Production method of malonic acid diester
By using a high-efficiency single-atom Pd/Co/Ni catalyst and a specific solvent for carbonylation reaction, the problems of low catalytic activity, poor stability and difficult separation in the production of malonate diester were solved, and efficient and low-energy production of malonate diester was achieved.
Patent Information
- Application Number
- CN202410448025.1
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-04-15
- Publication Date
- 2025-10-21
AI Technical Summary
The existing dimethyl malonate production process has problems such as the use of highly toxic sodium cyanide, complex process, low yield, low catalytic activity, high energy consumption, and unstable catalyst. In particular, the Pd-based catalyst system is prone to agglomeration, the Co-based catalyst system is easy to decompose, the Ni-based catalyst system is not resistant to hot water, and the homogeneous catalyst is difficult to separate.
By using a high-efficiency single-atom Pd/Co/Ni catalyst, combined with specific solvents and stabilizers such as phosphine ligands and quaternary phosphonium salts, a fixed-bed tubular reactor is used to carry out a one-step high-activity and high-selectivity carbonylation reaction to solve the problems of low catalytic activity and stability. The catalyst separation problem is solved through gas-liquid-solid three-phase separation and catalyst regeneration treatment.
It achieves efficient production of malonate diester, solves the stability and separation problems of the catalyst, has industrial application prospects, improves catalytic activity and selectivity, and reduces energy consumption.
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Figure CN120817857A_ABST
Abstract
Description
Technical Field
[0001] The present application relates to a method for producing a malonate diester, and belongs to the field of chemical catalytic conversion. Background Art
[0002] Dimethyl malonate (DMM) is a general-purpose organic reagent and a key raw material for the production of the pharmaceutical pipemidic acid. Overseas, DMM is primarily used as a raw material for the non-ethoxymethylene process to produce pipemidic acid, reacting with orthoformate and urea to produce pipemidic acid. Currently, the majority of DMM produced by Chinese companies, in addition to export, is used to produce pipemidic acid.
[0003] Traditionally, dimethyl malonate is produced using the cyanide esterification method. Chloroacetic acid is neutralized with sodium carbonate to produce sodium chloroacetate, which is then cyanated with sodium cyanide to produce sodium cyanoacetate. Sodium cyanoacetate is hydrolyzed to sodium malonate, which is then esterified with methanol in the presence of sulfuric acid to produce dimethyl malonate. The finished product is then washed and distilled. The industrial product contains ≥98% ester. Raw material consumption requirements include: 1120 kg / t chloroacetic acid, 551 kg / t sodium cyanide, and 955 kg / t methanol. Currently, this technology suffers from issues such as the use of highly toxic sodium cyanide, a complex process, low yield, and difficulty in product and wastewater disposal.
[0004] New processes developed abroad primarily rely on catalytic carbonylation, using chloroacetate, carbon monoxide, and methanol as raw materials in the presence of a catalyst to synthesize dimethyl malonate in a single step. While this process is technologically advanced, it also presents challenges, such as low catalytic activity, high energy consumption, and a complex process. For example, the carbonylation outlet requires three-phase separation of solid, gas, and liquid, with CO gas phase recirculation, followed by distillation of the liquid product to separate the alcohol and malonate diester. Alkali metal salts also require washing, making industrialization difficult. Furthermore, the catalyst mother liquor in the liquid phase must be recycled. Summary of the Invention
[0005] Based on the above-mentioned catalytic carbonylation method, the present invention innovates in the catalyst, reaction solvent, and reaction system. It proposes the use of high-efficiency single-atom Pd, Co, and Ni catalysts, focusing on the local chemical environment of the active site, and selecting a specific solvent to significantly improve the catalytic activity of the catalyst; in addition, a fixed-bed tubular reactor is selected.
[0006] The present invention aims to provide a one-step, highly active and highly selective carbonylation method for preparing malonate diesters using a homogeneous or heterogeneous single-active-site Pd / Co / Ni-based catalyst in the presence of methyl chloroacetate, ethyl chloroacetate, or dichloromethane, CO, alcohols, a base, a phosphine ligand, and a solvent. The method has promising industrial applications and addresses the low activity and instability of existing Pd-based catalytic systems, which are prone to aggregation and instability; and the issues of Co-based catalytic systems, which are prone to decomposition in the presence of air and water and unstable when heated, resulting in catalyst metal loss. The Ni-based catalytic system is a novel discovery, characterized by its heat, water, and air resistance, and its stability during the reaction and subsequent flash evaporation process. Furthermore, the system employs a quaternary phosphonium salt catalytic system, which addresses the difficulty in separating catalysts in homogeneous systems.
[0007] In one aspect of the present application, a method for producing a malonate diester is provided. According to the method provided in the present application, a malonate diester is prepared by a one-step high-activity and high-selectivity carbonylation reaction using a Pd / Co / Ni catalyst with methyl chloroacetate, ethyl chloroacetate, or dichloromethane, CO, an alcohol, a base, and a solvent.
[0008] A method for producing a malonate diester, comprising:
[0009] In the reactor, raw materials containing substrate, CO, alcohol, alkaline substance, solvent, and stabilizer react in a carbonylation reaction system containing a catalyst to obtain a malonate diester;
[0010] The catalyst includes an active component, the active component includes an active element, and the active element is at least one of Pd, Co, and Ni;
[0011] The substrate is at least one of methyl chloroacetate, ethyl chloroacetate, and dichloromethane;
[0012] When the catalyst is a neutral mononuclear complex catalyst, the stabilizer is a phosphine ligand stabilizer;
[0013] When the catalyst is an anionic mononuclear complex catalyst, the stabilizer is a quaternary phosphonium salt stabilizer and / or a quaternary ammonium salt stabilizer.
[0014] In the method of the present application, a phosphine ligand is added to the carbonylation system as a stabilizer for the neutral mononuclear complex catalyst and electronically modifies the metal active center. A quaternary phosphonium salt or a quaternary ammonium salt is added as a stabilizer for the anionic mononuclear complex catalyst.
[0015] Optionally, the phosphine ligand stabilizer is at least one of triphenylphosphine, triphenylphosphine oxide, triphenylphosphine sulfide, tributylphosphine, tributylphosphine oxide, tributylphosphine sulfide, 1,2-bistriphenylphosphine ethane, 1,3-bistriphenylphosphine propane, 1,4-bistriphenylphosphine butane, and 4,5-bisdiphenylphosphine xanthene.
[0016] Optionally, the quaternary phosphonium salt stabilizer is at least one of triphenylmethylphosphine iodide, triphenylmethylphosphine bromide, triphenylmethylphosphine chloride, tributylmethylphosphine iodide, tributylmethylphosphine iodide bromide, tributylmethylphosphine chloride, 1,2-bistriphenylmethylphosphine iodide ethane, 1,2-bistriphenylmethylphosphine bromide ethane, 1,2-bistriphenylmethylphosphine chloride ethane, 4,5-bisdiphenylphosphine methyl iodide xanthene, 4,5-bisdiphenylphosphine methyl bromide xanthene, and 4,5-bisdiphenylphosphine methyl chloride xanthene.
[0017] Optionally, the quaternary ammonium salt stabilizer is at least one of tetramethylammonium iodide, tetrabutylammonium iodide, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, and tetrabutylammonium chloride.
[0018] Optionally, the catalyst is at least one of palladium acetate, cobalt acetate, nickel acetate, palladium chloride, palladium bromide, palladium iodide, cobalt chloride, cobalt bromide, cobalt iodide, nickel chloride, nickel bromide, nickel iodide, tetrakis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)cobalt, bis(triphenylphosphine)cobalt, bis(triphenylphosphine)nickel, carbonylpalladium chloride, carbonylcobalt chloride, carbonylnickel chloride, bistriphenylphosphinepalladium chloride, bistriphenylphosphinecobalt chloride, and triphenylphosphinenickel chloride. That is, the Pd / Co / Ni catalyst is a homogeneous catalyst.
[0019] Optionally, in the catalyst, the loading amount of the active element is 0.1 to 3.0 wt%.
[0020] Optionally, the catalyst further comprises a carrier, that is, the Pd / Co / Ni catalyst is a supported heterogeneous supported catalyst;
[0021] In the catalyst, the precursor of the active component is at least one of palladium acetate, cobalt acetate, nickel acetate, palladium chloride, palladium bromide, palladium iodide, cobalt chloride, cobalt bromide, cobalt iodide, nickel chloride, nickel bromide, nickel iodide, carbonyl palladium, carbonyl cobalt, carbonyl nickel, tetrakis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)cobalt, bis(triphenylphosphine)cobalt, bis(triphenylphosphine)nickel, carbonyl palladium chloride, carbonyl cobalt chloride, carbonyl nickel chloride, bistriphenylphosphine palladium chloride, bistriphenylphosphine cobalt chloride, triphenylphosphine nickel chloride, 4,5-bisdiphenylphosphine-9,9-dimethylxanthene palladium, 4,5-bisdiphenylphosphine-9,9-dimethylxanthene cobalt, and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene nickel.
[0022] Optionally, the support is a porous organic carbon support and / or a porous inorganic carbon support, the surface of which contains oxygen functional groups, including activated carbon, mesoporous carbon, and artificial carbon;
[0023] The porous inorganic carbon support contains a modified functional group, and the modified functional group is at least one of nitrogen, oxygen, phosphine and sulfur functional groups.
[0024] Optionally, the specific surface area of the carrier is 800 to 3000 m 2 / g, pore volume is 1~2m 3 / g.
[0025] Optionally, in the reaction system, [M(CO) x N y ] z- With quaternary phosphonium salts [P] + or quaternary ammonium salt [N] + An ionic compound composed of: wherein M is at least one of Pd, Co, and Ni, N is at least one of Cl, Br, and I, and 0≤x≤4, 0≤y≤4, and 0≤z≤2;
[0026] The [M(CO) x N y ] z- Derived from the catalyst;
[0027] The quaternary phosphonium salt [P] + Derived from quaternary phosphonium salt stabilizer;
[0028] The quaternary ammonium salt [N] + Derived from quaternary ammonium salt stabilizer.
[0029] Optionally, the alcohol is at least one of methanol, ethanol, propanol, butanol, and isobutanol.
[0030] Optionally, the alkaline substance is an alkali metal salt containing an alkaline element;
[0031] The alkaline element is at least one of Li, Na, and K;
[0032] The alkali metal salt is at least one of phosphate, hydrogen phosphate, phosphite, carbonate, hydrogen carbonate, and sulfate.
[0033] Optionally, the alkali metal salt is a carbonate or a bicarbonate.
[0034] Optionally, the solvent is at least one of toluene, tetrahydrofuran, dimethyl malonate, diethyl malonate, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N,N-diethylacetamide.
[0035] Optionally, the molar ratio of the stabilizer to the catalyst is 2 to 100:1.
[0036] Optionally, the molar ratio of the stabilizer to the catalyst is independently selected from any value among 2, 5, 10, 30, 50, 100, or a range between any two of the above values.
[0037] Optionally, the molar ratio of the alkaline substance to the substrate is 1 to 2:1.
[0038] Optionally, the molar ratio of the substrate to the catalyst is 10 to 1000, wherein the molar amount of the catalyst is calculated based on the molar amount of the active element.
[0039] Optionally, the molar ratio of substrate to catalyst is independently selected from any value among 10, 100, 200, 400, 600, 800, 1000 or a range between any two of the above values.
[0040] Optionally, the molar ratio of the substrate to the alcohol is 1:5 to 2:1.
[0041] Optionally, the molar ratio of the substrate to the alcohol is independently selected from any value among 1:5, 1:4, 1:3, 1:2, 1:1, 2:1, or a range between any two of the above.
[0042] Optionally, the molar ratio of the substrate to CO is (0.5-2):1.
[0043] Optionally, the molar ratio of the substrate to CO is independently selected from any value among 0.5:1, 1:1, 1.5:1, 2:1, or a range between any two of the above values.
[0044] Optionally, the molar ratio of the substrate to the solvent is 1:1 to 1:10.
[0045] Optionally, the molar ratio of the substrate to the solvent is independently selected from any value of 1:1, 1:2, 1:5, 1:10, or a range between any two of the above.
[0046] Optionally, the malonate diester includes at least one of dimethyl malonate, diethyl malonate, methyl ethyl malonate, dipropyl malonate, dibutyl malonate, and diisobutyl malonate.
[0047] Optionally, the carbonylation product also includes trace by-products such as methyl acetate, ethyl acetate, propyl acetate, methyl glycolate, and methyl methoxyacetate.
[0048] Optionally, the reactor is at least one of a tank reactor or a slurry bed reactor.
[0049] Optionally, the reaction temperature is 60-120° C., the reaction pressure is 1-8 MPa, and the reaction time is 0.5-10.0 h.
[0050] Optionally, the reaction temperature is independently selected from any value among 60°C, 80°C, 100°C, 120°C or a range between any two of the above values.
[0051] Optionally, the reaction pressure is independently selected from any value among 1 MPa, 3 MPa, 5 MPa, 8 MPa, or a range between any two of the above values.
[0052] Optionally, the reaction time is independently selected from any value among 0.5h, 1h, 2h, 4h, 6h, 8h, 10h or a range between any two of the above values.
[0053] Optionally, when the catalyst does not include a carrier and the solvent is a low-boiling point solvent, after the reaction is completed, the gas phase, liquid phase and solid phase are separated; the separated liquid phase is sequentially subjected to one-stage distillation, two-stage distillation and three-stage distillation; after the one-stage distillation, the top product I is obtained and enters the two-stage distillation, wherein the top product I includes methanol, methyl acetate, methyl chloroacetate and solvent; the bottom product II obtained after the two-stage distillation is methyl chloroacetate and solvent, which is returned to the reactor, the top product II obtained after the two-stage distillation includes methanol, methyl acetate and solvent, and after three-stage distillation, the methanol and solvent are returned to the reactor; the bottom product I obtained after the one-stage distillation includes a liquid phase product and a solid phase product, the liquid phase product is refined to obtain the diester of malonate, and the solid phase product is the catalyst, which is returned to the reactor.
[0054] Optionally, when the catalyst does not include a carrier and the solvent is a high-boiling point solvent, after the reaction is completed, the gas phase, liquid phase, and solid phase are separated; the separated liquid phase is sequentially subjected to a first-stage distillation, a second-stage distillation, and a third-stage distillation; the top product I obtained after the first-stage distillation is subjected to a second-stage distillation, wherein the top product I includes methanol, methyl acetate, methyl chloroacetate, and malonate diester; after the second-stage distillation, the top product II obtained includes methyl acetate, methanol, and methyl chloroacetate, and after the top product II is subjected to a third-stage distillation, methanol and methyl chloroacetate are returned to the reactor; the bottom product II obtained by the second-stage distillation is refined to obtain the malonate diester product; the bottom product I obtained after the first-stage distillation includes the solvent and the catalyst and is returned to the reactor;
[0055] Alternatively, when the catalyst includes a carrier, after the reaction is completed, the gas phase, liquid phase, and solid phase are separated, and the solid phase is washed with alcohol and / or water to obtain the catalyst; the liquid phase is sequentially subjected to one-stage distillation, two-stage distillation, and three-stage distillation. The bottom product I obtained after the first-stage distillation is a malonate diester product, which enters a refining tower for refining, and the top product I enters the second-stage distillation, wherein the top product I includes methanol, methyl acetate, and methyl chloroacetate; after the second-stage distillation, the top product II obtained includes methanol and methyl acetate, and after three-stage distillation, the methanol is returned to the reactor; the bottom product obtained by the second-stage distillation includes methyl chloroacetate and a solvent, which is returned to the reactor. The top product I obtained by the first-stage distillation also includes a solvent and is returned to the reactor.
[0056] Optionally, the production method further includes regeneration of the catalyst; the conditions for catalyst regeneration include: heat treatment with CO\H2\CH3I, temperature 150-250°C, reaction time 1-5h, and pressure 1-5MPa.
[0057] As a specific embodiment, the method provided in the present application uses a homogeneous catalyst and a low-boiling point solvent, and the reaction can be carried out in parallel in multiple reactors. After the reaction is completed, the gas phase, liquid phase, and solid phase are separated. The separated liquid phase is distilled, and the distillation includes performing one-stage distillation, two-stage distillation, and three-stage distillation in sequence. After the first stage of distillation, the top products 1 methanol, methyl acetate, methyl chloroacetate, and solvent are obtained and enter the second stage of distillation. The bottom of the second stage distillation tower is methyl chloroacetate / solvent, which returns to the reactor, and the top of the tower is methanol, methyl acetate or solvent. After some methyl acetate is taken out through distillation in the three-stage distillation tower, methanol and solvent are returned to the reactor from the top of the tower. After the first stage of distillation, the bottom material includes the liquid product malonate diester and the solid phase product. The liquid phase product is refined to obtain the malonate diester, and the solid phase product is the catalyst, which is returned to the reactor;
[0058] By selecting a homogeneous catalyst and a high-boiling point solvent, the reaction can be carried out in parallel in multiple reactors. After the reaction is completed, the gas phase, liquid phase and solid phase are separated. The separated liquid phase undergoes one-stage distillation, two-stage distillation and three-stage distillation. The top products I obtained after the first distillation, such as methanol, methyl acetate, methyl chloroacetate, and diester of malonate, are subjected to two-stage distillation. The top product I of the two-stage distillation tower includes methyl acetate, methanol and methyl chloroacetate, and then after three distillations to take out methyl acetate, methanol and methyl chloroacetate are returned to the reactor. The diester of malonate product is obtained after refining the bottom product II of the two-stage distillation tower; the bottom components after the first distillation include solvent and catalyst, which are returned to the reactor;
[0059] A multiphase supported catalyst is selected. After gas, liquid, and solid phase separation, the catalyst and alkaline solid are washed with alcohol or solvent, then water is used to dissolve the alkaline solid. The dissolved liquid is then electrolyzed in a power plant, and the remaining solid, the catalyst, is returned to the reactor or regenerated. If the catalyst includes a support, after the reaction, the gas, liquid, and solid phases are separated, and the solid phase is washed with alcohol and water to obtain the catalyst. The liquid phase undergoes first-stage distillation, second-stage rectification, and third-stage rectification. After the first-stage distillation, the bottom of the tower contains the malonate diester product, which enters a refining tower for refining. The top product, consisting of methanol, methyl acetate, and a small amount of light components, along with a small amount of unreacted methyl chloroacetate, enters the second-stage rectification. The top components of the second-stage rectification tower are methanol and methyl acetate. After removing the methyl acetate, the methanol is returned to the reactor. The methyl chloroacetate and solvent in the bottom of the second-stage distillation tower are returned to the reactor. The first-stage rectification yields the second-stage product II, which also includes the solvent and is returned to the reactor. Catalyst regeneration: Catalyst regeneration is carried out by CO\H2\CH3I heat treatment at a temperature of 150-250°C, a reaction time of 1-5h, and a pressure of 1-5MPa.
[0060] The beneficial effects of this application include:
[0061] Over homogeneous or heterogeneous single-site Pd / Co / Ni-based catalysts, methyl chloroacetate, ethyl chloroacetate, or dichloromethane, in the presence of CO, alcohols, a base, a phosphine ligand, and a solvent, a highly active and selective one-step carbonylation reaction produces malonate diesters. This novel process addresses the low activity and instability of existing Pd-based catalytic systems, including their proneness to aggregation and instability; and the issues of Co-based catalytic systems, such as their tendency to decompose in the presence of air and water and their thermal instability, which can lead to catalyst metal loss. Furthermore, this novel Ni-based catalytic system is heat-resistant, water-resistant, and air-resistant, and is stable during the reaction and subsequent flash evaporation. Furthermore, the use of a quaternary phosphonium salt catalytic system in this system addresses the difficulty of catalyst separation in homogeneous systems. BRIEF DESCRIPTION OF THE DRAWINGS
[0062] Figure 1 This is the HAADF-STEM image of the multiphase single-atom Pd1 catalyst in Example 1 of the present application, where the scale is 5 nm;
[0063] Figure 2 The geometric molecular structure model of the homogeneous carbonylation single-site Co1 / QPs catalyst in Example 4 of the present application, wherein QPs is a quaternary phosphonium salt;
[0064] Figure 3 This is a process flow chart for an embodiment of the present application (homogeneous catalysis + high boiling point solvent);
[0065] Figure 4 This is a process flow chart for an embodiment of the present application (homogeneous catalysis + low boiling point solvent);
[0066] Figure 5 This is a process flow chart (heterogeneous catalysis + low boiling point solvent) for an embodiment of the present application. DETAILED DESCRIPTION
[0067] The present application is described in detail below with reference to embodiments, but the present application is not limited to these embodiments.
[0068] Unless otherwise specified, the raw materials in the examples of this application were purchased through commercial channels.
[0069] Possible implementation methods are described below: QPs is quaternary phosphonium salt, and AC is activated carbon.
[0070] Figure 1 The HAADF-STEM image of the heterogeneous single-atom Pd1 catalyst of Example 1 is shown in FIG. Figure 1 It can be seen that Pd is dispersed at the single-atom level.
[0071] Figure 2This is the geometric molecular structure model of the homogeneous carbonylation single-site Co1 / QPs catalyst in Example 4 of the present application.
[0072] Figure 3 The process flow chart of the present application using a homogeneous catalyst and a high boiling point solvent comprises the following steps:
[0073] In a reactor, raw materials containing methyl chloroacetate, CO, alcohols, Na salts, solvents, and stabilizers react in a reaction system containing a catalyst to obtain a malonate diester.
[0074] A homogeneous catalyst and a high-boiling-point solvent are used. After the reaction, the carbonylation reaction product undergoes phase separation to produce a gas phase, a liquid phase, and a solid phase. The gas phase is returned to a buffer tank by a compressor for secondary reuse, while the liquid and solid phases are separated by a cyclone. The separated solid phase is washed with alcohol in a washing tank, and the washing liquid is returned to the reactor. The washed solid NaCl is electrolyzed with water to produce NaOH, Cl2, and H2. The liquid phase undergoes first-stage distillation, second-stage distillation, and third-stage distillation. The first-stage distillation overhead product I, which includes methyl acetate, methanol, methyl chloroacetate, and dimethyl malonate, undergoes second-stage distillation. The second-stage distillation overhead components, methanol, methyl acetate, and methyl chloroacetate, undergo third-stage distillation, and the remaining methanol and methyl chloroacetate after removing methyl acetate are returned to the reactor. The second-stage distillation bottom product II is the dimethyl malonate product, which is then refined. After the first-stage bottom distillation, the products in the distillation bottom are the high-boiling-point solvent and catalyst, which are returned to the reactor.
[0075] Figure 4 The process flow chart of the present application using a homogeneous catalyst and a low-boiling-point solvent comprises the following steps:
[0076] In a reactor, raw materials containing methyl chloroacetate, CO, alcohols, Na salts, solvents, and stabilizers react in a reaction system containing a catalyst to obtain a malonate diester.
[0077] A homogeneous catalyst and a low-boiling-point solvent are used. After the reaction is completed, the carbonylation reaction product undergoes phase separation to produce a gas phase, a liquid phase, and a solid phase. The gas phase is returned to a buffer tank by a compressor for secondary use, while the liquid and solid phases are separated by a cyclone. The separated solid phase is washed with alcohol in a washing tank, and the washing liquid is returned to the reactor. The washed solid NaCl is electrolyzed into NaOH, Cl2, and H2 by adding water. The liquid phase undergoes first-stage distillation, second-stage distillation, and third-stage distillation. The first-stage distillation overhead products, methanol, methyl ester, methyl chloroacetate, and solvent, are distilled to the second stage. The second-stage distillation overhead components, including methanol, methyl acetate, and a small amount of light components, as well as a small amount of unreacted methyl chloroacetate, are distilled to the third stage. After removing methyl acetate, the methanol and chloroacetic acid are returned to the reactor. The bottom product of the second-stage distillation, including the solvent, is returned to the reactor. After the solvent is distilled off in the first stage distillation, the solid catalyst precipitates and is returned to the reactor. The liquid after the first stage distillation is the product, diester malonate, which can be phase-separated. The liquid product malonate diester enters the refining tower for refining.
[0078] Figure 5 The process flow chart of this application using a heterogeneous catalyst and a low boiling point solvent comprises the following steps:
[0079] In a reactor, raw materials containing methyl chloroacetate, CO, alcohols, Na salts, solvents, and stabilizers react in a reaction system containing a catalyst to obtain a malonate diester.
[0080] A heterogeneous supported catalyst is used. After the reaction is completed, the carbonylation reaction product undergoes phase separation to obtain a gas phase, a liquid phase, and a solid phase. The solid phase (catalyst and solid) is washed with alcohol, and then the NaCl solid is dissolved in water. The dissolved solution is electrolyzed to produce NaOH, Cl2, and H2. The remaining solid (catalyst) is returned to the reactor or regenerated. The liquid phase undergoes a first-stage distillation, a second-stage distillation, and a third-stage distillation. After the first-stage distillation, the diester product enters the bottom of the tower and enters a refining tower for refining. The overhead products, including methanol, methyl acetate, and a small amount of unreacted methyl chloroacetate, enter the second-stage distillation. The overhead components of the second-stage distillation tower are methanol and methyl acetate. After removing the methyl acetate, the methanol is returned to the reactor. The methyl chloroacetate and solvent in the bottom of the second-stage distillation tower are returned to the reactor. The first-stage distillation obtains the second-stage product II, which also includes the solvent and is returned to the reactor.
[0081] Example 1
[0082] according to Figure 5 The process is carried out.
[0083] Catalyst: Heterogeneous single-atom Pd1 / AC, metal loading 0.25 wt%
[0084] Raw materials: methyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylphosphine.
[0085] Production conditions: 80°C, CO 5.0 MPa, alcohol / methyl chloroacetate = 1 (molar ratio), Na / methyl chloroacetate = 2 (molar ratio), methyl chloroacetate / CO molar ratio = 1, methyl chloroacetate / solvent molar ratio = 0.2, stabilizer / Pd = 50, methyl chloroacetate / Pd = 1000 (molar ratio), reaction 1 h.
[0086] Example 2
[0087] according to Figure 5 The process is carried out.
[0088] Catalyst: heterogeneous single-atom Ni1 / AC, metal loading 1 wt%.
[0089] Raw materials: methyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide.
[0090] Production conditions: 80°C, CO 5.0 MPa, alcohol / methyl chloroacetate = 1 (molar ratio), Na / methyl chloroacetate = 2 (molar ratio), methyl chloroacetate / CO molar ratio = 1, methyl chloroacetate / solvent molar ratio = 0.2, stabilizer / Ni = 2, methyl chloroacetate / Ni = 1000 (molar ratio), reaction 1 h.
[0091] Example 3
[0092] according to Figure 5 The process is carried out.
[0093] Catalyst: Heterogeneous single-atom Co1 / AC, metal loading 1 wt%.
[0094] Raw materials: methyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide.
[0095] Production conditions: 80°C, CO 5.0 MPa, alcohol / methyl chloroacetate = 1 (molar ratio), Na / methyl chloroacetate = 2 (molar ratio), methyl chloroacetate / CO molar ratio = 1, methyl chloroacetate / solvent molar ratio = 0.2, stabilizer / Co = 2, methyl chloroacetate / Co = 1000 (molar ratio), reaction 1 h.
[0096] Example 4
[0097] according to Figure 3 The process is carried out.
[0098] Catalyst: Homogeneous single-atom Co1 / QPs.
[0099] Raw materials: methyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0100] Production conditions: 80°C, CO 5.0 MPa, alcohol / methyl chloroacetate = 1 (molar ratio), Na / methyl chloroacetate = 2 (molar ratio), methyl chloroacetate / CO molar ratio = 1, methyl chloroacetate / solvent molar ratio = 0.2, stabilizer / Co = 2, methyl chloroacetate / Co = 1000 (molar ratio), reaction 1 h.
[0101] Example 5
[0102] according to Figure 3 The process is carried out.
[0103] Catalyst: Homogeneous single-atom Ni1 / QP.
[0104] Raw materials: methyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0105] Production conditions: 80°C, CO 5.0 MPa, alcohol / methyl chloroacetate = 1 (molar ratio), Na / methyl chloroacetate = 2 (molar ratio), methyl chloroacetate / C molar ratio = 1, methyl chloroacetate / solvent molar ratio = 0.2, stabilizer / Ni = 2, methyl chloroacetate / Ni = 1000 (molar ratio), reaction 1 h.
[0106] Example 6
[0107] according to Figure 4 The process is carried out.
[0108] Catalyst: Homogeneous single-atom Pd1 / QPs.
[0109] Raw materials: methyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylphosphine
[0110] Production conditions: 80°C, CO 5.0 MPa, alcohol / methyl chloroacetate = 1 (molar ratio), Na / methyl chloroacetate = 2 (molar ratio), methyl chloroacetate / CO molar ratio = 1, methyl chloroacetate / solvent molar ratio = 0.2, stabilizer / Pd = 50, methyl chloroacetate / Pd = 1000 (molar ratio), reaction 1 h.
[0111] Example 7
[0112] according to Figure 5 The process is carried out.
[0113] Catalyst: heterogeneous single-atom Ni1 / AC, metal loading 1 wt%.
[0114] Raw materials: ethyl chloroacetate + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0115] Production conditions: 80°C, CO 5.0 MPa, alcohol / ethyl chloroacetate = 1 (molar ratio), Na / ethyl chloroacetate = 2 (molar ratio), molar ratio of ethyl chloroacetate / CO = 1, molar ratio of ethyl chloroacetate / solvent = 0.2, stabilizer / Ni = 2, ethyl chloroacetate / Ni = 1000 (molar ratio), reaction 1 h.
[0116] Example 8
[0117] according to Figure 5 The process is carried out.
[0118] Catalyst: Heterogeneous single-atom Co1 / AC, metal loading 1 wt%.
[0119] Raw materials: ethyl chloroacetate + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0120] Production conditions: 80°C, CO 5.0 MPa, alcohol / ethyl chloroacetate = 1 (molar ratio), Na / ethyl chloroacetate = 2 (molar ratio), molar ratio of ethyl chloroacetate / CO = 1, molar ratio of ethyl chloroacetate / solvent = 0.2, stabilizer / Co = 2, ethyl chloroacetate / Co = 1000 (molar ratio), reaction 1 h.
[0121] Example 9
[0122] according to Figure 5 The process is carried out.
[0123] Catalyst: Heterogeneous single-atom Pd1 / AC, metal loading 0.25 wt%.
[0124] Raw materials: ethyl chloroacetate + CO + ethanol + NaCl + diethyl malonate + triphenylphosphine
[0125] Production conditions: 80°C, CO 5.0 MPa, alcohol / ethyl chloroacetate = 1 (molar ratio), Na / ethyl chloroacetate = 2 (molar ratio), molar ratio of ethyl chloroacetate / CO = 1, molar ratio of ethyl chloroacetate / solvent = 0.2, stabilizer / Pd = 50, ethyl chloroacetate / Pd = 1000 (molar ratio), reaction 1 h.
[0126] Example 10
[0127] according to Figure 4 The process is carried out.
[0128] Catalyst: homogeneous single-atom Ni1 / QPs.
[0129] Raw materials: ethyl chloroacetate + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0130] Production conditions: 80°C, CO 5.0 MPa, alcohol / ethyl chloroacetate = 1 (molar ratio), Na / ethyl chloroacetate = 2 (molar ratio), molar ratio of ethyl chloroacetate / CO = 1, molar ratio of ethyl chloroacetate / solvent = 0.2, stabilizer / Ni = 2, ethyl chloroacetate / Ni = 1000 (molar ratio), reaction 1 h.
[0131] Example 11
[0132] according to Figure 3 The process is carried out.
[0133] Catalyst: Homogeneous single-atom Co1 / QPs.
[0134] Raw materials: ethyl chloroacetate + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0135] Production conditions: 80°C, CO 5.0 MPa, alcohol / ethyl chloroacetate = 1 (molar ratio), Na / ethyl chloroacetate = 2 (molar ratio), molar ratio of ethyl chloroacetate / CO = 1, molar ratio of ethyl chloroacetate / solvent = 0.2, stabilizer / Co = 2, ethyl chloroacetate / Co = 1000 (molar ratio), reaction 1 h.
[0136] Example 12
[0137] according to Figure 3 The process is carried out.
[0138] Catalyst: Homogeneous single-atom Pd1 / QPs.
[0139] Raw materials: ethyl chloroacetate + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylphosphine
[0140] Production conditions: 80°C, CO 5.0 MPa, alcohol / ethyl chloroacetate = 1 (molar ratio), Na / ethyl chloroacetate = 2 (molar ratio), molar ratio of ethyl chloroacetate / CO = 1, molar ratio of ethyl chloroacetate / solvent = 0.2, stabilizer / Pd = 50, ethyl chloroacetate / Pd = 1000 (molar ratio), reaction 1 h.
[0141] Example 13
[0142] according to Figure 3 The process is carried out.
[0143] Catalyst: Homogeneous nickel acetate, metal loading 1 wt%.
[0144] Raw materials: methyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0145] Production conditions: 80°C, CO 5.0 MPa, alcohol / methyl chloroacetate = 1 (molar ratio), Na / methyl chloroacetate = 2 (molar ratio), methyl chloroacetate / CO molar ratio = 1, methyl chloroacetate / solvent molar ratio = 0.2, stabilizer / Ni = 2, methyl chloroacetate / Ni = 1000 (molar ratio), reaction 1 h.
[0146] Example 14
[0147] according to Figure 3 The process is carried out.
[0148] Catalyst: homogeneous nickel acetate.
[0149] Raw materials: ethyl chloroacetate + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0150] Production conditions: 80°C, CO 5.0 MPa, alcohol / ethyl chloroacetate = 1 (molar ratio), Na / ethyl chloroacetate = 2 (molar ratio), molar ratio of ethyl chloroacetate / CO = 1, molar ratio of ethyl chloroacetate / solvent = 0.2, stabilizer / Ni = 2, ethyl chloroacetate / Ni = 1000 (molar ratio), reaction 1 h.
[0151] Malonate diesters were prepared using Examples 1-14, and their carbonylation activity TOF and product malonate diester selectivity are shown in Table 1.
[0152] Table 1 Example Methyl (ethyl) chloroacetate to dimethyl (ethyl) malonate Results Summary
[0153]
[0154]
[0155] The calculation of TOF refers to the ratio of the number of moles of product CO converted per unit time to the number of moles of catalyst.
[0156] Taking the reaction of dimethyl malonate as an example,
[0157] Dimethyl malonate selectivity = moles of dimethyl malonate / (moles of dimethyl malonate + moles of methyl acetate + moles of methyl methoxyacetate + moles of methyl glycolate)*100%;
[0158] Example 15
[0159] according to Figure 3 The process is carried out.
[0160] Catalyst: homogeneous single-atom Ni1 / QPs, metal loading 1.0 wt%.
[0161] Raw materials: dichloromethane + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0162] Production conditions: 80°C, CO 5.0 MPa, alcohol / dichloromethane = 1 (molar ratio), Na / dichloromethane = 2 (molar ratio), dichloromethane / CO molar ratio = 0.5, dichloromethane / solvent molar ratio = 0.2, stabilizer / Ni = 2, dichloromethane / Ni = 1000 (molar ratio), reaction 2h.
[0163] Example 16
[0164] according to Figure 3 The process is carried out.
[0165] Catalyst: homogeneous single-atom Co1 / QPs, metal loading 1.0 wt%.
[0166] Raw materials: dichloromethane + CO + methanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0167] Production conditions: 80°C, CO 5.0 MPa, alcohol / dichloromethane = 1 (molar ratio), Na / dichloromethane = 2 (molar ratio), dichloromethane / CO molar ratio = 0.5, dichloromethane / solvent molar ratio = 0.2, stabilizer / Co = 2, dichloromethane / Co = 1000 (molar ratio), reaction time 2 h.
[0168] Example 17
[0169] according to Figure 3 The process is carried out.
[0170] Catalyst: homogeneous single-atom Pd1 / QPs, metal loading 0.25 wt%.
[0171] Raw materials: dichloromethane + CO + methanol + NaCl + dimethyl malonate + triphenylphosphine
[0172] Production conditions: 80°C, CO 5.0 MPa, alcohol / dichloromethane = 1 (molar ratio), Na / dichloromethane = 2 (molar ratio), dichloromethane / CO molar ratio = 0.5, dichloromethane / solvent molar ratio = 0.2, stabilizer / Pd = 50, dichloromethane / Pd = 1000 (molar ratio), reaction 2h.
[0173] Example 18
[0174] according to Figure 3 The process is carried out.
[0175] Catalyst: homogeneous single-atom Ni1 / QPs, metal loading 1.0 wt%.
[0176] Raw materials: dichloromethane + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0177] Production conditions: 80°C, CO 5.0 MPa, alcohol / dichloromethane = 1 (molar ratio), Na / dichloromethane = 2 (molar ratio), dichloromethane / CO molar ratio = 0.5, dichloromethane / solvent molar ratio = 0.2, stabilizer / Ni = 2, dichloromethane / Ni = 1000 (molar ratio), reaction 2h.
[0178] Example 19
[0179] according to Figure 3 The process is carried out.
[0180] Catalyst: homogeneous single-atom Co1 / QPs, metal loading 1.0 wt%.
[0181] Raw materials: dichloromethane + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylmethylphosphine iodide
[0182] Production conditions: 80°C, CO 5.0 MPa, alcohol / dichloromethane = 1 (molar ratio), Na / dichloromethane = 2 (molar ratio), dichloromethane / CO molar ratio = 0.5, dichloromethane / solvent molar ratio = 0.2, stabilizer / Co = 2, dichloromethane / Co = 1000 (molar ratio), reaction time 2 h.
[0183] Example 20
[0184] according to Figure 3 The process is carried out.
[0185] Catalyst: homogeneous single-atom Pd1 / QPs, metal loading 0.25 wt%.
[0186] Raw materials: dichloromethane + CO + ethanol + NaCl + N,N-dimethylformamide + triphenylphosphine
[0187] Production conditions: 80°C, CO 5.0 MPa, alcohol / dichloromethane = 1 (molar ratio), Na / dichloromethane = 2 (molar ratio), dichloromethane / CO molar ratio = 0.5, dichloromethane / solvent molar ratio = 0.2, stabilizer / Pd = 50, dichloromethane / Pd = 1000 (molar ratio), reaction 2h.
[0188] Table 2 Summary of results of Examples 15-20 Preparation of dimethyl (ethyl) malonate from dichloromethane
[0189]
[0190] The calculation of TOF refers to the molar ratio of the product dimethyl (ethyl) malonate to the catalyst per unit time.
[0191] The reaction substrates are calculated as dichloromethane and methanol
[0192] Dimethyl malonate selectivity = moles of dimethyl malonate / (moles of dimethyl malonate + moles of methyl chloroacetate + moles of methyl acetate + moles of methyl methoxyacetate + moles of methyl glycolate)*100%;
[0193] The results show that:
[0194] The results of Examples 1-20 show that methyl (ethyl) chloroacetate or dichloromethane can be used to prepare dimethyl (ethyl) malonate with high activity and high selectivity.
[0195] The above descriptions are merely a few embodiments of the present application and do not constitute any form of limitation to the present application. Although the present application discloses the preferred embodiments as above, they are not intended to limit the present application. Any technical personnel familiar with the present profession, without departing from the scope of the technical solution of the present application, using the technical content disclosed above to make slight changes or modifications are equivalent to equivalent implementation cases and fall within the scope of the technical solution.
Claims
1. A method for producing a malonate diester, characterized in that: The production method comprises: In the reactor, raw materials containing substrate, CO, alcohol, alkaline substance, solvent, and stabilizer react in a carbonylation reaction system containing a catalyst to obtain a malonate diester; The catalyst includes an active component, the active component includes an active element, and the active element is at least one of Pd, Co, and Ni; The substrate is at least one of methyl chloroacetate, ethyl chloroacetate, and dichloromethane; When the catalyst is a neutral mononuclear complex catalyst, the stabilizer is a phosphine ligand stabilizer; When the catalyst is an anionic mononuclear complex catalyst, the stabilizer is a quaternary phosphonium salt stabilizer and / or a quaternary ammonium salt stabilizer.
2. The production method according to claim 1, characterized in that The phosphine ligand stabilizer is at least one of triphenylphosphine, triphenylphosphine oxide, triphenylphosphine sulfide, tributylphosphine, tributylphosphine oxide, tributylphosphine sulfide, 1,2-bistriphenylphosphine ethane, 1,3-bistriphenylphosphine propane, 1,4-bistriphenylphosphine butane, and 4,5-bisdiphenylphosphine xanthene; Preferably, the quaternary phosphonium salt stabilizer is at least one of triphenylmethylphosphine iodide, triphenylmethylphosphine bromide, triphenylmethylphosphine chloride, tributylmethylphosphine iodide, tributylmethylphosphine iodide bromide, tributylmethylphosphine chloride, 1,2-bistriphenylmethylphosphine iodide ethane, 1,2-bistriphenylmethylphosphine bromide ethane, 1,2-bistriphenylmethylphosphine chloride ethane, 4,5-bisdiphenylphosphine methyl iodide xanthene, 4,5-bisdiphenylphosphine methyl bromide xanthene, and 4,5-bisdiphenylphosphine methyl chloride xanthene; Preferably, the quaternary ammonium salt stabilizer is at least one of tetramethylammonium iodide, tetrabutylammonium iodide, tetramethylammonium bromide, tetrabutylammonium bromide, tetramethylammonium chloride, and tetrabutylammonium chloride.
3. The production method according to claim 1, characterized in that The catalyst is at least one of palladium acetate, cobalt acetate, nickel acetate, palladium chloride, palladium bromide, palladium iodide, cobalt chloride, cobalt bromide, cobalt iodide, nickel chloride, nickel bromide, nickel iodide, tetrakis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)cobalt, bis(triphenylphosphine)cobalt, bis(triphenylphosphine)nickel, carbonylpalladium chloride, carbonylcobalt chloride, carbonylnickel chloride, bistriphenylphosphinepalladium chloride, bistriphenylphosphinecobalt chloride, and triphenylphosphinenickel chloride.
4. The production method according to claim 1, characterized in that In the catalyst, the loading amount of the active element is 0.1 to 3.0 wt%; The catalyst further comprises a carrier, The precursor of the active component is at least one of palladium acetate, cobalt acetate, nickel acetate, palladium chloride, palladium bromide, palladium iodide, cobalt chloride, cobalt bromide, cobalt iodide, nickel chloride, nickel bromide, nickel iodide, carbonyl palladium, carbonyl cobalt, carbonyl nickel, tetrakis(triphenylphosphine)palladium, tetrakis(triphenylphosphine)cobalt, bis(triphenylphosphine)cobalt, bis(triphenylphosphine)nickel, carbonylpalladium chloride, carbonylcobalt chloride, carbonylnickel chloride, bistriphenylphosphinepalladium chloride, bistriphenylphosphinecobalt chloride, triphenylphosphinenickel chloride, 4,5-bisdiphenylphosphine-9,9-dimethylxanthene palladium, 4,5-bisdiphenylphosphine-9,9-dimethylxanthene cobalt, and 4,5-bisdiphenylphosphine-9,9-dimethylxanthene nickel; Preferably, the support is a porous organic carbon support and / or a porous inorganic carbon support, and the surface of the support contains oxygen functional groups; The porous inorganic carbon support contains a modified functional group, and the modified functional group is at least one of nitrogen, oxygen, phosphine and sulfur functional groups.
5. The production method according to claim 1, characterized in that In the reaction system, [M(CO) x N y ] z- With quaternary phosphonium salts [P] + or quaternary ammonium salt [N] + An ionic compound composed of: wherein M is at least one of Pd, Co, and Ni, N is at least one of Cl, Br, and I, 0≤x≤4, 0≤y≤4, and 0≤z≤2; The [M(CO) x N y ] z- Derived from the catalyst; The quaternary phosphonium salt [P] + Derived from quaternary phosphonium salt stabilizer; The quaternary ammonium salt [N] + Derived from quaternary ammonium salt stabilizer.
6. The production method according to claim 1, characterized in that The alcohol is at least one of methanol, ethanol, propanol, butanol, and isobutanol; Preferably, the alkaline substance is an alkali metal salt containing an alkaline element; The alkaline element is at least one of Li, Na, and K; The alkali metal salt is at least one of phosphate, hydrogen phosphate, phosphite, carbonate, hydrogen carbonate, and sulfate; Preferably, the solvent is at least one of toluene, tetrahydrofuran, dimethyl malonate, diethyl malonate, N,N-dimethylformamide, N,N-dimethylacetamide, N,N-diethylformamide, and N,N-diethylacetamide.
7. The production method according to claim 1, characterized in that: The molar ratio of the stabilizer to the catalyst is (2-100):1; Preferably, the molar ratio of the alkaline substance to the substrate is (1-2):1; Preferably, the molar ratio of substrate to catalyst is 10 to 1000, wherein the molar amount of catalyst is based on the molar amount of active element; Preferably, the molar ratio of the substrate to the alcohol is 1:5 to 2:1; Preferably, the molar ratio of the substrate to CO is 0.5:1 to 2:1; Preferably, the mass ratio of the substrate to the solvent is 1:1 to 1:10; Preferably, the malonate diester includes at least one of dimethyl malonate, diethyl malonate, methyl ethyl malonate, dipropyl malonate, dibutyl malonate, and diisobutyl malonate.
8. The production method according to claim 1, characterized in that The reactor is at least one of a tank reactor and a slurry bed reactor.
9. The production method according to claim 1, characterized in that The reaction temperature is 60-120° C., the reaction pressure is 1-8 MPa, and the reaction time is 0.5-10.0 h.
10. The production method according to claim 1, characterized in that When the catalyst does not include a carrier and the solvent is a low-boiling point solvent, after the reaction is completed, the gas phase, liquid phase, and solid phase are separated; the separated liquid phase is sequentially subjected to one-stage distillation, two-stage distillation, and three-stage distillation; after one-stage distillation, the top product I is obtained and enters the second-stage distillation, wherein the top product I includes methanol, methyl acetate, methyl chloroacetate, and solvent; the bottom product II obtained after the second-stage distillation is methyl chloroacetate and solvent, which is returned to the reactor, and the top product II obtained after the second-stage distillation includes methanol, methyl acetate, and solvent. After three-stage distillation, the methanol and solvent are returned to the reactor; the bottom product I obtained after the one-stage distillation includes a liquid product and a solid product, the liquid product is refined to obtain the malonate diester, and the solid product is the catalyst, which is returned to the reactor; Preferably, when the catalyst does not include a carrier and the solvent is a high-boiling point solvent, after the reaction is completed, the gas phase, liquid phase, and solid phase are separated; the separated liquid phase is sequentially subjected to a first-stage distillation, a second-stage distillation, and a third-stage distillation; the top product I obtained after the first-stage distillation is subjected to a second-stage distillation, wherein the top product I includes methanol, methyl acetate, methyl chloroacetate, and malonate diester; after the second-stage distillation, the top product II obtained includes methyl acetate, methanol, and methyl chloroacetate, and after the top product II is subjected to a third-stage distillation, methanol and methyl chloroacetate are returned to the reactor; the bottom product II obtained by the second-stage distillation is refined to obtain the malonate diester product; the bottom product I obtained after the first-stage distillation includes the solvent and the catalyst and is returned to the reactor; Preferably, when the catalyst includes a carrier, after the reaction is completed, the gas phase, liquid phase, and solid phase are separated, and the solid phase is washed with alcohol and / or water to obtain the catalyst; the liquid phase is sequentially subjected to one-stage distillation, two-stage distillation, and three-stage distillation. The bottom product I obtained after the first-stage distillation is a malonate diester product, which enters a refining tower for refining, and the top product I enters the second-stage distillation, wherein the top product I includes methanol, methyl acetate, and methyl chloroacetate; after the second-stage distillation, the top product II obtained includes methanol and methyl acetate, and after three-stage distillation, the methanol is returned to the reactor; the bottom product obtained by the second-stage distillation includes methyl chloroacetate and a solvent, which is returned to the reactor. The top product I obtained by the first-stage distillation also includes a solvent and is returned to the reactor; Preferably, the production method further comprises regeneration of the catalyst; the conditions for catalyst regeneration include: heat treatment with CO\H2\CH3I, temperature 150-250°C, reaction time 1-5h, and pressure 1-5MPa.