyst without addition of 10% Ni/Al₂O₃A catalyst. The reaction results are shown in Table 1.

Comparative example 3

The reaction was carried out according to the procedure of example 4, 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 4, 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.

As can be seen from the data in Table 1, the method for preparing the 3-hydroxypropionate derivative provided by the invention can well realize the conversion of glyceric acid to the important chemical raw material 3-hydroxypropionate derivative in an alcohol solvent. Starting from glyceric acid, a yield of methyl 3-hydroxypropionate of 92% or a yield of ethyl 3-hydroxypropionate of 90% can be obtained.

As can be seen from comparative examples 1 and 2, the 3-hydroxypropionate derivative product could not be obtained by adding the supported metal catalyst or the supported metal oxide catalyst alone. As can be seen from comparative examples 3 and 4, the use of the combination of the supported metal catalyst and the metal oxide or the metal and metal oxide co-supported catalyst failed to achieve the yield level of the 3-hydroxypropionate 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 3-hydroxypropionic acid yield of examples and comparative examples