Method and device for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate

Abstract

The invention relates to the technical field of preparation of succinic acid, in particular to a method and a device for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate, the method comprises the following steps: feeding dimethyl maleate and hydrogen into a hydrogenation reactor to carry out catalytic hydrogenation reaction to obtain a reaction product rich in dimethyl succinate; and feeding the reaction product rich in dimethyl succinate and water into a hydrolysis reactor for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components. The method is simple in technological process, high in raw material conversion rate and high in product selectivity, important monomeric compounds including butanediol, butyrolactone and tetrahydrofuran are co-produced, the preparation method of succinic acid is expanded, and the problems that an existing succinic acid preparation method is single, tedious in technological process and limited are solved.

Description

Technical Field

[0001] The invention relates to the technical field of succinic acid preparation, and is a method and device for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran. Background Art

[0002] Succinic acid, also known as succinic acid, is a widely used basic organic chemical and fine chemical raw material. It is an important intermediate for the synthesis of a variety of important organic chemical products and is widely used in the fields of medicine, dyes, construction, synthetic resins and pesticides. As a raw material monomer for the synthesis of biodegradable plastics (PBS / PBAT), the demand for succinic acid has also grown rapidly.

[0003] At present, the main production method of succinic acid is the liquid phase hydrogenation of maleic anhydride, and the hydrogenation process is divided into two processes: direct hydrogenation and solvent hydrogenation. The reaction selectivity of preparing succinic anhydride by hydrogenation of maleic anhydride decreases significantly with the increase of reaction temperature within a certain range, and the reaction process is a highly exothermic reaction, so the reaction temperature control of maleic anhydride hydrogenation is crucial to the process selectivity. The direct hydrogenation process requires injecting a large amount of cold hydrogen between the reactor stages to control the reaction temperature within a reasonable range through cold hydrogen, while the solvent hydrogenation process controls the reaction temperature by solvent dilution and injection of cold hydrogen between the stages. It can be seen that both hydrogenation processes require the use of cold hydrogen to reduce the reaction temperature, and a large amount of hydrogen causes the reactor to have a larger volume within the same residence time, and the investment in equipment and catalysts is also relatively high.

[0004] The Chinese patent document with publication number CN102389751A discloses a fixed bed reactor and method for preparing succinic anhydride by hydrogenating maleic anhydride solution. The method comprises the following steps: maleic anhydride solution and hydrogen enter the reactor, pass through the first stage catalytic bed, and generate succinic anhydride. The maleic anhydride solution has a space velocity of 0.5 h -1 Up to 1.5h -1 After the reaction, the reactants enter the first cooler for cooling. The supplemented primary hydrogen is mixed with the reaction products of the first stage catalyst bed and enters the second stage catalyst bed. The space velocity of the maleic anhydride solution in the second stage catalyst bed is 0.5h -1 Up to 1.5h -1 ; Then the reaction product flow of the second stage catalytic bed enters the second cooler for cooling, and the supplemented secondary hydrogen is mixed with the reaction product flow of the second stage catalytic bed and enters the third stage catalytic bed; the maleic anhydride solution space velocity of the three-stage catalytic bed is 0.2h -1 to 0.5h -1 The reaction product flows out of the reactor from the outlet. This patent provides a method for obtaining succinic anhydride from maleic anhydride solution, and the process flow is complicated, single and has limitations. Summary of the invention

[0005] The present invention provides a method and device for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate, which overcomes the deficiencies of the above-mentioned prior art and can effectively solve the problems of the existing succinic acid preparation method being single, the process flow being cumbersome and having limitations.

[0006] One of the technical solutions of the present invention is achieved by the following measures: A method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out according to the following method: S1, sending the preheated dimethyl maleate and hydrogen to a hydrogenation reactor filled with a hydrogenation catalyst for catalytic hydrogenation reaction to obtain a reaction product; S2, sending the reaction product after cooling and water into a hydrolysis reactor filled with a hydrolysis catalyst for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components.

[0007] The following is a further optimization and / or improvement of one of the above-mentioned technical solutions: In the above step S1, the hydrogenation catalyst is one or more of MCM-41 molecular sieve, ZSM-5 molecular sieve, ZSM-11 molecular sieve, Al2O3 catalyst loaded with metal active component copper and Al2O3 catalyst loaded with metal active component zinc.

[0008] The mass percentage of copper loaded in the above-mentioned Al2O3 catalyst loaded with metal active component copper is 0.1wt% to 10wt%, and the copper comes from one of copper nitrate, copper chloride and copper sulfate. The Al2O3 catalyst loaded with metal active component copper is prepared by an impregnation method, specifically, the Al2O3 carrier is mixed with a copper-containing solution, impregnated at 10°C to 100°C for 24h, and then dried (dried at 25°C to 200°C for 2h to 24h) and calcined (calcined at 500°C to 600°C for 3h to 8h) to obtain.

[0009] The mass percentage of zinc loaded in the above-mentioned Al2O3 catalyst loaded with metal active component zinc is 0.1wt% to 10wt%, and the zinc comes from one of zinc nitrate, zinc chloride and zinc sulfate. The Al2O3 catalyst loaded with metal active component zinc is prepared by an impregnation method, specifically, the Al2O3 carrier is mixed with a zinc-containing solution, impregnated at 10°C to 100°C for 24h, and then dried (dried at 25°C to 200°C for 2h to 24h) and calcined (calcined at 500°C to 600°C for 3h to 8h) to obtain.

[0010] In the above step S1, the preheating temperature is 30°C to 100°C.

[0011] In the above step S1, the hydrogenation reaction temperature is 150°C to 300°C, and the mass space velocity of dimethyl maleate is 0.1h -1Up to 2.5h -1 , the reaction pressure is 0.5MPa to 5.0MPa, and the hydrogen flow rate is 30ml / min to 300ml / min.

[0012] In the above step S1, the hydrogenation reactor is one of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor, and in step S2, the hydrolysis reactor is a fixed bed reactor.

[0013] In the above step S2, the molar ratio of the reaction product to water is (1 to 10):1, and the temperature is lowered to 20°C to 50°C.

[0014] In the above step S2, the hydrolysis catalyst is one or more of an ion exchange resin, an ionic liquid, and a HZSM-5 molecular sieve catalyst.

[0015] In the above step S2, the hydrolysis reaction temperature is 50°C to 200°C, and the mass space velocity of the reaction product is 0.3h -1 Up to 3.0h -1 , reaction pressure 0MPa to 2.0MPa.

[0016] The second technical solution of the present invention is achieved by the following measures: a device for implementing the method of preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran, comprising a heat exchanger, a preheater, a hydrogenation reactor and a hydrolysis reactor, wherein the first inlet of the heat exchanger is fixedly connected with a feed pipeline, the first outlet of the heat exchanger and the inlet of the preheater are fixedly connected with a first treatment pipeline, the first treatment pipeline is fixedly connected with a hydrogen pipeline, the outlet of the preheater and the inlet of the hydrogenation reactor are fixedly connected with a second treatment pipeline, the outlet of the hydrogenation reactor and the second inlet of the heat exchanger are fixedly connected with a third treatment pipeline, the second outlet of the heat exchanger and the inlet of the hydrolysis reactor are fixedly connected with a fourth treatment pipeline, the outlet of the hydrolysis reactor is fixedly connected with a fifth treatment pipeline, and the fourth treatment pipeline is fixedly connected with a water inlet pipeline and a nitrogen pipeline, respectively.

[0017] The following is a further optimization and / or improvement of the second technical solution of the above invention: The feed pipeline and the water inlet pipeline are respectively fixedly installed with a delivery pump.

[0018] The invention provides a method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran. The method has a simple process flow, high raw material conversion rate, high product selectivity, and co-produces important monomer compounds butanediol, butyrolactone and tetrahydrofuran, thereby expanding the preparation method of succinic acid and overcoming the problems of the existing succinic acid preparation method being single, complicated process flow and having limitations. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1This is a schematic diagram of the process flow of Example 21 of the present invention.

[0020] The codes in the accompanying drawings are: 1 is a heat exchanger, 2 is a preheater, 3 is a hydrogenation reactor, 4 is a hydrolysis reactor, 5 is a feed pipeline, 6 is a first treatment pipeline, 7 is a hydrogen pipeline, 8 is a second treatment pipeline, 9 is a third treatment pipeline, 10 is a fourth treatment pipeline, 11 is a fifth treatment pipeline, 12 is a water inlet pipeline, 13 is a nitrogen pipeline, and 14 is a delivery pump. DETAILED DESCRIPTION

[0021] The present invention is not limited by the following embodiments, and the specific implementation method can be determined according to the technical scheme of the present invention and the actual situation. Unless otherwise specified, the various chemical reagents and chemicals mentioned in the present invention are all chemical reagents and chemicals known and used in the prior art; unless otherwise specified, the percentages in the present invention are all mass percentages; unless otherwise specified, the solutions in the present invention are all aqueous solutions with water as the solvent, for example, hydrochloric acid solution is a hydrochloric acid aqueous solution; the normal temperature and room temperature in the present invention generally refer to a temperature of 15°C to 25°C, and are generally defined as 25°C.

[0022] The present invention will be further described below in conjunction with embodiments: Example 1: The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate is carried out as follows: S1, sending the preheated dimethyl maleate and hydrogen to a hydrogenation reactor filled with a hydrogenation catalyst for catalytic hydrogenation reaction to obtain a reaction product; S2, sending the reaction product after cooling and water into a hydrolysis reactor filled with a hydrolysis catalyst for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components.

[0023] Embodiment 2: As an optimization of the above embodiment, in step S1, the hydrogenation catalyst is one or more of MCM-41 molecular sieve, ZSM-5 molecular sieve, ZSM-11 molecular sieve, Al2O3 catalyst loaded with metal active component copper, and Al2O3 catalyst loaded with metal active component zinc. Among them, the molar ratio of SiO2 to Al2O3 in MCM-41 molecular sieve is (60 to 600):1; the molar ratio of SiO2 to Al2O3 in ZSM-5 molecular sieve is (30 to 1000):1, and can further be (60 to 400):1; the molar ratio of SiO2 to Al2O3 in ZSM-11 molecular sieve is (30 to 300):1, and can further be (120 to 300):1.

[0024] Example 3: As an optimization of the above example, the mass percentage of copper loaded in the Al2O3 catalyst loaded with the metal active component copper is 0.1wt% to 10wt%, and the copper comes from one of copper nitrate, copper chloride and copper sulfate. The Al2O3 catalyst loaded with the metal active component copper is prepared by an impregnation method, specifically, the Al2O3 carrier is mixed with a copper-containing solution, impregnated at 10°C to 100°C for 24h, and then dried (dried at 25°C to 200°C for 2h to 24h) and calcined (calcined at 500°C to 600°C for 3h to 8h) to obtain.

[0025] Example 4: As an optimization of the above example, the mass percentage of zinc loaded in the Al2O3 catalyst loaded with the metal active component zinc is 0.1wt% to 10wt%, the zinc comes from one of zinc nitrate, zinc chloride and zinc sulfate, and the Al2O3 catalyst loaded with the metal active component zinc is prepared by an impregnation method, specifically, the Al2O3 carrier is mixed with a zinc-containing solution, impregnated at 10°C to 100°C for 24h, and then dried (dried at 25°C to 200°C for 2h to 24h) and calcined (calcined at 500°C to 600°C for 3h to 8h) to obtain.

[0026] Embodiment 5: As an optimization of the above embodiment, in step S1, the preheating temperature is 30°C to 100°C.

[0027] Example 6: As an optimization of the above example, in step S1, the hydrogenation reaction temperature is 150°C to 300°C, and the mass space velocity of dimethyl maleate is 0.1h -1 Up to 2.5h -1 , the reaction pressure is 0.5MPa to 5.0MPa, and the hydrogen flow rate is 30ml / min to 300ml / min.

[0028] Example 7: As an optimization of the above example, in step S1, the hydrogenation reactor is one of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor, and in step S2, the hydrolysis reactor is a fixed bed reactor.

[0029] Example 8: As an optimization of the above example, in step S2, the molar ratio of the reaction product to water is (1 to 10):1, and the temperature is cooled to 20°C to 50°C.

[0030] Example 9: As an optimization of the above example, in step S2, the hydrolysis catalyst is one or more of an ion exchange resin (SK-1A, exchange capacity 4.5 mmol / g, purchased from Japan), an ionic liquid, and a HZSM-5 molecular sieve catalyst. The molar ratio of SiO2 to Al2O3 in the HZSM-5 molecular sieve catalyst is (15 to 150):1, and can further be (30 to 120):1.

[0031] Example 10: As an optimization of the above example, in step S2, the hydrolysis reaction temperature is 50°C to 200°C, and the mass space velocity of the reaction product is 0.3h -1 Up to 3.0h -1 , reaction pressure 0MPa to 2.0MPa.

[0032] Embodiment 11: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 50°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 300:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 220°C, and the mass space velocity of dimethyl maleate is 0.8h -1 , reaction pressure is 0.5MPa, hydrogen flow rate is 50ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ion exchange resin) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 2:1, the hydrolysis reaction temperature is 50°C, and the mass space velocity of the reaction product is 0.5h -1 , reaction pressure 0.5MPa (N2).

[0033] In Example 11 of the present invention, the conversion rate of dimethyl maleate was 85.5%, the selectivity of succinic acid was 89.3%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 93.2%.

[0034] Embodiment 12: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 50°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 300:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 200°C, and the mass space velocity of dimethyl maleate is 0.5h -1 , reaction pressure is 1.0MPa, hydrogen flow rate is 50ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 120:1) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 2:1, the hydrolysis reaction temperature is 50°C, and the mass space velocity of the reaction product is 0.5h -1 , reaction pressure 0.5MPa (N2).

[0035] In Example 12 of the present invention, the conversion rate of dimethyl maleate was 80.1%, the selectivity of succinic acid was 88.9%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 90.6%.

[0036] Embodiment 13: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 60°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (MCM-41 molecular sieve, SiO2 and Al2O3 with a molar ratio of 150:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 180°C, and the mass space velocity of dimethyl maleate is 0.3h -1 , reaction pressure is 2.0MPa, hydrogen flow rate is 100ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ion exchange resin) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 3:1, the hydrolysis reaction temperature is 60°C, and the mass space velocity of the reaction product is 0.4h -1 , reaction pressure 0.5MPa (N2).

[0037] In Example 13 of the present invention, the conversion rate of dimethyl maleate was 98.3%, the selectivity of succinic acid was 96.8%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 99.8%.

[0038] Embodiment 14: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 60°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (MCM-41 molecular sieve, SiO2 and Al2O3 with a molar ratio of 300:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 170°C, and the mass space velocity of dimethyl maleate is 1.0h -1 , the reaction pressure is 1.5MPa, and the hydrogen flow rate is 80ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ionic liquid) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 1:1, the hydrolysis reaction temperature is 60°C, and the mass space velocity of the reaction product is 0.5h -1 , reaction pressure 1.5MPa (N2).

[0039] In Example 14 of the present invention, the conversion rate of dimethyl maleate was 79.7%, the selectivity of succinic acid was 91.9%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 95.4%.

[0040] Embodiment 15: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 40°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 800:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 160°C, and the mass space velocity of dimethyl maleate is 2.0h -1 , reaction pressure is 2.0MPa, hydrogen flow rate is 250ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ion exchange resin) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 3:1, the hydrolysis reaction temperature is 80°C, and the mass space velocity of the reaction product is 1.0h -1 , reaction pressure 0.5MPa (N2).

[0041] In Example 15 of the present invention, the conversion rate of dimethyl maleate was 85.8%, the selectivity of succinic acid was 92.9%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 94.3%.

[0042] Embodiment 16: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 60°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 1000:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 200°C, and the mass space velocity of dimethyl maleate is 0.3h -1 , reaction pressure is 1.5MPa, hydrogen flow rate is 100ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ion exchange resin) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 4:1, the hydrolysis reaction temperature is 60°C, and the mass space velocity of the reaction product is 0.5h -1 , reaction pressure 1.0MPa (N2).

[0043] In Example 16 of the present invention, the conversion rate of dimethyl maleate was 98.4%, the selectivity of succinic acid was 99.3%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 99.7%.

[0044] Embodiment 17: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 70°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 1000:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 280°C, and the mass space velocity of dimethyl maleate is 2.0h -1 , reaction pressure is 3.0MPa, hydrogen flow rate is 50ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ionic liquid) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 2:1, the hydrolysis reaction temperature is 150°C, and the mass space velocity of the reaction product is 0.5h -1 , reaction pressure 0.5MPa (N2).

[0045] In Example 17 of the present invention, the conversion rate of dimethyl maleate was 88.6%, the selectivity of succinic acid was 85.8%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 89.4%.

[0046] Embodiment 18: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 80°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (Al2O3 catalyst loaded with 1wt% Cu) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 300°C, and the mass space velocity of dimethyl maleate is 0.6h -1 , reaction pressure is 1.0MPa, hydrogen flow rate is 250ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 100:1) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 8:1, the hydrolysis reaction temperature is 80°C, and the mass space velocity of the reaction product is 0.3h -1 , reaction pressure 0.5MPa (N2).

[0047] In Example 18 of the present invention, the conversion rate of dimethyl maleate was 75.1%, the selectivity of succinic acid was 80.4%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 82.7%.

[0048] Embodiment 19: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 50°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (Al2O3 catalyst loaded with 2wt% Cu) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 150°C, and the mass space velocity of dimethyl maleate is 0.2h -1 , reaction pressure is 1.5MPa, hydrogen flow rate is 300ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 90:1) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 5:1, the hydrolysis reaction temperature is 70°C, and the mass space velocity of the reaction product is 0.2h -1 , reaction pressure 0.5MPa (N2).

[0049] In Example 19 of the present invention, the conversion rate of dimethyl maleate was 89.5%, the selectivity of succinic acid was 89.2%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 93.4%.

[0050] Embodiment 20: The method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran is carried out as follows: S1, dimethyl maleate preheated to 40°C and hydrogen are sent to a hydrogenation reactor (fixed bed reactor) filled with a hydrogenation catalyst (MCM-41 molecular sieve, SiO2 and Al2O3 with a molar ratio of 200:1) for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); wherein the hydrogenation reaction temperature is 120°C, and the mass space velocity of dimethyl maleate is 0.1h -1 , reaction pressure is 2.0MPa, hydrogen flow rate is 150ml / min; S2, the reaction product after cooling and water are sent to a hydrolysis reactor (fixed bed reactor) filled with a hydrolysis catalyst (ZSM-5 molecular sieve, SiO2 and Al2O3 with a molar ratio of 60:1) for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components, wherein the molar ratio of the reaction product to water is 3:1, the hydrolysis reaction temperature is 80°C, and the mass space velocity of the reaction product is 0.2h -1 , reaction pressure 1.5MPa (N2).

[0051] In Example 20 of the present invention, the conversion rate of dimethyl maleate was 95.3%, the selectivity of succinic acid was 91.8%, and the total selectivity of succinic acid, butanediol, butyrolactone and tetrahydrofuran was 94.1%.

[0052] The invention provides a method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate. The method prepares succinic acid from dimethyl maleate, co-produces important monomer compounds butanediol, butyrolactone and tetrahydrofuran, and expands the method for preparing succinic acid. The method has mild reaction conditions, a simple process flow, high raw material conversion rate and product succinic acid selectivity, a dimethyl maleate conversion rate of 75% to 98%, a product succinic acid selectivity of 80% to 99%, and a total selectivity of the products succinic acid, butanediol, butyrolactone and tetrahydrofuran of 82% to 100%. The method overcomes the problems of the existing succinic acid preparation method being single, the process flow being cumbersome and having limitations.

[0053] Example 21: As shown in the attached Figure 1 As shown, an apparatus for implementing the method of preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate comprises a heat exchanger 1, a preheater 2, a hydrogenation reactor 3 and a hydrolysis reactor 4, wherein a feed pipeline 5 is fixedly connected to the first inlet of the heat exchanger 1, a first treatment pipeline 6 is fixedly connected between the first outlet of the heat exchanger 1 and the inlet of the preheater 2, a hydrogen pipeline 7 is fixedly connected to the first treatment pipeline 6, a second treatment pipeline 8 is fixedly connected between the outlet of the preheater 2 and the inlet of the hydrogenation reactor 3, a third treatment pipeline 9 is fixedly connected between the outlet of the hydrogenation reactor 3 and the second inlet of the heat exchanger 1, a fourth treatment pipeline 10 is fixedly connected between the second outlet of the heat exchanger 1 and the inlet of the hydrolysis reactor 4, a fifth treatment pipeline 11 is fixedly connected to the outlet of the hydrolysis reactor 4, and a water inlet pipeline 12 and a nitrogen pipeline 13 are fixedly connected to the fourth treatment pipeline 10, respectively.

[0054] Embodiment 22: As an optimization of the above embodiment, a delivery pump 14 is fixedly installed on the feed pipeline 5 and the water inlet pipeline 12 respectively.

[0055] The device for implementing the method for efficiently converting light hydrocarbons to increase added value of the present invention, during use, first, the raw material dimethyl maleate is sent to the heat exchanger 1 by a delivery pump for heat exchange, the dimethyl maleate and hydrogen after heat exchange are sent to the preheater 2 for preheating, and the preheated dimethyl maleate and hydrogen are sent to the hydrogenation reactor 3 for catalytic hydrogenation reaction to obtain a reaction product (rich in dimethyl succinate); then, the reaction product is sent to the heat exchanger 1 for heat exchange (the raw material dimethyl maleate and the reaction product are heat exchanged, and the raw material dimethyl maleate is heated by the heat of the reaction product), the reaction product after cooling and water are sent to the hydrolysis reactor 4 for hydrolysis reaction, and at the same time, nitrogen is introduced through the nitrogen pipeline 13 to ensure the reaction pressure of the hydrolysis reactor 4, and the obtained product mixture of succinic acid, butanediol, butyrolactone and tetrahydrofuran is sent to the subsequent device through the fifth processing pipeline for separation.

[0056] In summary, the present invention provides a method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran. The method has a simple process flow, high raw material conversion rate, high product selectivity, and co-produces important monomer compounds butanediol, butyrolactone and tetrahydrofuran, thereby expanding the preparation method of succinic acid and overcoming the problems of the existing succinic acid preparation method being single, complicated process flow and having limitations.

[0057] The above technical features constitute the embodiments of the present invention, which have strong adaptability and implementation effect. Non-essential technical features can be added or reduced according to actual needs to meet the requirements of different situations.

Claims

1. A method for preparing succinic acid from dimethyl maleate and co-producing butanediol, butyrolactone and tetrahydrofuran, characterized in that Proceed as follows: S1, sending the preheated dimethyl maleate and hydrogen to a hydrogenation reactor filled with a hydrogenation catalyst for catalytic hydrogenation reaction to obtain a reaction product; S2, sending the reaction product after cooling and water into a hydrolysis reactor filled with a hydrolysis catalyst for hydrolysis reaction to obtain a mixture containing succinic acid, butanediol, butyrolactone and tetrahydrofuran components.

2. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to claim 1, characterized in that In step S1, the hydrogenation catalyst is one or more of MCM-41 molecular sieve, ZSM-5 molecular sieve, ZSM-11 molecular sieve, Al2O3 catalyst loaded with metal active component copper, and Al2O3 catalyst loaded with metal active component zinc.

3. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to claim 2, characterized in that The mass percentage of copper loaded in the Al2O3 catalyst loaded with the metal active component copper is 0.1wt% to 10wt%, the copper comes from one of copper nitrate, copper chloride and copper sulfate, and the Al2O3 catalyst loaded with the metal active component copper is prepared by an impregnation method, specifically, the Al2O3 carrier is mixed with a copper-containing solution, impregnated at 10°C to 100°C for 24 hours, and then dried and calcined to obtain; or / and, the mass percentage of zinc loaded in the Al2O3 catalyst loaded with the metal active component zinc is 0.1wt% to 10wt%, the zinc comes from one of zinc nitrate, zinc chloride and zinc sulfate, and the Al2O3 catalyst loaded with the metal active component zinc is prepared by an impregnation method, specifically, the Al2O3 carrier is mixed with a zinc-containing solution, impregnated at 10°C to 100°C for 24 hours, and then dried and calcined to obtain.

4. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to any one of claims 1 to 3, characterized in that In step S1, the preheating temperature is 30°C to 100°C.

5. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to any one of claims 1 to 4, characterized in that In step S1, the hydrogenation reaction temperature is 150°C to 300°C, and the mass space velocity of dimethyl maleate is 0.1h -1 Up to 2.5h -1 , the reaction pressure is 0.5MPa to 5.0MPa, and the hydrogen flow rate is 30ml / min to 300ml / min.

6. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to any one of claims 1 to 5, characterized in that In step S1, the hydrogenation reactor is one of a fixed bed reactor, a fluidized bed reactor and a moving bed reactor, and in step S2, the hydrolysis reactor is a fixed bed reactor.

7. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to any one of claims 1 to 6, characterized in that In step S2, the molar ratio of the reaction product to water is 1 to 10:1, and the temperature is lowered to 20°C to 50°C.

8. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to any one of claims 1 to 7, characterized in that In step S2, the hydrolysis catalyst is one or more of an ion exchange resin, an ionic liquid, and a HZSM-5 molecular sieve catalyst.

9. The method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to any one of claims 1 to 8, characterized in that In step S2, the hydrolysis reaction temperature is 50°C to 200°C, and the mass space velocity of the reaction product is 0.3h -1 Up to 3.0h -1 , reaction pressure 0MPa to 2.0MPa.

10. A device for implementing the method for preparing succinic acid and co-producing butanediol, butyrolactone and tetrahydrofuran from dimethyl maleate according to any one of claims 1 to 9, characterized in that The invention comprises a heat exchanger, a preheater, a hydrogenation reactor and a hydrolysis reactor, wherein a first inlet of the heat exchanger is fixedly connected with a feed pipeline, a first outlet of the heat exchanger is fixedly connected with a first treatment pipeline and a preheater inlet, a hydrogen pipeline and a second treatment pipeline and a preheater outlet are fixedly connected with the inlet of the hydrogenation reactor, a third treatment pipeline and a second inlet of the heat exchanger are fixedly connected with the outlet of the hydrogenation reactor, a fourth treatment pipeline and a hydrolysis reactor inlet are fixedly connected with the outlet of the hydrolysis reactor, a fifth treatment pipeline and a water inlet pipeline and a nitrogen pipeline and fixedly connected with the fourth treatment pipeline, respectively.

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