A method for the production of a bio-based succinic acid
By using a supported metal catalyst in aqueous solution to react C4 hydroxydiacid with hydrogen, the problems of high production cost and harsh reaction conditions of bio-based succinic acid have been solved, and low-cost, high-yield succinic acid production has been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- PETROCHINA CO LTD
- Filing Date
- 2022-07-05
- Publication Date
- 2026-05-12
AI Technical Summary
Existing bio-based succinic acid production methods suffer from high production costs and demanding reaction conditions.
C4 hydroxydiacid reacts with hydrogen in aqueous solution using a supported metal catalyst. The reaction conditions are mild, with metal catalysts such as Pd, Pt, Ru, Ni, and Cu used. The support is titanium oxide. The reaction temperature is controlled at 90℃ to 150℃, the hydrogen partial pressure is 0.2 to 4 MPa, and the reaction time is 1 to 20 h.
This technology enables low-cost, environmentally friendly succinic acid production with high product yield, no pollution during the reaction process, and reduced production costs.
Abstract
Description
Technical fields:
[0001] This invention relates to the field of basic organic chemical raw material preparation technology, and in particular to a method for producing bio-based succinic acid. Background technology:
[0002] Succinic acid, also known as succinic acid, is widely used in the food, pharmaceutical, and agricultural industries. It is a key raw material in the production of biodegradable plastics such as polybutylene succinate (PBS) and polybutylene terephthalate (PBST). Furthermore, as an important organic chemical raw material, it can be further converted into important chemicals such as 1,4-butanediol, butyrolactone, tetrahydrofuran, succinimide, N-methylpyrrolidone, and their derivatives.
[0003] Industrially, petroleum-based succinic acid is mainly derived from the hydrogenation of maleic anhydride. Specifically, butane or benzene undergoes catalytic oxidation to produce maleic anhydride, which is then catalytically hydrogenated on a Ni-based catalyst to produce succinic acid. Bio-based succinic acid can also be synthesized through bio-fermentation. Currently, fermentation methods are becoming increasingly mature, using starch, glucose, cellulose, etc., as raw materials, and employing bacteria such as *Escherichia coli*, *Actinomyces succinate*, and *Anaerobic spirochetes* to produce succinic acid. However, this method also has some drawbacks, such as low selectivity, high cost, and difficulty in product separation. C4 hydroxy diacids such as D-tartaric acid, L-tartaric acid, D,L-tartaric acid, meso-tartaric acid, D-malic acid, L-malic acid, and D,L-malic acid can be produced by microbial fermentation. Utilizing these to produce higher value-added succinic acid has not only theoretical significance but also practical application value.
[0004] Currently, only a few patents report the production of succinic acid from C4 hydroxysuccinic acid. CN112574024A reports the conversion of 2,3-dihydroxysuccinic acid or 2-hydroxysuccinic acid to succinic acid using a mixture of a supported noble metal catalyst and at least one supported metal oxide catalyst and / or at least one supported heteropolyacid catalyst, such as a Pt / TiO2+WO3 / ZrO2 catalyst. This catalyst has a complex composition and high overall cost; moreover, the reaction temperature is nearly 200℃, making the reaction conditions quite harsh. Therefore, there is a need to develop catalytic systems with relatively simple catalyst compositions, milder reaction conditions, and lower production costs. Summary of the Invention:
[0005] The technical problem this invention aims to solve is to provide a method for producing bio-based succinic acid that achieves low production costs, mild reaction conditions, environmental friendliness, and high product yield. This overcomes the shortcomings of existing bio-based succinic acid production methods, which suffer from high production costs and demanding reaction conditions.
[0006] The technical solution adopted in this invention is: a method for producing bio-based succinic acid, the method comprising the following steps: in the presence of a supported metal catalyst, C4 hydroxydiacid is reacted with hydrogen in an aqueous solution, the partial pressure of hydrogen in the reaction is 0.2-4 MPa, the reaction temperature is 90℃-150℃, and the reaction time is 1-20 h, to obtain the succinic acid; wherein the metal in the above-mentioned supported metal catalyst includes at least one of Pd, Pt, Ru, Ni, and Cu, and the support for the supported metal catalyst is titanium oxide.
[0007] Furthermore, the C4 hydroxydiacid content in the aqueous solution is 0.05–20% by mass.
[0008] Furthermore, the C4 hydroxydiacid in the aqueous solution has a mass percentage of 2% or 5-15%.
[0009] Furthermore, the mass ratio of the C4 hydroxydiacid to the supported metal catalyst is 1:0.01 to 5.
[0010] Furthermore, the mass ratio of the C4 hydroxydiacid to the supported metal catalyst is 1:0.1, 1:1, or 1:2.
[0011] Furthermore, the reaction temperature is 120°C or 150°C.
[0012] Furthermore, the reaction time is 1 hour, 3 hours, or 5 to 10 hours.
[0013] Furthermore, the partial pressure of hydrogen in the reaction is 1 MPa or 2 MPa.
[0014] Furthermore, the loading of the metal in the supported metal catalyst is 0.2% to 10% by mass.
[0015] Furthermore, the loading of the metal in the supported metal catalyst is 1% by mass.
[0016] Furthermore, the metal in the supported metal catalyst is Pd.
[0017] Furthermore, the titanium oxide is synthesized via a hydrothermal method.
[0018] The beneficial effects of this invention are: this invention uses water as a reaction solvent, which not only makes the reaction process green and pollution-free and environmentally friendly, but also reduces production costs and increases product yield. Detailed implementation method:
[0019] The present invention will be described below through specific embodiments. Unless otherwise specified, the experimental methods used in the following embodiments are conventional methods.
[0020] Unless otherwise specified, all materials and reagents used in the following examples are commercially available.
[0021] In the following examples, the catalyst was prepared as follows:
[0022] 1. Preparation of TiO2-1
[0023] The specific steps are as follows: Add 50 mL of tetrabutyl titanate, 10 mL of deionized water, and a certain volume of hydrofluoric acid to a 100 mL hydrothermal reactor lined with polytetrafluoroethylene. After mixing thoroughly, carry out the hydrothermal reaction in a 453 K oven for 24 h. After the reaction is complete, cool to room temperature in a water bath, filter under reduced pressure, wash three times with ethanol and 0.1 M sodium hydroxide aqueous solution, and finally wash with deionized water until the filtrate is neutral. Then dry in an oven at 393 K for 8 h.
[0024] 2. Preparation of TiO2-
[0025] The specific steps are as follows: Titanium tetrachloride is dissolved in hydrochloric acid and mixed thoroughly. The mixed solution is then added dropwise to ammonia water, forming a white precipitate. The precipitate is filtered under reduced pressure and washed to obtain the titanium hydroxide precursor. Then, 2g of titanium hydroxide is dispersed in a mixed solvent of 15mL deionized water and 15mL isopropanol and ultrasonically mixed thoroughly. A hydrothermal reaction is then carried out in a 453K oven for 24 hours. After the reaction is complete, the mixture is cooled to room temperature in a water bath, filtered under reduced pressure, and washed three times with ethanol and 0.1M sodium hydroxide aqueous solution, respectively. Finally, it is washed with deionized water until the filtrate is neutral, and then dried in an oven at 393K for 8 hours.
[0026] 3. Preparation of TiO2-1 supported Pd catalyst
[0027] The preparation of a 1% Pd / TiO2-1 catalyst is used as an example for non-limiting explanation.
[0028] 560 mg of a 10 wt% Pd(NH3)4(NO3)2 aqueous solution was mixed with 20 mL of deionized water, and 2 g of TiO2-1 support was added. The mixture was stirred at room temperature for 8 h, the solvent was evaporated using a rotary evaporator, and then dried in an oven at 120 °C for 10 h. The mixture was then calcined in air at 300 °C for 3 h, followed by reduction in 20% H2+N2 at 100 °C for 1 h to obtain a 1% Pd / TiO2-1 catalyst. The Pd loading was 1% (mass percentage).
[0029] 4. Preparation of TiO2-1 supported Pt catalyst
[0030] The preparation of a 1% Pt / TiO2-1 catalyst is used as an example for non-limiting explanation.
[0031] 40 mg of Pt(NH3)4(NO3)2 and 20 mL of deionized water were mixed, and 2 g of TiO2-1 support was added. The mixture was stirred at room temperature for 8 h, the solvent was evaporated using a rotary evaporator, and then dried in an oven at 120 °C for 10 h. The mixture was calcined in air at 300 °C for 3 h, and then reduced in 20% H2+N2 at 100 °C for 1 h to obtain a 1% Pd / TiO2-1 catalyst. The Pt loading was 1% (mass percentage).
[0032] 5. Preparation of TiO2-supported Pt catalyst
[0033] The preparation of a 1% Pt / TiO2-2 catalyst is used as an example for non-limiting explanation.
[0034] 40 mg of Pt(NH3)4(NO3)2 and 20 mL of deionized water were mixed, and 2 g of TiO2-2 support was added. The mixture was stirred at room temperature for 8 h, the solvent was evaporated using a rotary evaporator, and then dried in an oven at 120 °C for 10 h. The mixture was calcined in air at 300 °C for 3 h, and then reduced in 20% H2+N2 at 100 °C for 1 h to obtain a 1% Pd / TiO2-2 catalyst. The Pd loading was 1% (mass percentage).
[0035] Example 1: Production of succinic acid from L-tartaric acid in aqueous solution
[0036] In a 50 mL high-pressure reactor, 0.3 g of 1% Pd / TiO2-1 catalyst, 0.3 g of L-tartaric acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 150 °C. The reaction was stirred at 600 rpm for 4 h. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 94%.
[0037] Example 2: Production of succinic acid from meso-tartaric acid in aqueous solution
[0038] In a 50 mL high-pressure reactor, 0.2 g of 1% Pd / TiO2-1 catalyst, 0.3 g of meso-tartaric acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 140 °C. The reaction was stirred at 600 rpm for 10 h. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 93%.
[0039] Example 3: Production of succinic acid from L-malic acid in aqueous solution
[0040] In a 50 mL high-pressure reactor, 0.2 g of 1% Pd / TiO2-1 catalyst, 0.3 g of L-malic acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 150 °C. The reaction was stirred at 600 rpm for 6 h. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 99%.
[0041] Example 4: Production of succinic acid from DL-malic acid in aqueous solution
[0042] In a 50 mL high-pressure reactor, 0.2 g of 1% Pd / TiO2-2 catalyst, 0.3 g of DL-malic acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 150 °C. The reaction was stirred at 600 rpm for 8 hours. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 98%.
[0043] Example 5: Production of succinic acid from DL-malic acid in aqueous solution
[0044] In a 50 mL high-pressure reactor, 0.2 g of 1% Pd / TiO2-2 catalyst, 0.3 g of DL-malic acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 1 MPa hydrogen gas. Then, 1 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 150 °C. The reaction was stirred at 600 rpm for 8 hours. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 98%.
[0045] Example 6: Production of succinic acid from L-tartaric acid in aqueous solution
[0046] In a 50 mL high-pressure reactor, 0.2 g of 1% Pt / TiO2-1 catalyst, 0.3 g of L-tartaric acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 150 °C. The reaction was stirred at 600 rpm for 6 h. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 91%.
[0047] Example 7: Production of succinic acid from L-tartaric acid in aqueous solution
[0048] In a 50 mL high-pressure reactor, 1 g of 1% Pd / TiO2-1 catalyst, 1.5 g of L-tartaric acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 150 °C. The reaction was stirred at 600 rpm for 5.5 h. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 90%.
[0049] Example 8: Production of succinic acid from L-tartaric acid in aqueous solution
[0050] In a 50 mL high-pressure reactor, 0.06 g of 1% Pd / TiO2-1 catalyst, 0.3 g of L-tartaric acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 150 °C. The reaction was stirred at 600 rpm for 16 h. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 91%.
[0051] Example 9: Production of succinic acid from L-tartaric acid in aqueous solution
[0052] In a 50 mL high-pressure reactor, 0.3 g of 1% Pd / TiO2-1 catalyst, 0.3 g of L-tartaric acid, and 15 mL of deionized water were added. After sealing the reactor, it was purged three times with 2 MPa hydrogen gas. Then, 2 MPa hydrogen gas was introduced into the reactor, and it was placed on a furnace and heated to a reaction temperature of 120 °C. The reaction was stirred at 600 rpm for 20 h. After the reaction was completed, the mixture was cooled to room temperature in an ice-water bath, filtered under reduced pressure, and then cooled to crystallize and separate, yielding succinic acid with a yield of 96%.
[0053] It is understood that the above specific description of the present invention is only for illustrating the present invention and is not limited to the technical solutions described in the embodiments of the present invention. Those skilled in the art should understand that modifications or equivalent substitutions can still be made to the present invention to achieve the same technical effect; as long as the use needs are met, they are all within the protection scope of the present invention.
Claims
1. A method for producing bio-based succinic acid, characterized in that: The method comprises the following steps: In the presence of a supported metal catalyst, C4 hydroxydiacid is reacted with hydrogen in an aqueous solution. The partial pressure of hydrogen is 0.2–4 MPa, the reaction temperature is 90–150 °C, and the reaction time is 1–20 h, to obtain the succinic acid. The metal in the supported metal catalyst is at least one of Pd and Pt, the C4 hydroxydiacid is one of L-tartaric acid, meso-tartaric acid, L-malic acid, and DL-malic acid, and the support for the supported metal catalyst is titanium dioxide. The titanium oxide is synthesized via a hydrothermal method, and the specific steps are selected from any one of the following two methods:
1. Add 50 mL of tetrabutyl titanate, 10 mL of deionized water, and a certain volume of hydrofluoric acid to a 100 mL hydrothermal reactor lined with polytetrafluoroethylene. After mixing evenly, carry out the hydrothermal reaction in an oven at 453 K for 24 h. After the reaction is completed, cool to room temperature in a water bath, filter under reduced pressure, wash three times with ethanol and 0.1 M sodium hydroxide aqueous solution, and finally wash with deionized water until the filtrate is neutral. Then dry in an oven at 393 K for 8 h.
2. Titanium tetrachloride was dissolved in hydrochloric acid and mixed thoroughly. The mixture was then added dropwise to ammonia water to form a white precipitate. The precipitate was filtered under reduced pressure and washed to obtain the titanium hydroxide precursor. Then, 2 g of titanium hydroxide was dispersed in a mixed solvent of 15 mL deionized water and 15 mL isopropanol and ultrasonically mixed thoroughly. The mixture was then subjected to a hydrothermal reaction in an oven at 453 K for 24 h. After the reaction was completed, the mixture was cooled to room temperature in a water bath, filtered under reduced pressure, and washed three times with ethanol and 0.1 M sodium hydroxide aqueous solution, respectively. Finally, the mixture was washed with deionized water until the filtrate was neutral and then dried in an oven at 393 K for 8 h.
2. The method for producing bio-based succinic acid according to claim 1, characterized in that: The aqueous solution contains 0.05-20% C4 hydroxydiacid by mass.
3. The method for producing bio-based succinic acid according to claim 2, characterized in that: The aqueous solution contains 2% or 5-15% C4 hydroxydiacid by mass.
4. The method for producing bio-based succinic acid according to claim 1, characterized in that: The mass ratio of the C4 hydroxydiacid to the supported metal catalyst is 1:0.01~5.
5. The method for producing bio-based succinic acid according to claim 4, characterized in that: The mass ratio of the C4 hydroxydiacid to the supported metal catalyst is 1:0.1, 1:1, or 1:
2.
6. The method for producing bio-based succinic acid according to claim 1, characterized in that: The reaction temperature is 120℃ or 150℃.
7. The method for producing bio-based succinic acid according to claim 1, characterized in that: The reaction time is 1 h, 3 h, or 5-10 h.
8. The method for producing bio-based succinic acid according to claim 1, characterized in that, The hydrogen partial pressure in the reaction is 1 MPa or 2 MPa.
9. A method for producing bio-based succinic acid according to claim 1, characterized in that, The metal loading in the supported metal catalyst is 0.2% to 10% by mass.
10. A method for producing bio-based succinic acid according to claim 9, characterized in that, The metal loading in the supported metal catalyst is 1% by mass.
11. A method for producing bio-based succinic acid according to claim 1, characterized in that, The metal in the supported metal catalyst is Pd.