Production method of ethyl 3-ethoxypropionate

Abstract

The invention provides a production method of ethyl 3-ethoxypropionate, and belongs to the technical field of organic synthesis. The preparation method comprises the following steps: adding ethanol and a catalyst into a reactor, dropwise adding ethyl acrylate, stirring for reaction, filtering, and recovering the catalyst to obtain ethyl 3-ethoxypropionate; the catalyst is a modified UiO-66-NH2 / layered metal oxide catalyst loaded with K2O (potassium oxide). The synthesis of the ethyl 3-ethoxypropionate is carried out under the catalytic action of the catalyst, the preparation method is simple, the conditions are mild, the product yield is high, the catalyst can be repeatedly utilized for multiple times, the method is green and environment-friendly, the cost is relatively low, and the method has a wide application prospect.

Description

Technical Field

[0001] The invention relates to the technical field of organic synthesis, and in particular to a method for producing ethyl 3-ethoxypropionate. Background Art

[0002] 3-Ethoxyethyl propionate (EEP) is a colorless liquid with a special aroma, a boiling point of 169-171℃, non-toxic to the human body, and an important organic solvent and organic synthesis intermediate. Its ether ester group, linear structure, and propionyl group in the molecular center give this material some properties that other solvents do not have, such as slow evaporation, no solvent cracking in baking applications, high solubility in a wide range of polymers, low solution viscosity (relative to its evaporation rate), good solvent release in the coating, and good flow and even coating properties in the coating. EEP solvent has a moderate odor, low surface tension, and high resistivity. It has a special function of preventing silver powder from coarsening and blackening. It is mainly used in automotive coatings (original paint, repair paint), daily electrical appliance coatings, and can be used in screen printing inks, other inks and graphic products. It is a slow-drying solvent for high-end inks and can also be used in the microelectronics industry (photoresist removal, diluent).

[0003] The sodium ethoxide catalytic method requires the addition of water or acid to destroy the sodium ethoxide after the reaction, which produces a lot of salt-containing wastewater; anion exchange resin has poor high temperature resistance, and the reaction temperature must be controlled below 35°C. Therefore, the development of highly active and easily separable heterogeneous solid base catalysts is of great significance for the efficient and clean production of EEP.

[0004] U.S. Patent No. 5,081,285 uses ethanol and ethyl acrylate as raw materials, methanesulfonic acid as catalyst, and reacts at 120-130° C. to obtain the product 3-ethoxypropionic acid ethyl ester. However, the reaction temperature is high, there are many side reactions, and the yield is low, about 41%, which is not suitable for industrial production.

[0005] In Chinese invention patent CN101423475B, an alkaline catalyst such as metallic sodium or sodium ethoxide is used to synthesize 3-ethoxypropionic acid ethyl ester using ethanol and ethyl acrylate as raw materials. The reaction is carried out in an intermittent reaction form. Although the reaction yield reaches 96%, the catalyst is sensitive to water and needs to be inactivated after the reaction is completed. The operation is cumbersome, the efficiency is low, and the pollution is heavy.

[0006] The literature (Tetrahedroletters, 46(19), 3279-3282: 2005) uses aluminum oxide-supported potassium fluoride as a catalyst to synthesize ethyl 3-ethoxypropionate from ethanol and ethyl acrylate. Acetonitrile is used as a solvent in the process. The yield is 90%, but a large amount of solvent needs to be recovered. In addition, the reaction time is 20 hours, which is too long and affects the production efficiency. Summary of the invention

[0007] The invention aims to provide a production method of ethyl 3-ethoxypropionate. The method comprises the following steps: reacting under the catalytic action of a catalyst, and the preparation method is simple, the conditions are mild, the product yield is high, the catalyst can be reused for many times, the method is green and environmentally friendly, the cost is low, and the method has broad application prospects.

[0008] The technical solution of the present invention is achieved in this way: The invention provides a production method of ethyl 3-ethoxypropionate. Ethanol and a catalyst are added into a reactor, ethyl acrylate is added dropwise, the reaction is stirred, filtered, and the catalyst is recovered to prepare ethyl 3-ethoxypropionate. The catalyst is a modified UiO-66-NH2 / layered metal oxide catalyst loaded with K2O.

[0009] As a further improvement of the present invention, the reaction temperature is 40-70° C. and the reaction time is 2-10 h.

[0010] As a further improvement of the present invention, the molar ratio of ethanol to ethyl acrylate is 1-3:0.5-1, and the added amount of the catalyst is 2-3wt% of the mass of ethanol.

[0011] As a further improvement of the present invention, the preparation method of the catalyst is as follows: S1. Preparation of UiO-66-NH2: zirconium tetrachloride and 2-aminoterephthalic acid are added to a mixed solvent, subjected to hydrothermal reaction, filtered, washed, and dried to obtain UiO-66-NH2; S2. Preparation of UiO-66-NH2 / layered metal oxide: dissolving magnesium nitrate, calcium nitrate and aluminum nitrate in water, dropping alkali solution, adding UiO-66-NH2, heating for crystallization, filtering, washing, drying and calcining to obtain UiO-66-NH2 / layered metal oxide; S3. Preparation of modified UiO-66-NH2 / layered metal oxide: adding UiO-66-NH2 / layered metal oxide to water, adding dopamine hydrochloride and a catalyst, heating and stirring to react, filtering, washing, and drying to obtain modified UiO-66-NH2 / layered metal oxide; S4. Preparation of a catalyst precursor: dissolving potassium nitrate in water, adding modified UiO-66-NH2 / layered metal oxide, uniformly dispersing by ultrasonication, and evaporating the solvent to obtain a catalyst precursor; S5. Preparation of catalyst: The catalyst precursor is calcined under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst.

[0012] As a further improvement of the present invention, the molar ratio of zirconium tetrachloride and 2-aminoterephthalic acid in step S1 is 1:1, the mixed solvent is a mixed solvent of N,N-dimethylformamide and acetic acid in a volume ratio of 35-40:2-4, the temperature of the hydrothermal reaction is 120-130°C, and the time is 20-24h.

[0013] As a further improvement of the present invention, the mass ratio of magnesium nitrate, calcium nitrate, aluminum nitrate and UiO-66-NH2 in step S2 is 3-5:2-3:5-7:12-15, the pH value of the solution is adjusted to 7.5-8.5 by dropping alkali solution, the heating crystallization temperature is 85-95°C, the time is 20-40min, the calcination temperature is 600-700°C, the time is 1-3h, and the alkali solution is NaOH or KOH solution.

[0014] As a further improvement of the present invention, the mass ratio of UiO-66-NH2 / layered metal oxide, dopamine hydrochloride and catalyst in step S3 is 10:4-6:1-2, the catalyst is a Tris-HCl solution with a pH of 8.5-9.5, the temperature of the heating and stirring reaction is 45-55°C, and the time is 3-5h.

[0015] As a further improvement of the present invention, the mass ratio of potassium nitrate, modified UiO-66-NH2 / layered metal oxide in step S4 is 4-7:10, the power of the ultrasonic dispersion is 1000-2000 W, and the time is 10-20 min.

[0016] As a further improvement of the present invention, the volume ratio of the mixed gas of methanol and nitrogen in step S5 is 3-5:10, the calcination temperature is 600-700° C., and the time is 4-6 hours.

[0017] As a further improvement of the present invention, the reaction is carried out in a continuous, semi-continuous or batch manner, with the catalyst being solid and the rest being liquid, and the mixed materials are passed through a catalyst fixed bed or the materials and the catalyst are stirred and mixed.

[0018] The present invention has the following beneficial effects: KNO3, as a neutral compound, can generate strong alkaline sites after being loaded on a suitable carrier and calcined, showing excellent catalytic activity, and is an efficient and economical solid base catalyst. However, the strong alkaline sites of K2O generated after calcination of KNO3 are easily dissolved in the reaction liquid and fall off the carrier in the liquid phase reaction, resulting in reduced reusability of the catalyst. In addition, the decomposition temperature of KNO3 (>700°C) is high, and if the calcination is not complete, it will lead to low catalyst alkalinity.

[0019] The present invention prepares a catalyst, which uses a metal organic framework material UiO-NH2 as a carrier, and is a crystalline material formed by metal ions or clusters and organic ligands connected to each other through coordination bonds, has a large specific surface area and abundant basic site centers, and is compounded with Mg / Ca / Al layered metal oxides through surface amino groups, greatly improving the specific surface area and catalytic active sites of the catalyst, and improving the catalytic activity of the catalyst. After the surface is further coated and modified by polydopamine, on the one hand, it can be easy to fix K2O through its active groups amino, carboxyl, etc., and on the other hand, after high-temperature calcination, polydopamine is decomposed and carbonized, and the generated C undergoes an oxidation-reduction reaction with undecomposed KNO3, promoting the further decomposition of KNO3, thereby generating more basic sites. At the same time, KNO3 is calcined in a mixed gas containing methanol, and a reducing substance is introduced, which undergoes an oxidation-reduction reaction with KNO3, thereby further promoting the decomposition of KNO3 without destroying the carrier structure.

[0020] The synthesis of ethyl 3-ethoxypropionate of the invention is carried out under the catalytic action of a catalyst, the preparation method is simple, the conditions are mild, the product yield is high, the catalyst can be reused multiple times, the invention is green and environmentally friendly, the cost is low, and the invention has broad application prospects. DETAILED DESCRIPTION

[0021] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0022] Preparation Example 1 Preparation of Catalyst The following steps are involved: S1. Preparation of UiO-66-NH2: 10 mmol zirconium tetrachloride and 10 mmol 2-aminoterephthalic acid were added to 100 mL of a mixed solvent, and subjected to a hydrothermal reaction at 120° C. for 20 h. The mixture was filtered, washed, and dried to obtain UiO-66-NH2. The mixed solvent is a mixed solvent of N,N-dimethylformamide and acetic acid in a volume ratio of 35:2; S2. Preparation of UiO-66-NH2 / layered metal oxide: 3 g of magnesium nitrate, 2 g of calcium nitrate, and 5 g of aluminum nitrate were dissolved in 200 mL of water, and NaOH solution was added dropwise to adjust the solution pH to 7.5, and 12 g of UiO-66-NH2 was added, heated to 85°C, crystallized for 20 min, filtered, washed, dried, and calcined at 600°C for 1 h to obtain UiO-66-NH2 / layered metal oxide; S3. Preparation of modified UiO-66-NH2 / layered metal oxide: 10 g of UiO-66-NH2 / layered metal oxide was added to 200 mL of water, 4 g of dopamine hydrochloride and 1 g of catalyst were added, heated to 45° C., stirred for reaction for 3 h, filtered, washed, and dried to obtain modified UiO-66-NH2 / layered metal oxide; The catalyst is a Tris-HCl solution with a pH of 8.5; S4. Preparation of a catalyst precursor: 4 g of potassium nitrate was dissolved in 200 mL of water, 10 g of modified UiO-66-NH2 / layered metal oxide was added, ultrasonic dispersion was performed at 1000 W for 10 min, and the solvent was evaporated to obtain a catalyst precursor; S5. Preparation of the catalyst: The catalyst precursor was calcined at 600° C. for 4 h under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst; The volume ratio of the mixed gas of methanol and nitrogen is 3:10.

[0023] Preparation Example 2 Preparation of Catalyst The following steps are involved: S1. Preparation of UiO-66-NH2: 10 mmol zirconium tetrachloride and 10 mmol 2-aminoterephthalic acid were added to 100 mL of a mixed solvent, and subjected to a hydrothermal reaction at 130° C. for 24 h. The mixture was filtered, washed, and dried to obtain UiO-66-NH2. The mixed solvent is a mixed solvent of N,N-dimethylformamide and acetic acid in a volume ratio of 40:4; S2. Preparation of UiO-66-NH2 / layered metal oxide: 5 g of magnesium nitrate, 3 g of calcium nitrate, and 7 g of aluminum nitrate were dissolved in 200 mL of water, KOH solution was added dropwise to adjust the solution pH to 8.5, 15 g of UiO-66-NH2 was added, heated to 95°C, crystallized for 40 min, filtered, washed, dried, and calcined at 700°C for 3 h to obtain UiO-66-NH2 / layered metal oxide; S3. Preparation of modified UiO-66-NH2 / layered metal oxide: 10 g of UiO-66-NH2 / layered metal oxide was added to 200 mL of water, 6 g of dopamine hydrochloride and 2 g of catalyst were added, heated to 55° C., stirred for reaction for 5 h, filtered, washed, and dried to obtain modified UiO-66-NH2 / layered metal oxide; The catalyst is a Tris-HCl solution with a pH of 9.5; S4. Preparation of a catalyst precursor: 7 g of potassium nitrate was dissolved in 200 mL of water, 10 g of modified UiO-66-NH2 / layered metal oxide was added, ultrasonic dispersion was performed at 2000 W for 20 min, and the solvent was evaporated to obtain a catalyst precursor; S5. Preparation of the catalyst: The catalyst precursor was calcined at 700°C for 6h under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst; The volume ratio of the mixed gas of methanol and nitrogen is 5:10.

[0024] Preparation Example 3 Preparation of Catalyst The following steps are involved: S1. Preparation of UiO-66-NH2: 10 mmol zirconium tetrachloride and 10 mmol 2-aminoterephthalic acid were added to 100 mL of a mixed solvent, and subjected to a hydrothermal reaction at 125°C for 22 h. The mixture was filtered, washed, and dried to obtain UiO-66-NH2. The mixed solvent is a mixed solvent of N,N-dimethylformamide and acetic acid in a volume ratio of 37:3; S2. Preparation of UiO-66-NH2 / layered metal oxide: 4 g of magnesium nitrate, 2.5 g of calcium nitrate, and 6 g of aluminum nitrate were dissolved in 200 mL of water, and NaOH solution was added dropwise to adjust the solution pH to 8, and 13 g of UiO-66-NH2 was added, heated to 90°C, crystallized for 30 min, filtered, washed, dried, and calcined at 650°C for 2 h to obtain UiO-66-NH2 / layered metal oxide; S3. Preparation of modified UiO-66-NH2 / layered metal oxide: 10 g of UiO-66-NH2 / layered metal oxide was added to 200 mL of water, 5 g of dopamine hydrochloride and 1.5 g of catalyst were added, heated to 50° C., stirred for reaction for 4 h, filtered, washed, and dried to obtain modified UiO-66-NH2 / layered metal oxide; The catalyst is a Tris-HCl solution with a pH of 9; S4. Preparation of a catalyst precursor: 5.5 g of potassium nitrate was dissolved in 200 mL of water, 10 g of modified UiO-66-NH2 / layered metal oxide was added, ultrasonic dispersion was performed at 1500 W for 15 min, and the solvent was evaporated to obtain a catalyst precursor; S5. Preparation of the catalyst: The catalyst precursor was calcined at 650° C. for 5 h under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst; The volume ratio of the mixed gas of methanol and nitrogen is 4:10.

[0025] Comparative Preparation Example 1 Compared with Preparation Example 3, the difference is that step S1 is not performed.

[0026] The details are as follows: S1. Preparation of layered metal oxide: 4 g of magnesium nitrate, 2.5 g of calcium nitrate, and 6 g of aluminum nitrate were dissolved in 200 mL of water, and a NaOH solution was added dropwise to adjust the solution pH to 8, heated to 90°C, crystallized for 30 min, filtered, washed, dried, and calcined at 650°C for 2 h to obtain a layered metal oxide; S2. Preparation of modified layered metal oxide: 10 g of layered metal oxide was added to 200 mL of water, 5 g of dopamine hydrochloride and 1.5 g of catalyst were added, heated to 50° C., stirred for reaction for 4 h, filtered, washed, and dried to obtain a modified layered metal oxide; The catalyst is a Tris-HCl solution with a pH of 9; S3. Preparation of a catalyst precursor: 5.5 g of potassium nitrate was dissolved in 200 mL of water, 10 g of a modified layered metal oxide was added, and ultrasonic dispersion was performed at 1500 W for 15 min, and the solvent was evaporated to obtain a catalyst precursor; S4. Preparation of the catalyst: The catalyst precursor was calcined at 650° C. for 5 h under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst; The volume ratio of the mixed gas of methanol and nitrogen is 4:10.

[0027] Comparative Preparation Example 2 Compared with Preparation Example 3, the difference is that step S2 is not performed.

[0028] The details are as follows: S1. Preparation of UiO-66-NH2: 10 mmol zirconium tetrachloride and 10 mmol 2-aminoterephthalic acid were added to 100 mL of a mixed solvent, and subjected to a hydrothermal reaction at 125°C for 22 h. The mixture was filtered, washed, and dried to obtain UiO-66-NH2. The mixed solvent is a mixed solvent of N,N-dimethylformamide and acetic acid in a volume ratio of 37:3; S2. Preparation of modified UiO-66-NH2: 10 g of UiO-66-NH2 / layered metal oxide was added to 200 mL of water, 5 g of dopamine hydrochloride and 1.5 g of catalyst were added, heated to 50°C, stirred for 4 h, filtered, washed, and dried to obtain modified UiO-66-NH2; The catalyst is a Tris-HCl solution with a pH of 9; S3. Preparation of catalyst precursor: 5.5 g of potassium nitrate was dissolved in 200 mL of water, 10 g of modified UiO-66-NH2 was added, ultrasonic dispersion was performed at 1500 W for 15 min, and the solvent was evaporated to obtain a catalyst precursor; S4. Preparation of the catalyst: The catalyst precursor was calcined at 650° C. for 5 h under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst; The volume ratio of the mixed gas of methanol and nitrogen is 4:10.

[0029] Comparative Preparation Example 3 Compared with Preparation Example 3, the difference is that step S3 is not performed.

[0030] The details are as follows: S1. Preparation of UiO-66-NH2: 10 mmol zirconium tetrachloride and 10 mmol 2-aminoterephthalic acid were added to 100 mL of a mixed solvent, and subjected to a hydrothermal reaction at 125°C for 22 h. The mixture was filtered, washed, and dried to obtain UiO-66-NH2. The mixed solvent is a mixed solvent of N,N-dimethylformamide and acetic acid in a volume ratio of 37:3; S2. Preparation of UiO-66-NH2 / layered metal oxide: 4 g of magnesium nitrate, 2.5 g of calcium nitrate, and 6 g of aluminum nitrate were dissolved in 200 mL of water, and NaOH solution was added dropwise to adjust the solution pH to 8, and 13 g of UiO-66-NH2 was added, heated to 90°C, crystallized for 30 min, filtered, washed, dried, and calcined at 650°C for 2 h to obtain UiO-66-NH2 / layered metal oxide; S3. Preparation of catalyst precursor: 5.5 g of potassium nitrate was dissolved in 200 mL of water, 10 g of UiO-66-NH2 / layered metal oxide was added, ultrasonic dispersion was performed at 1500 W for 15 min, and the solvent was evaporated to obtain a catalyst precursor; S4. Preparation of the catalyst: The catalyst precursor was calcined at 650° C. for 5 h under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst; The volume ratio of the mixed gas of methanol and nitrogen is 4:10.

[0031] Comparative Preparation Example 4 Compared with Preparation Example 3, the difference is that the mixed gas of methanol and nitrogen in step S5 is replaced by nitrogen.

[0032] The details are as follows: S5. Preparation of catalyst: The catalyst precursor was calcined at 650° C. for 5 h under nitrogen to obtain a catalyst.

[0033] Test Example 1 The specific surface area and total pore volume of the catalysts prepared in Preparation Examples 1-3 and Comparative Preparation Examples 1-4 were measured using a 3-FLEX 3500 multi-station high-throughput gas adsorption instrument.

[0034] The results are shown in Table 1.

[0035] Table 1 Group <![CDATA[Specific surface area (m 2 / g)]]> <![CDATA[Total pore volume (cm 3 / g)]]> Example 1 815.2 0.689 Example 2 814.9 0.688 Example 3 817.0 0.691 Comparative Example 1 678.5 0.514 Comparative Example 2 725.7 0.591 Comparative Example 3 775.1 0.624 Comparative Example 4 801.5 0.681 It can be seen from the above table that the catalysts prepared in Preparation Examples 1-3 of the present invention have larger specific surface areas and total pore volumes.

[0036] Example 1 A method for producing ethyl 3-ethoxypropionate comprises the following steps: adding 1 mol of ethanol and a catalyst obtained in Preparation Example 1 into a reactor, wherein the amount of the catalyst added is 2 wt% of the mass of the ethanol; dropping 0.5 mol of ethyl acrylate into the reactor, stirring the reactor at 40° C. for 5 h, filtering the reactor, recovering the catalyst, and producing ethyl 3-ethoxypropionate.

[0037] Example 2 A method for producing ethyl 3-ethoxypropionate comprises the following steps: adding 3 mol of ethanol and a catalyst prepared in Preparation Example 2 into a reactor, wherein the amount of the catalyst added is 3 wt% of the mass of the ethanol; dropping 1 mol of ethyl acrylate into the reactor, stirring the reaction at 70° C. for 5 h, filtering, recovering the catalyst, and preparing ethyl 3-ethoxypropionate.

[0038] Example 3 A method for producing ethyl 3-ethoxypropionate comprises the following steps: adding 2 mol of ethanol and a catalyst obtained in Preparation Example 3 into a reactor, wherein the amount of the catalyst added is 2.5 wt% of the mass of the ethanol; dropping 0.7 mol of ethyl acrylate into the reactor, stirring the reactor at 55° C. for 5 h, filtering the reactor, recovering the catalyst, and producing ethyl 3-ethoxypropionate.

[0039] Comparative Example 1 Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 1.

[0040] Comparative Example 2 Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 2.

[0041] Comparative Example 3 Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 3.

[0042] Comparative Example 4 Compared with Example 3, the difference is that the catalyst is prepared by Comparative Preparation Example 4.

[0043] Test Example 2 The reactions in Examples 1-3 and Comparative Examples 1-4 were evaluated and the results are shown in Table 2.

[0044] Table 2 Group Yield of 3-ethoxypropionic acid ethyl ester (%) Purity of ethyl 3-ethoxypropionate (%) Example 1 99.95 >99.99 Example 2 99.93 >99.99 Example 3 99.97 >99.99 Comparative Example 1 91.72 95.10 Comparative Example 2 87.18 93.35 Comparative Example 3 89.49 94.92 Comparative Example 4 92.72 92.48 It can be seen from the above table that the methods in Examples 1-3 of the present invention can obtain high-purity ethyl 3-ethoxypropionate with a high reaction yield.

[0045] Test Example 3 The catalysts after the reaction in Examples 1-3 and Comparative Examples 1-4 were separated by filtration, washed, and dried. The same operation was repeated 5 times to carry out the catalytic reaction. The fifth reaction was evaluated. The results are shown in Table 3.

[0046] Table 3 Group Yield of 3-ethoxypropionic acid ethyl ester (%) Purity of ethyl 3-ethoxypropionate (%) Example 1 99.88 >99.99 Example 2 99.85 >99.99 Example 3 99.90 >99.99 Comparative Example 1 87.92 92.19 Comparative Example 2 84.51 90.58 Comparative Example 3 81.49 86.25 Comparative Example 4 85.92 89.79 It can be seen from the above table that the catalysts in Examples 1-3 of the present invention still maintain relatively high catalytic activity after multiple catalytic reactions.

[0047] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims

1. A method for producing ethyl 3-ethoxypropionate, characterized in that, Ethanol and a catalyst are added into a reactor, ethyl acrylate is added dropwise, the reaction is stirred, filtered, and the catalyst is recovered to obtain ethyl 3-ethoxypropionate; the catalyst is a modified UiO-66-NH2 / layered metal oxide catalyst loaded with K2O.

2. The production method according to claim 1, characterized in that The reaction temperature is 40-70°C and the reaction time is 2-10h.

3. The production method according to claim 1, characterized in that The molar ratio of ethanol to ethyl acrylate is 1-3:0.5-1, and the added amount of the catalyst is 2-3wt% of the mass of ethanol.

4. The production method according to claim 1, characterized in that The preparation method of the catalyst is as follows: S1. Preparation of UiO-66-NH2: zirconium tetrachloride and 2-aminoterephthalic acid are added to a mixed solvent, subjected to hydrothermal reaction, filtered, washed, and dried to obtain UiO-66-NH2; S2. Preparation of UiO-66-NH2 / layered metal oxide: dissolving magnesium nitrate, calcium nitrate and aluminum nitrate in water, dropping alkali solution, adding UiO-66-NH2, heating for crystallization, filtering, washing, drying and calcining to obtain UiO-66-NH2 / layered metal oxide; S3. Preparation of modified UiO-66-NH2 / layered metal oxide: adding UiO-66-NH2 / layered metal oxide to water, adding dopamine hydrochloride and a catalyst, heating and stirring to react, filtering, washing, and drying to obtain modified UiO-66-NH2 / layered metal oxide; S4. Preparation of a catalyst precursor: dissolving potassium nitrate in water, adding modified UiO-66-NH2 / layered metal oxide, uniformly dispersing by ultrasonication, and evaporating the solvent to obtain a catalyst precursor; S5. Preparation of catalyst: The catalyst precursor is calcined under the condition of passing a mixed gas of methanol and nitrogen to obtain a catalyst.

5. The production method according to claim 4, characterized in that: In step S1, the molar ratio of zirconium tetrachloride to 2-aminoterephthalic acid is 1:1, the mixed solvent is a mixed solvent of N,N-dimethylformamide and acetic acid in a volume ratio of 35-40:2-4, the temperature of the hydrothermal reaction is 120-130° C., and the time is 20-24 hours.

6. The production method according to claim 4, characterized in that: The mass ratio of magnesium nitrate, calcium nitrate, aluminum nitrate and UiO-66-NH2 in step S2 is 3-5:2-3:5-7:12-15, the pH value of the solution is adjusted to 7.5-8.5 by dropping alkali solution, the heating crystallization temperature is 85-95°C, the time is 20-40min, the calcination temperature is 600-700°C, the time is 1-3h, and the alkali solution is NaOH or KOH solution.

7. The production method according to claim 4, characterized in that: In step S3, the mass ratio of UiO-66-NH2 / layered metal oxide, dopamine hydrochloride and catalyst is 10:4-6:1-2, the catalyst is a Tris-HCl solution with a pH of 8.5-9.5, the temperature of the heating and stirring reaction is 45-55°C, and the time is 3-5h.

8. The production method according to claim 4, characterized in that: In step S4, the mass ratio of potassium nitrate, modified UiO-66-NH2 / layered metal oxide is 4-7:10, the power of the ultrasonic dispersion is 1000-2000 W, and the time is 10-20 min.

9. The production method according to claim 4, characterized in that: In step S5, the volume ratio of the mixed gas of methanol and nitrogen is 3-5:10, the calcination temperature is 600-700° C., and the calcination time is 4-6 hours.

10. The production method according to claim 4, characterized in that: The reaction is carried out in a continuous, semi-continuous or batch manner by passing the mixed materials through a catalyst fixed bed or stirring and mixing the materials and the catalyst.