Catalyst, preparation method thereof, and synthesis method of malonic ester compounds

Abstract

The present invention relates to a catalyst and a preparation method thereof. The catalyst comprises a mesoporous γ-Al2O3 / SiO2 support and an active component supported on the support. The active component is a complex formed by a metal salt and a modifier. The modifier is a reaction product of a first component selected from organic acids and / or inorganic acids and a second component selected from organic bases. The catalyst is weakly acidic. The present invention also relates to a method for synthesizing malonic ester compounds, comprising: mixing cyanoacetic acid, water and the catalyst and performing an activation treatment, then carrying out a hydrolysis reaction on the first mixed material obtained by the activation treatment in the presence of a catalyst for cyanoacetic acid hydrolysis reaction, and then adding an alcohol to the second mixed material obtained by the hydrolysis reaction to carry out an esterification reaction to obtain malonic ester compounds. The catalyst of the present invention can effectively solve problems such as low yield, serious equipment corrosion, and large amounts of "three wastes", and environmentally friendly and efficiently realizes the synthesis of malonic ester compounds.

Description

Technical Field

[0001] The present invention relates to the technical field of fine chemical engineering, and particularly to a catalyst and a preparation method thereof, and a synthesis method of malonic ester compounds. Background Art

[0002] Malonic esters are important fine chemicals, mainly including dimethyl malonate, diethyl malonate, diisopropyl malonate, etc. Among them, dimethyl malonate (DMM) is a colorless transparent liquid with an aromatic odor, slightly soluble in water, and soluble in various organic solvents such as ether, alcohol, benzene, and chloroform. The industrial product is a light yellow transparent liquid. The dimethyl malonate molecule contains an active methylene group and can undergo various substitution reactions such as alkylation reaction, acylation reaction, hydroxyalkylation reaction, and amidation reaction. It is an important raw material for synthesizing various fine chemicals such as pharmaceuticals, pesticides, fragrances, dyes, and antioxidants. For example, dimethyl malonate is an important raw material for synthesizing the precious fragrance methyl dihydrojasmonate, can also be used as a hydrogenation raw material to synthesize 1,3-propanediol, and is also a key raw material for producing the medicine pipemidic acid and dimethyl malonate coumarin.

[0003] The main production methods of dimethyl malonate include cyanation esterification method, carbonylation method, and Claisen ester condensation method. Among them, the cyanation esterification method uses chloroacetic acid as the raw material, which is neutralized by sodium carbonate, cyanated by sodium cyanide, acidified, and then esterified with methanol to obtain dimethyl malonate. This method is currently the main method for industrial production of dimethyl malonate in China. The technology is relatively mature and stable production can be achieved. However, it has a long process flow, low yield, generates a large amount of waste salt and wastewater, making the post-treatment more complicated, and is prone to cause serious environmental pollution, resulting in a relatively high production cost of dimethyl malonate.

[0004] Patent CN106496031A discloses a synthesis method of malonic ester, using cyanoacetic acid and alcohol as raw materials and carrying out an esterification reaction under the catalysis of hydrogen chloride gas. This method uses hydrogen chloride gas instead of concentrated sulfuric acid as a catalyst, and the obtained crude product still needs post-treatment operations such as washing and neutralization, which not only causes equipment corrosion but also generates a large amount of waste salt and wastewater, and does not fundamentally solve the problems existing in the synthesis of malonic ester by the cyanation esterification method.

[0005] Patent CN103319338A discloses a method for synthesizing dimethyl malonate using chloroacetic acid as a raw material, through processes such as neutralization, cyanidation, acidification, and esterification, and also discloses the method and catalyst for the esterification reaction. Specifically, concentrated sulfuric acid, methanol 4 - 6 times the weight of chloroacetic acid, and a catalyst are added to a solution of cyanoacetic acid for reaction. The catalyst consists of 8 - 10wt% lead chloride, 65 - 72wt% triphenylphosphine, 10 - 15wt% dimethyl sulfoxide, and 8 - 12wt% hydrazine hydrate. This method still uses concentrated sulfuric acid as one of the catalytic components, and the catalyst cannot be recycled, unable to avoid problems such as environmental pollution and equipment corrosion, and does not conform to the development concept of green chemistry today.

[0006] The literature "Improvement of the Synthesis Process of Dimethyl Malonate" ([J] Henan Chemical Industry, 1999, 15, (1), 90 - 92.) studied the synthesis process of dimethyl malonate. The core technologies of the cyanidation esterification method are two aspects: one is the hydrolysis of cyanoacetic acid to form malonic acid, and the other is the esterification of malonic acid with methanol to form dimethyl malonate. These two-step reactions are usually carried out under the action of strong inorganic acids (such as concentrated sulfuric acid), causing serious equipment corrosion and environmental pollution problems. Among them, esterification is the rate-determining step, and the rate of the esterification step determines the rate of the entire reaction. In addition, during the esterification process, as the evaporation temperature increases, the decomposition of cyanoacetic acid intensifies, resulting in a low total yield. Under strong acidic conditions, the esterification reaction is a reversible process, and the large equilibrium conversion rate greatly limits its esterification rate. Therefore, improving the esterification reaction rate, reducing the decomposition of cyanoacetic acid, increasing the reaction yield and esterification rate, reducing waste salts and waste water, and simplifying the post-treatment process are the key points and difficulties in the synthesis of dimethyl malonate by the cyanidation esterification method. Developing a more economical and green synthesis process for dimethyl malonate has important economic and environmental protection significance. Summary of the Invention

[0007] Based on this, it is necessary to provide a catalyst and its preparation method for the above problems. When the catalyst is used for catalytic synthesis of malonic ester compounds, it has high activity and selectivity, effectively improves the yield and selectivity of malonic esters, solves problems such as low yield, serious equipment corrosion, and large amounts of "three wastes", and environmentally friendly and efficiently realizes the synthesis of malonic ester compounds.

[0008] To achieve the above object, the technical solution adopted by the present invention is: A catalyst for catalytic synthesis of malonic ester compounds, the catalyst includes a carrier and an active component supported on the carrier. Among them, the carrier is selected from mesoporous γ - Al2O3 / SiO2, the active component is a complex formed by a metal salt and a modifier, the modifier is a reaction product of a first component and a second component, the first component is selected from organic acids and / or inorganic acids, the second component is selected from organic bases, and the catalyst is weakly acidic.

[0009] In one embodiment, the first component is selected from at least one of hydrochloric acid, hydrobromic acid, methanesulfonic acid, trifluoroacetic acid, benzenesulfonic acid or formic acid;

[0010] and / or, the second component is selected from at least one of ethylenediamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine or pyridine;

[0011] and / or, the metal salt is selected from at least one of iron salts, zinc salts, cobalt salts or copper salts.

[0012] In one embodiment, the mass ratio of the metal ion in the metal salt to the carrier is 0.03:1 - 0.09:1;

[0013] and / or, the molar ratio of the modifier to the metal ion in the metal salt is 10:1 - 30:1.

[0014] The present invention also provides a method for preparing the catalyst as described above, comprising the following steps:

[0015] Mix the first component and the second component and adjust the pH to 4.0 - 6.5 to obtain a mixed solution containing the modifier;

[0016] Add the metal salt to the mixed solution to form a formulation;

[0017] Then add a carrier to the formulation for adsorption, and after the adsorption is completed, separate to obtain the catalyst.

[0018] In one embodiment, in the step of adding a carrier to the formulation for adsorption, the temperature is 60°C - 80°C and the time is 4 hours - 6 hours.

[0019] The present invention also provides a method for synthesizing malonic ester compounds, comprising the following steps:

[0020] Mix cyanoacetic acid, water and the catalyst as described above and carry out an activation treatment to obtain a first mixed material;

[0021] In the presence of a catalyst for cyanoacetic acid hydrolysis reaction, carry out a hydrolysis reaction on the first mixed material to obtain a second mixed material containing malonic acid;

[0022] Add an alcohol to the second mixed material for an esterification reaction to obtain malonic ester compounds.

[0023] In one embodiment, in the step of mixing cyanoacetic acid, water and the catalyst and performing activation treatment, the mass ratio of the catalyst to the cyanoacetic acid is 0.05:1 - 0.09:1, and / or, the molar ratio of the cyanoacetic acid to the water is 1:1 - 2:1, and / or, the temperature of the activation treatment is 60°C - 80°C, and the time is 0.5 hour - 1 hour.

[0024] In one embodiment, the catalyst for the hydrolysis reaction of cyanoacetic acid is selected from strongly acidic cation exchange resins with sulfonic acid groups;

[0025] and / or, in the step of performing the hydrolysis reaction on the first mixed material, the temperature is 60°C - 80°C.

[0026] In one embodiment, in the step of adding an alcohol to the second mixed material for an esterification reaction, the alcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol or n-butanol, and / or, the mass ratio of the cyanoacetic acid to the alcohol is 1:3 - 1:4, and / or, the temperature of the esterification reaction is 70°C - 100°C.

[0027] In one embodiment, after the esterification reaction, it further includes a step of separating the catalyst and recycling it for the activation treatment.

[0028] In the catalyst provided by the present invention, the mesoporous γ-Al2O3 / SiO2 support has a large specific surface area, pore diameter and pore volume, and the active components are uniformly distributed on the support, which can provide more active sites and enhance the activity of the catalyst. Thus, when the catalyst is used for catalytic synthesis of malonic esters, the metal ions in the active components can attract the cyano group in cyanoacetic acid and coordinate with it, reducing the decomposition of cyanoacetic acid and improving the selectivity of the reaction; on the one hand, the modifier can form hydrogen bonds with the cyano group to activate the cyano carbon and promote the hydrolysis of the cyano group in an acidic environment, and on the other hand, the modifier can protonate the carbonyl group of the carboxylic acid to enhance the electrophilicity of the carbonyl carbon, thereby increasing the rate of the esterification reaction. At the same time, there are strong acid and weak acid centers in the mesoporous γ-Al2O3 / SiO2 support, increasing the acid concentration in the reaction system, promoting the forward reaction and increasing the conversion rate of the reaction substrate.

[0029] Therefore, the catalyst of the present invention can effectively improve the yield and selectivity of malonic esters, solve the problem of low reaction yield, and moreover, there is no need to use alkali for neutralization and washing after the reaction, and no waste salt and waste water are generated, solving the problem of a large amount of "three wastes"; in addition, the catalyst of the present invention is overall weakly acidic, solving the problem of equipment corrosion, reducing equipment investment, and the catalyst is a supported solid catalyst, which is easy to recycle and can realize the recycling of the catalyst, and has good industrial application prospects. Detailed implementation manners

[0030] For the convenience of understanding the present invention, the present invention will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. On the contrary, these embodiments or examples are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0031] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the technical field to which the present invention belongs. The terms used in the specification of the present invention herein are only for the purpose of describing specific embodiments or examples and are not intended to limit the present invention. The optional scope of the term "and / or" used herein includes any one of two or more related listed items, and also includes any and all combinations of the related listed items, and the any and all combinations include any two related listed items, any more related listed items, or all combinations of the related listed items.

[0032] The catalyst provided by the present invention is mainly used for catalyzing the synthesis of malonic ester compounds. The catalyst includes a carrier and an active component supported on the carrier. Among them, the carrier is selected from mesoporous γ-Al2O3 / SiO2, and the active component is a complex formed by a metal salt and a modifier. The modifier is a reaction product of a first component and a second component. The first component is selected from organic acids and / or inorganic acids, and the second component is selected from organic bases. The catalyst is weakly acidic.

[0033] Optionally, the first component is selected from at least one of hydrochloric acid, hydrobromic acid, methanesulfonic acid, trifluoroacetic acid, benzenesulfonic acid or formic acid, and further preferably from at least one of methanesulfonic acid, benzenesulfonic acid or formic acid.

[0034] Optionally, the second component is selected from at least one of ethylenediamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine or pyridine, and further preferably from at least one of ethylenediamine, diethylamine or diethanolamine.

[0035] Optionally, the metal salt is selected from at least one of iron salts, zinc salts, cobalt salts or copper salts, and specifically can be selected from at least one of their chlorides, nitrates, sulfates, acetylacetonates or their hydrates. As a preference, when the metal salt is selected from at least two of iron salts, zinc salts, cobalt salts or copper salts, the effect is better.

[0036] Optionally, the mass ratio of the metal ions in the metal salt to the carrier is 0.03:1 - 0.09:1, and further preferably 0.03:1 - 0.07:1, including but not limited to 0.03:1, 0.04:1, 0.05:1, 0.06:1, 0.07:1.

[0037] Optionally, the molar ratio of the modifier to the metal ions in the metal salt is 10:1 - 30:1, more preferably 20:1 - 30:1, including but not limited to 20:1, 21:1, 22:1, 23:1, 24:1, 25:1, 26:1, 27:1, 28:1, 29:1, 30:1.

[0038] The present invention also provides a method for preparing the catalyst, comprising the following steps:

[0039] S11, mixing the first component and the second component and adjusting the pH to 4.0 - 6.5 to obtain a mixed solution containing the modifier;

[0040] S12, adding the metal salt to the mixed solution to form a formulation;

[0041] S13, then adding a support to the formulation for adsorption, and separating to obtain the catalyst after the adsorption is completed.

[0042] In step S11, by adjusting the pH value, it can be ensured that the overall catalyst is weakly acidic.

[0043] In step S12, the metal salt can be first dissolved in a solvent and then added to the mixed solution, where the solvent can completely dissolve the metal salt, and no special requirements are made for its type and dosage.

[0044] In step S13, in the step of adding a support to the formulation for adsorption, the temperature is 60°C - 80°C and the time is 4 hours - 6 hours, which is beneficial to improving the adsorption rate and adsorption effect of the formulation on the support.

[0045] The preparation method of the catalyst of the present invention is simple, the conditions are mild, and the preparation process is environmentally friendly; moreover, the mesoporous γ - Al2O3 / SiO2 support of the present invention has a large specific surface area, pore diameter and pore volume, which can make the active components evenly distributed on the support, and thus can provide more active sites and enhance the activity of the catalyst.

[0046] Therefore, the present invention also provides a method for synthesizing malonic acid esters, comprising the following steps:

[0047] S21, mixing cyanoacetic acid, water and the catalyst and performing an activation treatment to obtain a first mixed material;

[0048] S22, performing a hydrolysis reaction on the first mixed material in the presence of a catalyst for cyanoacetic acid hydrolysis reaction to obtain a second mixed material containing malonic acid;

[0049] S23. Add an alcohol to the second mixed material for an esterification reaction to obtain a malonic ester compound.

[0050] In step S21, in the step of mixing cyanoacetic acid, water and the catalyst and performing an activation treatment, the mass ratio of the catalyst to the cyanoacetic acid is preferably 0.05:1 - 0.09:1, more preferably 0.05:1 - 0.07:1. The water can ensure the complete hydrolysis of cyanoacetic acid. Preferably, the molar ratio of cyanoacetic acid to water is 1:1 - 2:1. The temperature of the activation treatment is preferably 60°C - 80°C, and the time is 0.5 hour - 1 hour.

[0051] In step S22, the catalyst for the cyanoacetic acid hydrolysis reaction is selected from strongly acidic cation exchange resins with sulfonic acid groups, such as D001, D061, etc.

[0052] Optionally, in the step of performing a hydrolysis reaction on the first mixed material, the temperature is preferably 60°C - 80°C.

[0053] In step S23, in the step of adding an alcohol to the second mixed material for an esterification reaction, the alcohol is selected from at least one of methanol, ethanol, n - propanol, isopropanol or n - butanol. The mass ratio of cyanoacetic acid to the alcohol is 1:3 - 1:4. The temperature of the esterification reaction is preferably 70°C - 100°C, more preferably 80°C - 100°C.

[0054] After the esterification reaction, it further includes separating the catalyst and recycling it for use in the activation treatment step.

[0055] In the synthesis method of the malonic ester compound of the present invention, the metal ions in the active component can attract the cyano group in cyanoacetic acid and coordinate with it, reducing the decomposition of cyanoacetic acid and improving the selectivity of the reaction. On the one hand, the modifier can form a hydrogen bond with the cyano group, activate the cyano carbon, and promote the hydrolysis of the cyano group in an acidic environment. On the other hand, the modifier can protonate the carbonyl group of the carboxylic acid, enhancing the electrophilicity of the carbonyl carbon, thereby increasing the rate of the esterification reaction. At the same time, the mesoporous γ - Al2O3 / SiO2 support has strong acid and weak acid centers, increasing the acid concentration in the reaction system, promoting the forward reaction, and improving the conversion rate of the reaction substrate.

[0056] Therefore, the catalyst of the present invention can effectively improve the yield and selectivity of malonic esters, solve the problem of low reaction yield, and moreover, there is no need to use alkali for neutralization and washing after the reaction, and no waste salt and waste water are generated, solving the problem of a large amount of "three wastes". In addition, the catalyst of the present invention is overall weakly acidic, solving the problem of equipment corrosion, reducing equipment investment, and the catalyst is a supported solid catalyst, which is easy to recycle and can realize the recycling of the catalyst, having good industrial application prospects.

[0057] Hereinafter, the catalyst, its preparation method, and the synthesis method of malonic ester compounds will be further described by the following specific examples.

[0058] Unless otherwise specified, the inorganic salts, acids, bases, cyanoacetic acid (AR grade, 98%, Aladdin), methanol, ethanol, n-propanol, n-butanol, isopropanol, etc. used in the following examples are all commercially available.

[0059] Metal mass = metal salt mass * metal element mass / metal salt molecular weight * 100%;

[0060] Theoretical loading = metal mass / carrier mass * 100%;

[0061] Mass space velocity = feed mass per unit time / packing mass.

[0062] Catalyst Preparation Example 1

[0063] At room temperature, 6.17 g of formic acid was weighed, and an appropriate amount of diethanolamine was added dropwise while stirring. The mixture was detected with a pH meter, and the addition was stopped when pH = 5.0 to obtain a modifier-containing mixture.

[0064] 1.45 g of anhydrous FeCl3 and 1.07 g of Zn(OAc)2·2H2O were completely dissolved in 5.0 g of purified water. The solution was added to the above mixture, the temperature was raised to 80 °C, and the mixture was stirred for 2 hours while maintaining the temperature. Then, the temperature was lowered to 40 °C, and 10.0 g of dry mesoporous γ-Al2O3 / SiO2 carrier was added, and the mixture was adsorbed for 4 hours while maintaining the temperature. After the adsorption was completed, it was rotary evaporated to dryness, and then placed in an 80 °C drying oven and dried to a constant weight to obtain a catalyst, labeled as Catalyst 1#, with the expression 5.0% Fe - 3.0% Zn / γ-Al2O3 / SiO2 - modifier.

[0065] Catalyst Preparation Example 2

[0066] At room temperature, 14.43 g of methanesulfonic acid was weighed, and an appropriate amount of ethylenediamine was added dropwise while stirring. The mixture was detected with a pH meter, and the addition was stopped when pH = 5.5 to obtain a modifier-containing mixture.

[0067] Dissolve 2.03 g of anhydrous FeCl3 and 1.68 g of Zn(OAc)2·2H2O completely in 5.0 g of purified water. Add the solution to the above-mentioned mixture, raise the temperature to 90 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 5 hours. After the adsorption is completed, rotary evaporate to dryness, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 2#, with the expression 7.0% Fe - 5.0% Zn / γ-Al2O3 / SiO2 - modifier.

[0068] Catalyst Preparation Example 3

[0069] At room temperature, weigh 13.61 g of methanesulfonic acid, dropwise add an appropriate amount of ethylenediamine while stirring. Use a pH meter to detect the mixture, and stop dropping when pH = 6.0 to obtain a mixture containing the modifier.

[0070] Dissolve 2.83 g of Cu(OAc)2·H2O and 1.04 g of ZnCl2 completely in 5.0 g of purified water. Add the solution to the above-mentioned mixture, raise the temperature to 90 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 5 hours. After the adsorption is completed, rotary evaporate to dryness, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 3#, with the expression 9.0% Cu - 5.0% Zn / γ-Al2O3 / SiO2 - modifier.

[0071] Catalyst Preparation Example 4

[0072] At room temperature, weigh 21.16 g of methanesulfonic acid, dropwise add an appropriate amount of diethanolamine while stirring. Use a pH meter to detect the mixture, and stop dropping when pH = 5.0 to obtain a mixture containing the modifier.

[0073] Dissolve 1.07 g of FeCl2·4H2O and 2.66 g of Cu(NO3)2·3H2O completely in 5.0 g of purified water. Add the solution to the above-mentioned mixture, raise the temperature to 90 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 5 hours. After the adsorption is completed, rotary evaporate to dryness, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 4#, with the expression 3.0% Fe - 7.0% Cu / γ-Al2O3 / SiO2 - modifier.

[0074] Catalyst Preparation Example 5

[0075] At room temperature, 13.26 g of hydrochloric acid (37 wt.%) was weighed, and an appropriate amount of diethanolamine was added dropwise with stirring. The mixed solution was detected using a pH meter, and the addition was stopped when pH = 5.0 to obtain a mixed solution containing a modifier.

[0076] 1.07 g of FeCl2·4H2O and 2.66 g of Cu(NO3)2·3H2O were completely dissolved in 5.0 g of purified water. The solution was added to the above mixed solution, the temperature was raised to 90 °C, and the mixture was stirred for 2 hours while maintaining the temperature. Then, the temperature was lowered to 40 °C, and 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support was added, and the mixture was adsorbed for 5 hours while maintaining the temperature. After the adsorption was completed, the solution was rotary evaporated to dryness and then dried in an 80 °C drying oven until a constant weight was obtained to obtain a catalyst labeled as Catalyst 5#, with the expression 3.0% Fe - 7.0% Cu / γ-Al2O3 / SiO2 - modifier.

[0077] Catalyst Preparation Example 6

[0078] At room temperature, 24.68 g of hydrochloric acid (37 wt.%, MW 36.46) was weighed, and an appropriate amount of diethanolamine was added dropwise with stirring. The mixed solution was detected using a pH meter, and the addition was stopped when pH = 5.5 to obtain a mixed solution containing a modifier.

[0079] 5.06 g of Fe(NO3)3·9H2O and 2.02 g of CoCl2·6H2O were completely dissolved in 10.0 g of purified water. The solution was added to the above mixed solution, the temperature was raised to 80 °C, and the mixture was stirred for 2 hours while maintaining the temperature. Then, the temperature was lowered to 40 °C, and 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support was added, and the mixture was adsorbed for 5 hours while maintaining the temperature. After the adsorption was completed, the solution was rotary evaporated to dryness and then dried in an 80 °C drying oven until a constant weight was obtained to obtain a catalyst labeled as Catalyst 6#, with the expression 7.0% Fe - 5.0% Co / γ-Al2O3 / SiO2 - modifier.

[0080] Catalyst Preparation Example 7

[0081] At room temperature, 23.21 g of hydrobromic acid (48 wt.%) was weighed, and an appropriate amount of diethanolamine was added dropwise with stirring. The mixed solution was detected using a pH meter, and the addition was stopped when pH = 6.5 to obtain a mixed solution containing a modifier.

[0082] Dissolve 3.96 g of ZnSO4·7H2O and 3.21 g of Co(NO3)2·6H2O completely in 8.0 g of purified water. Add the solution to the above-mentioned mixed solution, raise the temperature to 80 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 5 hours. After the adsorption is completed, rotary evaporate to dryness, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 7#, with the expression 9.0% Zn - 7.0% Co / γ-Al2O3 / SiO2 - modifier.

[0083] Catalyst Preparation Example 8

[0084] At room temperature, weigh 35.81 g of hydrobromic acid (48 wt.%), dropwise add an appropriate amount of ethanolamine, stir while adding dropwise, and use a pH meter to detect the mixed solution. Stop adding dropwise when pH = 5.5 to obtain a mixed solution containing the modifier.

[0085] Dissolve 3.54 g of CuSO4·5H2O and 3.21 g of Co(NO3)2·6H2O completely in 8.0 g of purified water. Add the solution to the above-mentioned mixed solution, raise the temperature to 80 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 5 hours. After the adsorption is completed, rotary evaporate to dryness, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 8#, with the expression 9.0% Cu - 7.0% Co / γ-Al2O3 / SiO2 - modifier.

[0086] Catalyst Preparation Example 9

[0087] At room temperature, weigh 28.58 g of trifluoroacetic acid, dropwise add an appropriate amount of diethylamine, stir while adding dropwise, and use a pH meter to detect the mixed solution. Stop adding dropwise when pH = 4.0 to obtain a mixed solution containing the modifier.

[0088] Dissolve 2.03 g of anhydrous FeCl3 and 1.68 g of Zn(OAc)2·2H2O completely in 5.0 g of purified water. Add the solution to the above-mentioned modifier mixed solution, raise the temperature to 80 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 6 hours. After the adsorption is completed, rotary evaporate to dryness, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 9#, with the expression 7.0% Fe - 5.0% Zn / γ-Al2O3 / SiO2 - modifier.

[0089] Catalyst Preparation Example 10

[0090] At room temperature, 35.69 g of benzenesulfonic acid was weighed, and an appropriate amount of triethylamine was added dropwise with stirring. The mixed solution was detected using a pH meter, and the addition was stopped when pH = 5.0 to obtain a mixed solution containing a modifier.

[0091] 5.06 g of Fe(NO3)3·9H2O and 2.02 g of CoCl2·6H2O were completely dissolved in 5.0 g of purified water. The solution was added to the above mixed solution, the temperature was raised to 80 °C, and the mixture was stirred for 2 hours while maintaining the temperature. Then the temperature was lowered to 40 °C, and 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support was added, and the mixture was adsorbed for 6 hours while maintaining the temperature. After the adsorption was completed, the mixture was rotary evaporated to dryness and then dried in an 80 °C drying oven to constant weight to obtain a catalyst, labeled as Catalyst 10#, with the expression 7.0% Fe - 5.0% Co / γ-Al2O3 / SiO2 - modifier.

[0092] Catalyst Preparation Example 11

[0093] At room temperature, 24.08 g of methanesulfonic acid was weighed, and an appropriate amount of morpholine was added dropwise with stirring. The mixed solution was detected using a pH meter, and the addition was stopped when pH = 5.0 to obtain a mixed solution containing a modifier.

[0094] 5.06 g of Fe(NO3)3·9H2O and 1.20 g of anhydrous CuCl2·2H2O were completely dissolved in 8.0 g of purified water. The solution was added to the above mixed solution, the temperature was raised to 80 °C, and the mixture was stirred for 2 hours while maintaining the temperature. Then the temperature was lowered to 40 °C, and 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support was added, and the mixture was adsorbed for 6 hours while maintaining the temperature. After the adsorption was completed, the mixture was rotary evaporated to dryness and then dried in an 80 °C drying oven to constant weight to obtain a catalyst, labeled as Catalyst 11#, with the expression 7.0% Fe - 5.0% Co / γ-Al2O3 / SiO2 - modifier.

[0095] Catalyst Preparation Example 12

[0096] At room temperature, 18.04 g of methanesulfonic acid was weighed, and an appropriate amount of pyridine was added dropwise with stirring. The mixed solution was detected using a pH meter, and the addition was stopped when pH = 6.0 to obtain a mixed solution containing a modifier.

[0097] Dissolve 2.03 g of anhydrous FeCl3 and 1.68 g of Zn(OAc)2·2H2O completely in 5.0 g of purified water. Add the solution to the above mixed solution, raise the temperature to 80 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 6 hours. After the adsorption is completed, evaporate to dryness by rotary evaporation, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 12#, with the expression 7.0% Fe - 5.0% Zn / γ-Al2O3 / SiO2 - modifier.

[0098] Catalyst Preparation Example 13

[0099] At room temperature, weigh 24.06 g of methanesulfonic acid (MW 96.11), add a proper amount of diethanolamine dropwise while stirring, detect the mixed solution with a pH meter, and stop adding when pH = 5.0 to obtain a mixed solution containing the modifier.

[0100] Dissolve 2.03 g of anhydrous FeCl3 and 1.68 g of Zn(OAc)2·2H2O completely in 5.0 g of purified water. Add the solution to the above mixed solution, raise the temperature to 90 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 5 hours. After the adsorption is completed, evaporate to dryness by rotary evaporation, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 13#, with the expression 7.0% Fe - 5.0% Zn / γ-Al2O3 / SiO2 - modifier.

[0101] Catalyst Preparation Example 14

[0102] At room temperature, weigh 24.06 g of methanesulfonic acid, add a proper amount of diethanolamine dropwise while stirring, detect the mixed solution with a pH meter, and stop adding when pH = 5.0 to obtain a mixed solution containing the modifier.

[0103] Dissolve 2.03 g of anhydrous FeCl3 completely in 5.0 g of purified water. Add the solution to the above mixed solution, raise the temperature to 90 °C, keep stirring for 2 hours, then cool down to 40 °C, add 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support, and keep adsorbing for 5 hours. After the adsorption is completed, evaporate to dryness by rotary evaporation, and then place it in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Catalyst 14#, with the expression 7.0% Fe / γ-Al2O3 / SiO2 - modifier.

[0104] Catalyst Preparation Comparative Example 1

[0105] At room temperature, 24.06 g of methanesulfonic acid was weighed, and an appropriate amount of diethanolamine was added dropwise with stirring. The pH meter was used to detect the mixed solution, and the addition was stopped when pH = 5.0 to obtain a mixed solution containing a modifier.

[0106] 2.03 g of anhydrous FeCl3 and 1.68 g of Zn(OAc)2·2H2O were completely dissolved in 20.0 g of purified water. γ-Al2O3 and SiO2 mixed powder (the mass ratio of the two is 1:1) was added, and the mixture was kept at 40 °C for adsorption for 8 hours. After the adsorption was completed, it was rotary evaporated to dryness, the temperature was raised to 80 °C, and the mixture was kept stirring for 2 hours and then rotary evaporated to dryness to obtain a catalyst, labeled as Comparative Catalyst 1#, with the expression of 7.0% Fe - 5.0% Zn / γ-Al2O3 / SiO2 - modifier.

[0107] Preparation of Catalyst Comparative Example 2

[0108] At room temperature, 2.03 g of anhydrous FeCl3 and 1.68 g of Zn(OAc)2·2H2O were completely dissolved in 20.0 g of purified water. 10.0 g of dry mesoporous γ-Al2O3 / SiO2 support was added, and the mixture was kept at 40 °C for adsorption for 5 hours. After the adsorption was completed, it was rotary evaporated to dryness, and then placed in an 80 °C drying oven to dry to constant weight to obtain a catalyst, labeled as Comparative Catalyst 2#, with the expression of 7.0% Fe - 5.0% Zn / γ-Al2O3 / SiO2.

[0109] Synthesis of Malonic Ester Compound - Example 1

[0110] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of Catalyst 1# were added to a three-necked flask. Stirring was started at 400 r / min, and the temperature was heated to 60 °C and kept stirring for 1.0 hour. After the activation was completed, the first mixed material was obtained.

[0111] The first mixed material entered a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor was controlled at 60 °C, and the space velocity was 0.5 h -1 , and after hydrolysis, the second mixed material was obtained.

[0112] The second mixed material was added to a three-necked flask, and 69.11 g of ethanol was added. The temperature was raised to 80 °C and kept reacting for 5 hours. After the reaction was completed, the catalyst 1# was separated by cooling and filtration and washed. 22.6 g of unreacted ethanol was recovered at atmospheric pressure, and 74.80 g of the finished product diethyl malonate was obtained by rectification, with a yield of 93.4%.

[0113] Synthesis of Malonic Ester Compound - Example 2

[0114] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 2# were added to a three-necked flask. Stirring was started at 400 r / min, and the mixture was heated to 60 °C and stirred at a constant temperature for 1.0 hour. After the activation was completed, the first mixed material was obtained.

[0115] The first mixed material entered a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor was controlled at 60 °C, and the space velocity was 0.5 h -1 , and after the hydrolysis was completed, the second mixed material was obtained.

[0116] The second mixed material was added to a three-necked flask, and then 69.11 g of ethanol was added. The temperature was raised to 85 °C and the reaction was carried out at a constant temperature for 5 hours. After the reaction was completed, the catalyst 2# was separated by cooling and filtration and washed. 22.5 g of unreacted ethanol was recovered at atmospheric pressure, and 76.08 g of the finished product diethyl malonate was obtained by rectification, and the yield was 95.0%.

[0117] Synthesis Example 3 of malonic ester compounds

[0118] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 1# were added to a three-necked flask. Stirring was started at 400 r / min, and the mixture was heated to 60 °C and stirred at a constant temperature for 1.0 hour. After the activation was completed, the first mixed material was obtained.

[0119] The first mixed material entered a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor was controlled at 60 °C, and the space velocity was 0.5 h -1 , and after the hydrolysis was completed, the second mixed material was obtained.

[0120] The second mixed material was added to a three-necked flask, and then 64.08 g of methanol was added. The temperature was raised to 80 °C and the reaction was carried out at a constant temperature for 5 hours. After the reaction was completed, the catalyst 1# was separated by cooling and filtration and washed. 15.9 g of unreacted methanol was recovered at atmospheric pressure, and 64.21 g of the finished product dimethyl malonate was obtained by rectification, and the yield was 97.2%.

[0121] Synthesis Example 4 of malonic ester compounds

[0122] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 3# were added to a three-necked flask. Stirring was started at 400 r / min, and the mixture was heated to 60 °C and stirred at a constant temperature for 1.0 hour. After the activation was completed, the first mixed material was obtained.

[0123] The first mixed material enters the fixed-bed reactor, which is filled with D001. The temperature of the fixed-bed reactor is controlled at 60 °C, and the space velocity is 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0124] The second mixed material is added to a three-necked flask, and then 48.06 g of methanol is added. The temperature is raised to 90 °C and the reaction is carried out under insulation for 6 hours. After the reaction is completed, the catalyst 3# is separated by cooling and filtration and washed. 15.8 g of unreacted methanol is recovered at atmospheric pressure, and 62.23 g of the finished product dimethyl malonate is obtained by rectification, with a yield of 94.2%.

[0125] Synthesis Example 5 of malonic ester compounds

[0126] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 3.83 g (9.0 wt%) of catalyst 4# are added to a three-necked flask. Stirring is started at 400 r / min, and the temperature is raised to 60 °C and stirred constantly for 1.0 hour. After the activation is completed, a first mixed material is obtained.

[0127] The first mixed material enters the fixed-bed reactor, which is filled with D001. The temperature of the fixed-bed reactor is controlled at 60 °C, and the space velocity is 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0128] The second mixed material is added to a three-necked flask, and then 111.18 g of n-butanol is added. The temperature is raised to 85 °C and the reaction is carried out under insulation for 6 hours. After the reaction is completed, the catalyst 4# is separated by cooling and filtration and washed. 36.8 g of unreacted n-butanol is recovered at atmospheric pressure, and 103.49 g of the finished product di-n-butyl malonate is obtained by rectification, with a yield of 95.7%.

[0129] Synthesis Example 6 of malonic ester compounds

[0130] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of catalyst 5# are added to a three-necked flask. Stirring is started at 400 r / min, and the temperature is raised to 60 °C and stirred constantly for 1.0 hour. After the activation is completed, a first mixed material is obtained.

[0131] The first mixed material enters the fixed-bed reactor, which is filled with D001. The temperature of the fixed-bed reactor is controlled at 60 °C, and the space velocity is 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0132] Add the second mixed material into a three-necked flask, then add 111.18 g of n-butanol, heat up to 90 °C, and keep the temperature for reaction for 4 hours. After the reaction is completed, cool and filter to separate out the catalyst 5# and wash it. Recover 36.8 g of unreacted n-butanol under normal pressure, and obtain 104.46 g of the finished product dibutyl malonate by rectification, with a yield of 96.6%.

[0133] Synthesis Example 7 of malonic ester compounds

[0134] Add 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of catalyst 6# into a three-necked flask, start stirring at 400 r / min, heat up to 60 °C, and keep stirring at a constant temperature for 1.0 hour. After the activation is completed, obtain the first mixed material.

[0135] The first mixed material enters a fixed-bed reactor filled with D001, and control the temperature of the fixed-bed reactor to be 60 °C, and the space velocity to be 0.5 h -1 , after hydrolysis, obtain the second mixed material.

[0136] Add the second mixed material into a three-necked flask, then add 48.06 g of methanol, heat up to 80 °C, and keep the temperature for reaction for 5 hours. After the reaction is completed, cool and filter to separate out the catalyst 6# and wash it. Recover 15.6 g of unreacted methanol under normal pressure, and obtain 61.57 g of the finished product dimethyl malonate by rectification, with a yield of 93.2%.

[0137] Synthesis Example 8 of malonic ester compounds

[0138] Add 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of catalyst 7# into a three-necked flask, start stirring at 400 r / min, heat up to 60 °C, and keep stirring at a constant temperature for 1.0 hour. After the activation is completed, obtain the first mixed material.

[0139] The first mixed material enters a fixed-bed reactor filled with D001, and control the temperature of the fixed-bed reactor to be 60 °C, and the space velocity to be 0.5 h -1 , after hydrolysis, obtain the second mixed material.

[0140] Add the second mixed material into a three-necked flask, then add 48.06 g of methanol, heat up to 80 °C, and keep the temperature for reaction for 5 hours. After the reaction is completed, cool and filter to separate out the catalyst 7# and wash it. Recover 15.7 g of unreacted methanol under normal pressure, and obtain 60.44 g of the finished product dimethyl malonate by rectification, with a yield of 91.5%.

[0141] Synthesis Example 9 of malonic ester compounds

[0142] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of catalyst 8# were added to a three-necked flask. Stirring was started at 400 r / min, and the mixture was heated to 60 °C and stirred constantly for 1.0 hour. After the activation was completed, a first mixed material was obtained.

[0143] The first mixed material entered a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor was controlled at 60 °C, and the space velocity was 0.5 h -1 , and after the hydrolysis was completed, a second mixed material was obtained.

[0144] The second mixed material was added to a three-necked flask, and then 48.06 g of methanol was added. The temperature was raised to 90 °C and the reaction was carried out for 7 hours while maintaining the temperature. After the reaction was completed, the catalyst 8# was separated by cooling and filtration and washed. 15.7 g of unreacted methanol was recovered at atmospheric pressure, and 59.98 g of the finished product dimethyl malonate was obtained by rectification, with a yield of 90.8%.

[0145] Synthesis Example 10 of malonic ester compounds

[0146] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 9# were added to a three-necked flask. Stirring was started at 400 r / min, and the mixture was heated to 60 °C and stirred constantly for 1.0 hour. After the activation was completed, a first mixed material was obtained.

[0147] The first mixed material entered a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor was controlled at 60 °C, and the space velocity was 0.5 h -1 , and after the hydrolysis was completed, a second mixed material was obtained.

[0148] The second mixed material was added to a three-necked flask, and then 48.06 g of methanol was added. The temperature was raised to 70 °C and the reaction was carried out for 5 hours while maintaining the temperature. After the reaction was completed, the catalyst 9# was separated by cooling and filtration and washed. 15.7 g of unreacted methanol was recovered at atmospheric pressure, and 63.95 g of the finished product dimethyl malonate was obtained by rectification, with a yield of 97.8%.

[0149] Synthesis Example 11 of malonic ester compounds

[0150] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of catalyst 10# were added to a three-necked flask. Stirring was started at 400 r / min, and the mixture was heated to 60 °C and stirred constantly for 1.0 hour. After the activation was completed, a first mixed material was obtained.

[0151] The first mixed material enters the fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C with an airspeed of 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0152] The second mixed material is added to a three-necked flask, and then 48.06 g of methanol is added. The temperature is raised to 90 °C and the reaction is carried out under insulation for 5 hours. After the reaction is completed, the catalyst 10# is separated by cooling and filtration and washed. 15.5 g of unreacted methanol is recovered at atmospheric pressure, and 63.15 g of the finished product dimethyl malonate is obtained by rectification, with a yield of 95.6%.

[0153] Synthesis Example 12 of malonic ester compounds

[0154] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of catalyst 11# are added to a three-necked flask. Stirring is started at 400 r / min and heated to 60 °C, and stirring is carried out at a constant temperature for 1.0 hour. After the activation is completed, a first mixed material is obtained.

[0155] The first mixed material enters the fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C with an airspeed of 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0156] The second mixed material is added to a three-necked flask, and then 48.06 g of methanol is added. The temperature is raised to 100 °C and the reaction is carried out under insulation for 5 hours. After the reaction is completed, the catalyst 11# is separated by cooling and filtration and washed. 15.5 g of unreacted methanol is recovered at atmospheric pressure, and 61.83 g of the finished product dimethyl malonate is obtained by rectification, with a yield of 93.6%.

[0157] Synthesis Example 13 of malonic ester compounds

[0158] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of catalyst 12# are added to a three-necked flask. Stirring is started at 400 r / min and heated to 60 °C, and stirring is carried out at a constant temperature for 1.0 hour. After the activation is completed, a first mixed material is obtained.

[0159] The first mixed material enters the fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C with an airspeed of 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0160] Add the second mixed material into a three-necked flask, then add 48.06 g of methanol, heat up to 100 °C, and keep the temperature for reaction for 6 hours. After the reaction is completed, cool and filter to separate out the catalyst 12# and wash it. Recover 15.9 g of unreacted methanol under atmospheric pressure, and obtain 63.29 g of the finished product dimethyl malonate by rectification, with a yield of 95.8%.

[0161] Synthesis Example 14 of malonic ester compounds

[0162] Add 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 13# into a three-necked flask, start stirring at 400 r / min, heat to 60 °C, and keep stirring at a constant temperature for 1.0 hour. After the activation is completed, the first mixed material is obtained.

[0163] The first mixed material enters a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C, and the space velocity is 0.5 h -1 , after hydrolysis, the second mixed material is obtained.

[0164] Add the second mixed material into a three-necked flask, then add 48.06 g of methanol, heat up to 85 °C, and keep the temperature for reaction for 4 hours. After the reaction is completed, cool and filter to separate out the catalyst 13# and wash it. Recover 15.9 g of unreacted methanol under atmospheric pressure, and obtain 64.87 g of the finished product dimethyl malonate by rectification, with a yield of 98.2%.

[0165] Carry out the recycling of the recovered catalyst 13#, and the experimental operation is the same as above. The recycling data are shown in the following table.

[0166] Table 1

[0167] Experimental batch Recycled methanol / g Dimethyl malonate / g Yield % Recycling *1 15.9 64.94 98.3 Recycling *2 15.9 64.80 98.1 Recycling *3 15.7 64.47 97.6 Recycling *4 15.7 64.41 97.5 Recycling *5 15.7 64.21 97.2

[0168] As can be seen from Table 1, when the catalyst 13# is continuously recycled 5 times, the yield only decreases by 1.1%. The reason for the decrease may be due to the loss of the catalyst during the recycling experiment. If continuous recycling is required, a small amount can be supplemented.

[0169] Synthesis Example 15 of malonic ester compounds

[0170] Add 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 13# into a three-necked flask, start stirring at 400 r / min, heat to 60 °C, and keep stirring at a constant temperature for 1.0 hour. After the activation is completed, the first mixed material is obtained.

[0171] The first mixed material enters a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C with a space velocity of 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0172] The second mixed material is added to a three-necked flask, and then 69.11 g of ethanol is added. The temperature is raised to 80 °C and the reaction is carried out under insulation for 5 hours. After the reaction is completed, the catalyst 13# is separated by cooling and filtration and washed. 22.7 g of unreacted ethanol is recovered at atmospheric pressure, and 78.88 g of the finished product diethyl malonate is obtained by rectification, with a yield of 98.5%.

[0173] Synthesis Example 16 of malonic ester compounds

[0174] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 13# are added to a three-necked flask. Stirring is started at 400 r / min and heated to 60 °C, and stirring is carried out at a constant temperature for 1.0 hour. After the activation is completed, a first mixed material is obtained.

[0175] The first mixed material enters a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C with a space velocity of 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0176] The second mixed material is added to a three-necked flask, and then 90.15 g of isopropanol is added. The temperature is raised to 90 °C and the reaction is carried out under insulation for 5 hours. After the reaction is completed, the catalyst 13# is separated by cooling and filtration and washed. 29.5 g of unreacted isopropanol is recovered at atmospheric pressure, and 90.35 g of the finished product diisopropyl malonate is obtained by rectification, with a yield of 96.0%.

[0177] Synthesis Example 17 of malonic ester compounds

[0178] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.13 g (5.0 wt%) of catalyst 13# are added to a three-necked flask. Stirring is started at 400 r / min and heated to 60 °C, and stirring is carried out at a constant temperature for 1.0 hour. After the activation is completed, a first mixed material is obtained.

[0179] The first mixed material enters a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C with a space velocity of 0.5 h -1 , and after the hydrolysis is completed, a second mixed material is obtained.

[0180] Add the second mixed material into a three-necked flask, then add 90.15 g of n-propanol, heat up to 80 °C, and keep the temperature for reaction for 5 hours. After the reaction is completed, cool and filter to separate the catalyst 13# and wash it. Recover 29.6 g of unreacted n-propanol under normal pressure, and obtain 92.13 g of the finished product of dipropyl malonate by rectification, with a yield of 97.9%.

[0181] Synthesis Example 18 of malonic ester compounds

[0182] Add 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 3.83 g (9.0 wt%) of catalyst 14# into a three-necked flask, start stirring at 400 r / min, heat up to 60 °C, and keep stirring at a constant temperature for 1.0 hour. After the activation is completed, the first mixed material is obtained.

[0183] The first mixed material enters a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C, and the space velocity is 0.5 h -1 , after the hydrolysis is completed, the second mixed material is obtained.

[0184] Add the second mixed material into a three-necked flask, then add 48.06 g of methanol, heat up to 100 °C, and keep the temperature for reaction for 5 hours. After the reaction is completed, cool and filter to separate the catalyst 14# and wash it. Recover 15.6 g of unreacted methanol under normal pressure, and obtain 53.64 g of the finished product of dimethyl malonate by rectification, with a yield of 81.2%.

[0185] Synthesis Comparative Example 1 of malonic ester compounds

[0186] Add 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of comparative catalyst 1# into a three-necked flask, start stirring at 400 r / min, heat up to 60 °C, and keep stirring at a constant temperature for 1.0 hour. After the activation is completed, the first mixed material is obtained.

[0187] The first mixed material enters a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor is controlled at 60 °C, and the space velocity is 0.5 h -1 , after the hydrolysis is completed, the second mixed material is obtained.

[0188] Add the second mixed material into a three-necked flask, then add 48.06 g of methanol, heat up to 100 °C, and keep the temperature for reaction for 7 hours. After the reaction is completed, cool and filter to separate the comparative catalyst 1# and wash it. Recover 15.6 g of unreacted methanol under normal pressure, and obtain 43.14 g of the finished product of dimethyl malonate by rectification, with a yield of 65.3%.

[0189] Synthesis Comparative Example 2 of Malonic Acid Esters Compounds

[0190] 42.53 g (0.5 mol) of cyanoacetic acid, 18.0 g (1.0 mol) of purified water, and 2.98 g (7.0 wt%) of Comparative Catalyst 2# were added to a three-necked flask. Stirring was started at 400 r / min, and the mixture was heated to 60 °C and stirred at a constant temperature for 1.0 hour. After the activation was completed, the first mixed material was obtained.

[0191] The first mixed material entered a fixed-bed reactor filled with D001, and the temperature of the fixed-bed reactor was controlled at 60 °C, and the space velocity was 0.5 h -1 , and after the hydrolysis was completed, the second mixed material was obtained.

[0192] The second mixed material was added to a three-necked flask, and then 48.06 g of methanol was added. The temperature was raised to 100 °C and the reaction was carried out at a constant temperature for 7 hours. After the reaction was completed, Comparative Catalyst 2# was separated by cooling and filtration and washed. 15.2 g of unreacted methanol was recovered at atmospheric pressure, and 45.05 g of dimethyl malonate as the finished product was obtained by rectification, and the yield was 68.2%.

[0193] The technical features of the above-described embodiments can be combined arbitrarily. For the sake of brevity of description, not all possible combinations of the technical features in the above embodiments are described. However, as long as there is no contradiction in the combination of these technical features, it should be considered as the scope described in this specification.

[0194] The above-described embodiments merely represent several implementation manners of the present invention, and the description thereof is relatively specific and detailed, but it should not be construed as a limitation on the scope of the invention patent. It should be noted that for those of ordinary skill in the art, without departing from the concept of the present invention, several modifications and improvements can still be made, and these all belong to the protection scope of the present invention. Therefore, the protection scope of the present invention patent shall be subject to the appended claims.

Claims

1. A catalyst for catalyzing the synthesis of malonic ester compounds, characterized in that, The catalyst includes a support and an active component supported on the support. Among them, the support is mesoporous γ-Al2O3 / SiO2, the active component is a complex formed by a metal salt and a modifier, the modifier is a reaction product of a first component and a second component, the first component is selected from at least one of hydrochloric acid, hydrobromic acid, methanesulfonic acid, trifluoroacetic acid, benzenesulfonic acid or formic acid, the second component is selected from at least one of ethylenediamine, diethylamine, triethylamine, ethanolamine, diethanolamine, triethanolamine, morpholine or pyridine, the metal salt is selected from at least one of iron salt, zinc salt, cobalt salt or copper salt, and the catalyst is weakly acidic.

2. The catalyst according to claim 1, characterized in that, The mass ratio of the metal ion in the metal salt to the support is 0.03:1 - 0.09:1; and / or, the molar ratio of the modifier to the metal ion in the metal salt is 10:1 - 30:

1.

3. A method for preparing a catalyst according to any one of claims 1-2, characterized in that, It includes the following steps: Mix the first component and the second component and adjust the pH to 4.0 - 6.5 to obtain a mixed solution containing the modifier; Add the metal salt to the mixed solution to form a formulation; Then add the support to the formulation for adsorption, and after the adsorption is completed, separate to obtain the catalyst.

4. The preparation method of the catalyst according to claim 3, wherein, In the step of adding the support to the formulation for adsorption, the temperature is 60°C - 80°C and the time is 4 hours - 6 hours.

5. A method for synthesizing a malonic ester compound, characterized in that, It includes the following steps: Mix cyanoacetic acid, water and the catalyst as described in any one of claims 1 - 2 and carry out activation treatment to obtain a first mixed material; Under the presence of a catalyst for cyanoacetic acid hydrolysis reaction, carry out hydrolysis reaction on the first mixed material to obtain a second mixed material containing malonic acid; Add an alcohol to the second mixed material for esterification reaction to obtain a malonic acid ester compound.

6. The method for synthesizing the malonic ester compound according to claim 5, wherein In the step of mixing cyanoacetic acid, water and the catalyst and carrying out activation treatment, the mass ratio of the catalyst to cyanoacetic acid is 0.05:1 - 0.09:1, and / or, the molar ratio of cyanoacetic acid to water is 1:1 - 2:1, and / or, the temperature of the activation treatment is 60°C - 80°C and the time is 0.5 hour - 1 hour.

7. The synthesis method of the malonic ester compound according to claim 5, characterized in that The catalyst for cyanoacetic acid hydrolysis reaction is selected from strongly acidic cation exchange resins with sulfonic groups; and / or, in the step of carrying out hydrolysis reaction on the first mixed material, the temperature is 60°C - 80°C.

8. The method for synthesizing the malonic ester compound according to claim 5, wherein In the step of adding an alcohol to the second mixed material for esterification reaction, the alcohol is selected from at least one of methanol, ethanol, n-propanol, isopropanol or n-butanol, and / or, the mass ratio of cyanoacetic acid to the alcohol is 1:3 - 1:4, and / or, the temperature of the esterification reaction is 70°C - 100°C.

9. The method for synthesizing the malonic ester compound according to any one of claims 5-8, characterized in that, After the esterification reaction, it further includes the step of separating to obtain the catalyst and recycling it to the activation treatment step.