A method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid

Abstract

This invention relates to the field of compound synthesis, specifically to a one-step method for synthesizing succinic anhydride via the carbonylation of acrylic acid. The method uses acrylic acid and carbon monoxide as raw materials, and the carbonylation reaction is carried out in a solvent under the action of a catalyst system comprising a Pd precursor, a phosphine ligand, and an auxiliary agent to synthesize succinic anhydride in one step. This invention not only significantly reduces the raw material cost for synthesizing succinic anhydride, but also achieves mild operation through optimized reaction conditions and catalyst system, significantly reducing energy consumption in the reaction and subsequent separation processes, and improving the overall economic and environmental benefits of the process.

Description

Technical Field

[0001] This invention relates to the field of compound synthesis, and specifically to a catalyst system and method for one-step synthesis of succinic anhydride via carbonylation reaction using acrylic acid and CO as raw materials. Background Technology

[0002] Succinic anhydride, also known as succinic anhydride, is an important organic synthesis intermediate widely used in industries such as pesticides, pharmaceuticals, petrochemicals, dyes, food additives, surfactants, coatings, and plastics, and has broad market prospects.

[0003] In recent years, the downstream applications of succinic anhydride have been rapidly expanding from traditional fields to emerging high-value-added areas, mainly including the following aspects: Biodegradable plastics: As a key monomer of polybutylene succinate (PBS), succinic anhydride is experiencing rapid growth in demand in areas such as packaging materials, agricultural mulch films, and disposable tableware, becoming its most important consumer driver.

[0004] Pharmaceutical intermediates: As a key raw material in the synthesis of vitamin A, sulfonamide drugs and some antibiotics, the demand for pharmaceutical-grade succinic anhydride is steadily increasing.

[0005] Electronic chemicals: High-purity succinic anhydride is gradually replacing imports in electronic chemicals such as semiconductor packaging materials, liquid crystal display materials, photoresists, and cleaning agents, but the technological barriers are relatively high.

[0006] New energy materials: Breakthroughs are being made in research on lithium-ion battery electrolyte additives and solid polymer electrolytes, which are expected to form a new growth engine.

[0007] Against the backdrop of the global chemical industry's transformation towards green and low-carbon development, succinic anhydride, as a key bridge connecting traditional petrochemical raw materials and bio-based chemicals, is facing a dual transformation in both technological routes and market structure.

[0008] Currently, the industrial production of succinic anhydride mainly includes the following three routes: (1) Electrochemical synthesis method This method uses maleic anhydride as a raw material to synthesize succinic anhydride on the electrode surface through a redox reaction. However, high-performance electrode materials (such as precious metals) are expensive and generally have low current efficiency, resulting in large power loss and low energy efficiency, which restricts their large-scale application.

[0009] (2) Biological fermentation method This process uses renewable biomass such as sugars and starches as carbon sources, and generates succinic acid through microbial metabolism, which is then dehydrated to produce succinic anhydride. While its raw materials are renewable, the reaction conditions are mild, and it is environmentally friendly, it suffers from problems such as long fermentation cycles, high energy consumption for product separation, and complex steps, resulting in relatively high overall costs and challenges for large-scale industrialization.

[0010] (3) Maleic anhydride hydrogenation method This route uses maleic anhydride as a raw material, which undergoes a hydrogenation reaction with hydrogen in the presence of a catalyst to produce succinic anhydride. Industrially, fixed-bed or fluidized-bed reactors are commonly used, with typical process conditions of 100–200 °C and 1–5 MPa. Too low a temperature results in a slow reaction rate, while too high a temperature easily triggers side reactions; moderate pressure facilitates hydrogen dissolution and mass transfer. However, this process consumes a large amount of hydrogen, and the high temperature and high pressure conditions lead to significant energy consumption, limiting its further promotion.

[0011] To overcome the aforementioned technical bottlenecks, researchers have been continuously exploring more economical synthetic routes. As early as 1963, Heck et al. (J. Am. Chem. Soc., 1963, 85(10): 1460–1463) reported the synthesis of HCo(CO)4 / Co(CO)4. - The carbonylation reaction of ethylene oxide was catalyzed. Subsequently, the Coates research group at Cornell University (Angew. Chem. Int. Ed., 2002, 41(15): 2781–2784; J. Am. Chem. Soc., 2002, 124(7): 1174–1175; WO3050154, 2003) systematically proposed a Lewis acid / cobalt carbonyl composite catalytic system, clarifying that cobalt carbonyl is the core catalytic species, while Lewis acid significantly enhances the carbonylation activity of epoxides. The team further used tetrachlorophenylporphyrin aluminum chloride as a catalyst to achieve a highly efficient conversion of epoxides to succinic anhydride at 90 °C, with a yield of 98% (J. Am. Chem. Soc., 2007, 129(7): 4948–4960). However, the synthesis of this type of porphyrin ligand catalyst is complex, costly, and requires harsh operating conditions, making it difficult to meet industrial needs. In recent years, Marie-Hélène Pietraru et al. (ChemCatChem2023, 15, e202300720) reported a new route for the carbonylation synthesis of succinic anhydride using cobalt octacarbonyl as a catalyst and acrylic acid as a raw material in a CO / H2 mixed atmosphere, providing a new approach for green and efficient synthesis. However, cobalt octacarbonyl is extremely sensitive to air and water, limiting its industrial application and recycling. Summary of the Invention

[0012] The purpose of this invention is to overcome the shortcomings of existing technologies and provide a one-step method for synthesizing succinic anhydride via the carbonylation reaction of acrylic acid, which is widely available and inexpensive, as a starting material. This method not only significantly reduces raw material costs but also achieves mild operation through optimized reaction conditions and catalyst systems, significantly reducing energy consumption in the reaction and subsequent separation processes, thus improving the overall economic and environmental benefits of the process. It effectively solves the problems of high raw material costs, complex reaction processes, low product yields, and difficulty in product separation inherent in existing technologies.

[0013] Another objective of this invention is to protect the application of a catalyst system comprising a Pd precursor, a phosphine ligand, and an auxiliary agent in the one-step synthesis of succinic anhydride from acrylic acid and carbon monoxide via carbonylation.

[0014] This catalytic system, when applied to the one-step carbonylation synthesis of succinic anhydride, exhibits high catalytic activity, high catalyst stability, high conversion rate, and high product selectivity.

[0015] To achieve the above-mentioned objectives, the specific technical solution of this invention is as follows: The application of a catalyst system consisting of a Pd precursor, phosphine ligand, and auxiliaries in the one-step synthesis of succinic anhydride from acrylic acid and carbon monoxide via carbonylation.

[0016] The catalyst system includes a Pd precursor, a phosphine ligand, and an additive.

[0017] In the catalyst system of the present invention, the Pd precursor is one or more of palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate, palladium chloride, palladium bromide, and palladium acetylacetonate.

[0018] In the catalyst system of this invention, the phosphine ligand is one or more of dppe, dppb, dppp, dppee, Tetraphos, Xantphos, DPEphos, BINAP, H8-BINAP, DTBPX, and BPX; the structural formulas of each compound are as follows: .

[0019] The catalyst system of the present invention includes one or more of the following additives: methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, aluminum trifluoromethanesulfonate, iron trifluoromethanesulfonate, benzenesulfonic acid, and p-methylbenzenesulfonic acid.

[0020] A method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid is disclosed. The method uses acrylic acid and carbon monoxide as raw materials, and carries out a carbonylation reaction in a solvent under the action of a catalyst system consisting of a Pd precursor, a phosphine ligand and an auxiliary agent to synthesize succinic anhydride in one step.

[0021] Based on the catalyst system of this invention, the method for synthesizing succinic anhydride in one step using acrylic acid and CO as raw materials via carbonylation reaction specifically includes the following steps: (1) Weigh out the acrylic acid and solvent and add them to the reaction vessel, and add the corresponding amount of polymerization inhibitor. Stir at a constant temperature until completely dissolved. (2) Add the weighed Pd precursor to the reaction vessel after step (1) and stir at a constant temperature under N2 gas protection until completely dissolved. After complete dissolution, continue stirring for a period of time. (3) Add the weighed phosphine ligand to the reaction vessel after step (2) and stir at a constant temperature under N2 gas protection; (4) Add the weighed additives to the reaction vessel after step (3) and stir at a constant temperature under N2 gas protection; (5) Replace the reactor treated in step (4) with high-purity N2 until the O2 content in the reactor is <0.01% (volume percentage); (6) CO is charged into the reactor after step (5) to a certain pressure, stirred and heated to the reaction temperature to start the reaction. During the reaction, CO is continuously added to the reactor so that the pressure of CO in the reactor remains constant. (7) The reaction ends and the product succinic anhydride is obtained.

[0022] In a preferred embodiment of this application, in step (1) of a method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, the solvent is one or more of toluene, o-xylene, p-xylene, ethyl acetate, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, and 1,4-dioxane; the polymerization inhibitor is one or more of hydroquinone, p-benzoquinone, p-hydroxyanisole, and tetramethylpiperidine oxide; and the temperature of the constant-temperature stirring is 40±5℃.

[0023] As a preferred embodiment of this application, in step (2) of a method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, the Pd precursor is any one or a mixture of several of palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate, palladium chloride, palladium bromide, and palladium acetylacetonate; the constant temperature stirring temperature is 40±5℃; and the stirring time after complete dissolution is 20±5min.

[0024] As a preferred embodiment of this application, in step (3) of a method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, the phosphine ligand is one or more of dppe, dppb, dppp, dppee, Tetraphos, Xantphos, DPEphos, BINAP, H8-BINAP, DTBPX, and BPX; the temperature of the constant temperature stirring is 40±5℃; and the stirring time is 40±5min.

[0025] As a preferred embodiment of this application, in step (4) of a method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, the auxiliary agent is one or more of methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, aluminum trifluoromethanesulfonate, iron trifluoromethanesulfonate, benzenesulfonic acid, and p-methylbenzenesulfonic acid; the constant temperature stirring temperature is 40±5℃; and the stirring time is 20±5min.

[0026] In a preferred embodiment of this application, in a method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, the molar ratio of acrylic acid to solvent is 1:1-8; more preferably, the molar ratio of acrylic acid to solvent is 1:2-4; the total volume of acrylic acid and solvent is 10%-60% of the effective volume inside the reactor, and more preferably, the total volume of acrylic acid and solvent is 25%-40% of the effective volume inside the reactor.

[0027] As a preferred embodiment of this application, in step (6) of a method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, the reaction temperature is 60-160°C, more preferably 70-100°C; and the reaction time is 0.5-8h, more preferably 2-6h.

[0028] In a preferred embodiment of this application, in a method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, CO is introduced into the reaction vessel to a pressure of 0.5-5.0 MPa, more preferably 1.2-3.0 MPa.

[0029] In the synthesis method of the present invention, CO is added to the reaction vessel during the reaction process to maintain a constant pressure.

[0030] Compared with existing technologies, this invention demonstrates significant technological advancements and comprehensive advantages in process route design, catalytic system construction, and separation and purification efficiency, specifically reflected in the following beneficial effects: 1. This invention uses widely available and inexpensive acrylic acid and carbon monoxide as raw materials to synthesize succinic anhydride in one step via a carbonylation reaction. This route utilizes low-cost acrylic acid as a raw material, is compatible with both petroleum-based and bio-based sources, and adapts to the needs of different industrial transformation stages, significantly reducing raw material sourcing limitations and process operating costs from the source.

[0031] 2. By optimizing the key components and ratios of the catalytic system, the reaction rate and target product selectivity of the carbonylation reaction were significantly improved. The lower reaction temperature and pressure reduced the requirements for reaction equipment and processing costs, effectively suppressed the occurrence of side reactions, thereby achieving deep utilization of raw materials and improving the overall atom economy and greenness of the process. Detailed Implementation

[0032] A method for one-step synthesis of succinic anhydride by acrylic acid carbonylation, comprising the following steps: using acrylic acid and carbon monoxide as raw materials, the carbonylation reaction is carried out in a solvent under the action of a catalyst system consisting of a Pd precursor, a phosphine ligand, and an auxiliary agent to synthesize succinic anhydride in one step. (1) Weigh a certain amount of acrylic acid and solvent and add them to the reaction vessel, and add the corresponding amount of polymerization inhibitor. Keep the temperature at 40°C and stir until completely dissolved. (2) Weigh a certain amount of Pd precursor and add it to the reactor. Under N2 gas protection, keep the temperature at 40°C and stir until completely dissolved, and continue stirring for 20 minutes. (3) Weigh a certain amount of phosphine ligand and add it to the reaction vessel. Continue stirring for 40 min at a constant temperature of 40°C under N2 gas protection. (4) Weigh a certain amount of additives and add them to the reactor. Under N2 gas protection, continue stirring at a constant temperature of 40°C for 20 minutes. (5) The reactor was replaced with high-purity N2 until the O2 content in the reactor was <0.01%; (6) CO is introduced into the reactor to a certain pressure, stirred and heated to the reaction temperature to start the reaction. During the reaction, CO is continuously added to the reactor so that the pressure of CO in the reactor remains constant. (7) The reaction ends and the succinic anhydride product is obtained.

[0033] Furthermore, the solvent mentioned in step (1) is one or more of toluene, o-xylene, p-xylene, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, and 1,4-dioxane.

[0034] Furthermore, the polymerization inhibitor mentioned in step (1) is one or more of hydroquinone, p-benzoquinone, p-hydroxyanisole, and tetramethylpiperidine oxide.

[0035] Furthermore, the Pd precursor mentioned in step (2) is one or more of palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate, palladium chloride, palladium bromide, and palladium acetylacetone.

[0036] Furthermore, the phosphine ligand mentioned in step (3) is one or more of the following compounds:

[0037] Furthermore, the auxiliary agent mentioned in step (4) is one or more of methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, aluminum trifluoromethanesulfonate, iron trifluoromethanesulfonate, benzenesulfonic acid, and p-methylbenzenesulfonic acid.

[0038] Furthermore, in step (1), the molar ratio of acrylic acid to solvent is 1:1-8, and the total volume of acrylic acid and solvent is 10%-60% of the effective volume in the reactor.

[0039] Furthermore, the molar ratio of Pd precursor, phosphine ligand and auxiliaries to acrylic acid is 0.00001-0.0005:0.00002-0.001:0.00005-0.005:1.

[0040] Furthermore, in step (6), the CO pressure at the reaction temperature is 0.5-5.0 MPa, and CO is added to the reactor during the reaction to maintain a constant pressure; Furthermore, the reaction temperature in step (6) is 60-160℃.

[0041] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to specific embodiments and examples. It should be understood that the specific examples described herein are merely illustrative and not intended to limit the invention. Furthermore, it should be understood that after reading this invention, those skilled in the art can make various modifications and alterations to it, but these equivalent forms also fall within the scope defined by the appended claims.

[0042] Unless otherwise specified, "%" in the following examples refers to mol percentage content.

[0043] Example 1: 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppb was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0044] The test results showed that the acrylic acid conversion rate was 84.2% and the succinic anhydride yield was 78.3%.

[0045] Example 2 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppp was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0046] The test results showed that the acrylic acid conversion rate was 82.6% and the succinic anhydride yield was 75.9%.

[0047] Example 3 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of Xantphos was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0048] The test results showed that the acrylic acid conversion rate was 79.4% and the succinic anhydride yield was 76.7%.

[0049] Example 4 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium chloride was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of Xantphos was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0050] The test results showed that the acrylic acid conversion rate was 76.9% and the succinic anhydride yield was 72.5%.

[0051] Example 5 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of Xantphos was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of p-toluenesulfonic acid was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0052] The test results showed that the acrylic acid conversion rate was 84.7% and the succinic anhydride yield was 79.7%.

[0053] Example 6 0.5 mol of acrylic acid, 2 mol of N-methylpyrrolidone, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of Xantphos was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of p-toluenesulfonic acid was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0054] The test results showed that the acrylic acid conversion rate was 87.5% and the succinic anhydride yield was 82.6%.

[0055] Example 7 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of DTBPX was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0056] The test results showed that the acrylic acid conversion rate was 81.7% and the succinic anhydride yield was 77.9%.

[0057] Example 8 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppb was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of methanesulfonic acid was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa. The reactor was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0058] The test results showed that the acrylic acid conversion rate was 82.1% and the succinic anhydride yield was 76.4%.

[0059] Example 9: 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppb was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 100 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0060] The test results showed that the acrylic acid conversion rate was 92.6% and the succinic anhydride yield was 76.9%.

[0061] Example 10: 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of palladium acetate was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppb was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 3.2 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0062] The test results showed that the acrylic acid conversion rate was 85.4% and the succinic anhydride yield was 80.6%.

[0063] Comparative Example 1 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of chloroplatinic acid was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppb was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0064] The test results showed that the acrylic acid conversion rate was 15.3% and the succinic anhydride yield was 0%.

[0065] Comparative Example 2 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of rhodium iodide was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppb was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0066] The test results showed that the acrylic acid conversion rate was 7.6% and the succinic anhydride yield was 1.4%.

[0067] Comparative Example 3 0.5 mol of acrylic acid, 2 mol of o-xylene, and 0.003 mol of hydroquinone were added to a 1000 mL high-pressure reactor. The mixture was stirred at 40 °C for 20 min until completely dissolved. 0.15 mmol of cobalt octacarbonyl was added, and the mixture was stirred under N2 protection until completely dissolved. 0.3 mmol of dppb was added, and the mixture was stirred at 40 °C for 40 min under N2 protection. 1.0 mmol of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at 40 °C for 20 min under N2 protection until completely dissolved. The reactor was purged three times with high-purity N2. CO was introduced into the reactor to a pressure of 2.5 MPa, and the mixture was stirred at 600 rpm and heated to 90 °C to initiate the reaction. During the reaction, syngas was continuously supplied to the reactor to maintain a constant pressure. The reaction was stopped after 6 h, and the reaction solution was analyzed by liquid chromatography.

[0068] The test results showed that the acrylic acid conversion rate was 11.9% and the succinic anhydride yield was 8.4%.

[0069] Comparing the above data, it can be seen that the above embodiments all use the one-step method of acrylic acid carbonylation to prepare succinic anhydride, which is simple in preparation process; and by comparing the product yields of Example 1 and Comparative Examples 1-3, it can be seen that under the same reaction conditions, the product yield is significantly improved under the catalyst system of the present invention.

[0070] In summary, the method for preparing succinic anhydride by acrylic acid carbonylation of the present invention can achieve one-step production of succinic anhydride. The process is simple, the reaction conditions are mild, the catalyst activity is high, the catalyst life is long, and the product yield is high, giving it a strong technological competitive advantage.

[0071] The embodiments described above merely illustrate specific implementation methods of this application, and while the descriptions are detailed, they should not be construed as limiting the scope of protection of this application. It should be noted that those skilled in the art can make various modifications and improvements without departing from the concept of the technical solution of this application, and these modifications and improvements all fall within the scope of protection of this application.

[0072] This background section is provided to generally present the context of the invention. The work of the currently named inventors, the work to the extent described in this background section, and aspects of this section that did not constitute prior art at the time of application are neither expressly nor impliedly acknowledged as prior art to the invention.

Claims

1. A method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid, characterized in that: This method uses acrylic acid and carbon monoxide as raw materials, and carries out a carbonylation reaction in a solvent under the action of a catalyst system consisting of a Pd precursor, a phosphine ligand, and an auxiliary agent to synthesize succinic anhydride in one step; specifically, it includes the following steps: (1) Weigh out the acrylic acid and solvent and add them to the reaction vessel, and add the corresponding amount of polymerization inhibitor. Stir at a constant temperature until completely dissolved. (2) Add the weighed Pd precursor to the reaction vessel after step (1) and stir at a constant temperature under N2 gas protection until completely dissolved. Continue stirring for a period of time after complete dissolution. (3) Add the weighed phosphine ligand to the reaction vessel after step (2) and stir at a constant temperature under N2 gas protection; (4) Add the weighed additives to the reaction vessel after step (3) and stir at a constant temperature under N2 gas protection; (5) Replace the reactor treated in step (4) with high-purity N2 until the volume fraction of O2 in the reactor is <0.01%; (6) CO is charged into the reactor after step (5) to a certain pressure, stirred and heated to the reaction temperature to start the reaction. During the reaction, CO is continuously added to the reactor so that the pressure of CO in the reactor remains constant. (7) The reaction ends and the product succinic anhydride is obtained.

2. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that: The solvent mentioned in step (1) is any one or a mixture of several of toluene, o-xylene, p-xylene, tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, and 1,4-dioxane; the temperature for constant temperature stirring is 40±5℃.

3. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that: The polymerization inhibitor mentioned in step (1) is any one or a mixture of several of hydroquinone, p-benzoquinone, p-hydroxyanisole, and tetramethylpiperidine oxide.

4. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that: The Pd precursor mentioned in step (2) is any one or a mixture of several of palladium nitrate, palladium sulfate, palladium acetate, palladium trifluoroacetate, palladium chloride, palladium bromide, and palladium acetylacetone; the constant temperature stirring temperature is 40±5℃; and the stirring time continues for 20±5 min after complete dissolution.

5. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that, The phosphine ligand mentioned in step (3) is one or more of the following compounds: The temperature for constant temperature stirring is 40±5℃; the stirring time is 40±5min.

6. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that, The additives mentioned in step (4) are one or more of methanesulfonic acid, ethanesulfonic acid, trifluoromethanesulfonic acid, aluminum trifluoromethanesulfonate, iron trifluoromethanesulfonate, benzenesulfonic acid, and p-methylbenzenesulfonic acid; the constant temperature stirring temperature is 40±5℃; the stirring time is 20±5min.

7. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that: In step (1), the molar ratio of acrylic acid to solvent is 1:1-8; the total volume of acrylic acid and solvent is 10%-60% of the effective volume in the reactor.

8. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that: The molar ratio of Pd precursor, phosphine ligand and auxiliaries to acrylic acid is 0.00001-0.0005:0.00002-0.001:0.00005-0.005:

1.

9. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that: In step (6), the CO pressure at the reaction temperature is 0.5-5.0 MPa, and CO is added to the reactor during the reaction to maintain a constant pressure.

10. The method for one-step synthesis of succinic anhydride by carbonylation of acrylic acid as described in claim 1, characterized in that: The reaction temperature in step (6) is 60-160℃.

Images