CN112979449A - Preparation method of succinic acid - Google Patents
Preparation method of succinic acid Download PDFInfo
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Abstract
The application discloses a preparation method of succinic acid, which takes malic acid as a raw material, and the malic acid is reacted in one step in a hydrogen atmosphere in the presence or absence of a nonpolar medium and under the action of a metal-solid acid bifunctional catalyst to obtain the succinic acid. In the preparation method, the raw materials can be derived from biomass resources, so that the dependence on petroleum resources is reduced. Succinic acid can be obtained in high yield by controlling the process conditions. The preparation method has simple process and mild conditions.
Description
Technical Field
The application belongs to the field of chemistry and chemical engineering, relates to a preparation method of succinic acid, and particularly relates to a method for preparing succinic acid by taking malic acid as a raw material.
Background
Succinic acid (Succinic acid) is an organic dicarboxylic acid containing four carbon atoms, and has very wide application in the fields of chemical industry, food industry, pharmaceutical industry and the like. The C4 platform compound is commonly used for synthesizing general chemicals such as gamma-butyrolactone, 1, 4-butanediol, tetrahydrofuran, 2-pyrrolidone and the like, and can also be dehydrated to generate succinic anhydride so as to prepare a series of five-membered heterocyclic compounds such as N-bromosuccinimide and the like. The succinic acid as a monomer can also be used for synthesizing biodegradable polymer materials such as polybutylene succinate (PBS) and the like. In industry, succinic acid is mainly prepared by hydrogenation of petroleum-based maleic anhydride (maleic acid or fumaric acid) as a raw material, a catalyst used is nickel or noble metal, and the reaction temperature is about 130-140 ℃. Further, a method for producing succinic acid by microbial fermentation using glucose or the like as a raw material has been developed. The current global annual output of succinic acid is only 3-5 ten thousand tons, and the market demand of the monomer for preparing the degradable polymer is very large and can be developed to a million-ton level. However, the existing succinic acid production routes cannot meet the increasing market demand thereof, and thus, there is a high necessity to develop novel succinic acid production routes.
Malic acid (Malic acid), an important natural organic acid, is widely distributed in plant, animal and microbial cells. Among them, L-malic acid is regarded as the "most ideal food acid" in the biological and nutritional communities because of its ability to be utilized by living organisms and safety. Malic acid is generally obtained in large quantities by microbial fermentation of biomass-based carbohydrates (glucose, sucrose, starch, etc.). CN 103159624A discloses a technical route for converting malic acid into malonic diester in one step by coupling esterification and oxidation reactions, wherein malic acid is used as a raw material, oxygen or air is used as an oxygen source, alcohol is used as a solvent, and a vanadium oxide compound is used as a catalyst. Although this route is green and efficient, one carbon atom is lost. By comparing the molecular structures of succinic acid and malic acid, it can be found that the two differ by only one hydroxyl group. The existing functional groups in the biomass derivatives are fully utilized, and the further preparation of important chemicals is an important way for utilizing biomass resources, is favorable for getting rid of the dependence on stone resources such as petroleum and the like, and meets the requirements of sustainable development of human society. So far, no research report on the synthesis of succinic acid by using malic acid as a raw material is found in the literature. The malic acid can form butenedioic acid containing carbon-carbon double bonds through dehydration reaction under the action of a solid acid catalyst, and the hydrogenation of the carbon-carbon double bonds under the catalysis of metal is very easy to realize. The metal-solid acid bifunctional catalyst is constructed, so that the succinic acid can be prepared by one step through dehydration and hydrogenation reaction of malic acid through continuous coupling.
Disclosure of Invention
The invention discloses a new route for preparing succinic acid with high yield by a step-by-step dehydration and hydrogenation coupling reaction of malic acid in a solvent-free system or a nonpolar aliphatic hydrocarbon solvent or an aromatic hydrocarbon solvent under the action of a metal-solid acid bifunctional catalyst, which is shown as follows. The solid acid can catalyze malic acid to carry out dehydration reaction to form butenedioic acid, the active metal component promotes carbon-carbon double bond hydrogenation to obtain succinic acid, and the hydrogenation process of the butenedioic acid can promote the dehydration reaction, so that the two processes are coupled. The route has rich raw material sources, is renewable and environment-friendly, and fully utilizes the carboxyl functional group of the malic acid. Therefore, the direct preparation of succinic acid by using biomass-based malic acid as a raw material is a novel synthetic method in a non-petrochemical process.
The invention provides a preparation method of succinic acid, which takes malic acid as raw material, and the malic acid is reacted in one step in hydrogen atmosphere in the presence or absence of a nonpolar medium and under the action of a metal-solid acid bifunctional catalyst to obtain the succinic acid.
In a preferred embodiment, the metal-solid acid bifunctional catalyst catalyzes a one-step reaction coupling dehydration and hydrogenation of malic acid.
In a preferred embodiment, the metal-solid acid bifunctional catalyst comprises an acidic support and a metal element supported on the acidic support;
the metal elements comprise at least one of non-noble metal elements and noble metal elements;
the non-noble metal element comprises at least one of nickel, copper, iron, cobalt, molybdenum and manganese;
the noble metal element comprises at least one of ruthenium, rhodium, palladium, platinum, iridium and gold;
the acidic carrier is molecular sieve or acidic metal oxide.
In a preferred embodiment, the molecular sieve comprises at least one of protonated Y-type molecular sieve, beta-molecular sieve, mordenite, ZSM-5, ZSM-23, SAPO-34, SBA-15, and MCM-41; the acidic metal oxide comprises gamma-Al2O3、ZnO、CeO2、ZrO2、La2O3、ZnO-Al2O3Solid solution, ZnO-ZrO2Solid solution, CeO2-ZrO2At least one of solid solutions.
In a preferred embodiment, the metal-solid acid bifunctional catalyst comprises Ni/HY, Ni/H beta, Ni/ZSM-5, Ni/SAPO-34, Ni/SBA-15, Ni/MCM-41, Ni/gamma-Al2O3、Ni/ZnO、Ni/CeO2、Ni/ZrO2、Ni/La2O3、Ni/ZnO-Al2O3、Ni/ZnO-ZrO2、Ni/CeO2-ZrO2、Ru/γ-Al2O3、Ru/ZrO2At least one of Ru/HY, Pd/HY and Pt/HY.
In a preferred embodiment, the non-polar medium comprises aliphatic hydrocarbons and aromatic hydrocarbons, the aliphatic hydrocarbons comprising C5～C9N-alkanes, C5～C9At least one of branched isomers of n-alkanes; said C is5～C9The n-alkane comprises any one of n-pentane, n-hexane, n-heptane, n-octane and n-nonane; the aromatic hydrocarbon includes at least one of toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene.
In a preferred embodiment, the feed amount of the malic acid is 0.5-50% of the mass of the reaction medium in percentage by mass; preferably, the feed amount of the malic acid is 1-40% of the mass of the reaction medium; more preferably, the feed amount of the malic acid is 5-30% of the mass of the reaction medium. Wherein the reaction medium is a non-polar medium.
In a preferred embodiment, in the metal-solid acid bifunctional catalyst, the ratio of the usage amount of the metal element to the molar amount of the initial charge of the malic acid is 0.01-20%; preferably, the molar ratio of the usage amount of the metal elements to the initial charging amount of the malic acid is 0.1-10%; more preferably, the ratio of the usage amount of the metal element to the molar amount of the malic acid initial feeding is 0.5-5%.
In a preferred embodiment, the reaction temperature is 20-300 ℃; preferably, the reaction temperature is 50-220 ℃; more preferably, the reaction temperature is 80 to 200 ℃.
In a preferred embodiment, the reaction time is 0.1 to 24 hours; preferably, the reaction time is 0.5-10 hours; more preferably, the reaction time is 1 to 6 hours.
In a preferred embodiment, the hydrogen replacement is carried out after adding a suitable amount of reaction medium, the initial hydrogen pressure being 1 to 100 bar; preferably, the initial hydrogen pressure is 1.5 to 50 bar; more preferably, the initial hydrogen pressure is 2 to 20 bar.
The beneficial effects that this application can produce include:
1) the invention adopts a synthetic route for preparing succinic acid by using biomass-based malic acid as a raw material, and compared with the original synthetic route, the raw material used by the invention can be derived from biomass resources, and the dependence on petroleum resources can be reduced.
2) The preparation method of the invention is a one-step method, i.e. malic acid is dehydrated and hydrogenated, and succinic acid can be obtained with high yield by controlling the process conditions.
3) The preparation method has simple process and mild conditions.
Detailed Description
The present application will be described in detail with reference to examples, but the present application is not limited to these examples.
In the application, the preparation of the Ni-solid acid bifunctional catalyst is represented by Ni/HY, and an ion exchange method is adopted. Weighing a certain mass of nickel nitrate hexahydrate, completely dissolving the nickel nitrate hexahydrate in deionized water, adding an HY carrier, violently stirring at 50 ℃ for 12 hours, separating, drying and roasting. Use ofPreviously activated with hydrogen. Preparation of Ru-solid acid bifunctional catalyst from Ru/gamma-Al2O3For representing and introducing a specific preparation method, the difference with the preparation process of Ni/HY is that an equal volume impregnation method is adopted. Weighing a certain mass of ruthenium trichloride hydrate, completely dissolving the ruthenium trichloride hydrate into deionized water, and adding gamma-Al2O3The carrier is stirred vigorously, the volume of the deionized water is ensured to be the same as that of the carrier, and the carrier is immersed for 24 hours and dried for standby. Hydrogen activation prior to use.
The preparation of Pd-Pt-solid acid double-function catalyst is characterized by that it uses Pd/HY as representative material to introduce concrete preparation method, and is different from Ni/HY preparation process in that excess impregnation method is adopted. Weighing a certain mass of palladium chloride, completely dissolving the palladium chloride in excessive deionized water, adding an HY carrier, violently stirring for 24 hours, separating, drying and roasting. Activation with hydrogen was performed prior to use.
EXAMPLE 1 dehydration and hydrogenation of malic acid in different reaction media
This example investigated the performance of dehydration and hydrogenation reactions of malic acid in different reaction media. Since the nonpolar reaction medium is advantageous for the dehydration reaction, the medium of the present invention is concentrated on nonpolar aliphatic hydrocarbons or aromatic hydrocarbons, etc., and specific reaction media are shown in table 1.
And (3) carrying out qualitative analysis on the product by adopting a nuclear magnetic resonance technology. The conversion rate of malic acid and the selectivity of the product are quantitatively determined by adopting a high performance liquid chromatography. High performance liquid chromatography: waters e2695, UV-detector (2489, Waters); a chromatographic column: SunAire C18 column,5 μm,4.6 mm. times.150 mm; chromatographic analysis conditions: ultraviolet detection wavelength, 210nm, mobile phase: 0.1 wt% H3PO4Water soluble/CH3OH-80/20 (ultrasonic degassing), mobile phase flow rate: 0.5ml/min, sample size: 5 μ L, column temperature: 35 ℃ is carried out.
In an autoclave with a polytetrafluoroethylene lining, 2.68g of malic acid, together with a suitable amount of Ni/HY catalyst (5% active metal Ni in relation to the molar amount of the initial charge of malic acid), under solvent-free conditions or with a suitable amount of reaction medium (so that the mass ratio of malic acid to reaction medium is 20% by weight), are introduced, the hydrogen is replaced 5 times with an initial hydrogen pressure of 10bar,the temperature is raised to 140 ℃ by adopting an electric heating mode, and the reaction is carried out for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and centrifugally filtering the reaction liquid to remove a reaction medium; washing the mixture of the catalyst and the reaction sample with cyclohexane for several times; dissolving the reaction sample completely with anhydrous methanol, filtering to obtain catalyst, evaporating the filtrate to remove solvent, vacuum drying at 50 deg.C overnight to obtain total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and treated with deuterated dimethyl sulfoxide (DMSO-d)6) Dissolving, and carrying out qualitative analysis on reaction products by using nuclear magnetism; 0.20g of reaction sample m was accurately weighedsampleIn a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The mass of the reactants and products detected by chromatographic analysis is recorded as mdetectedMass m of the remaining reactant and each product after the reactioni＝mdetected×(mtotal/msample). The conversion rate of malic acid and the selectivity of the product were calculated based on the following formulas:
the results of the malic acid reaction in different solvents are shown in table 1.
TABLE 1 dehydration and hydrogenation of malic acid in the absence of solvent in different reaction media
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 2 Effect of the feed ratio of malic acid to reaction Medium on dehydration and hydrogenation reactions
This example investigated the effect of the feed ratio of malic acid to reaction medium on the dehydration and hydrogenation reactions. The product was qualitatively and quantitatively analyzed by the analytical method of example 1.
Adding 13.4g of n-octane medium into an autoclave with a polytetrafluoroethylene lining, adding 0.67-4.02g of malic acid and a proper amount of Ni/HY catalyst (the molar ratio of the active metal Ni to the initial charge of the malic acid is 5%), replacing 5 times with hydrogen, increasing the initial hydrogen pressure to 10bar, heating to 140 ℃ by adopting an electric heating mode, and reacting for 2 hours under magnetic stirring at 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and centrifugally filtering the reaction liquid to remove a reaction medium; washing the mixture of the catalyst and the reaction sample with cyclohexane for several times; dissolving the reaction sample completely with anhydrous methanol, filtering to obtain catalyst, evaporating the filtrate to remove solvent, vacuum drying at 50 deg.C overnight to obtain total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and treated with deuterated dimethyl sulfoxide (DMSO-d)6) Dissolving, and carrying out qualitative analysis on reaction products by using nuclear magnetism; accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The reaction results of different charge ratios of malic acid and solvent are shown in Table 2.
TABLE 2 reaction results at different charge ratios of malic acid to solvent
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 3 evaluation of the Performance of the Metal solid acid bifunctional catalyst for dehydration and hydrogenation of malic acid
The performance of different solid acid supported metal catalyzed malic acid dehydration and hydrogenation reactions was studied. The analytical method of example 1 was used to determine the nature and quantity of the reaction products.
Autoclave with polytetrafluoroethylene liningIn the reaction, 2.68g of malic acid and 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 20 wt%) are added, a metal-solid acid bifunctional catalyst (the molar ratio of the active metal to the initial charge of the malic acid: 5% of metallic nickel catalyst; 2% of Ru, Pd and Pt) is added, hydrogen displacement is performed for 5 times, the initial hydrogen pressure is 10bar, the temperature is raised to 140 ℃ by adopting an electric heating mode, and the reaction is performed for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and centrifugally filtering the reaction liquid to remove a reaction medium; washing the mixture of the catalyst and the reaction sample with cyclohexane for several times; dissolving the reaction sample completely with anhydrous methanol, filtering to obtain catalyst, evaporating the filtrate to remove solvent, vacuum drying at 50 deg.C overnight to obtain total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and treated with deuterated dimethyl sulfoxide (DMSO-d)6) Dissolving, and carrying out qualitative analysis on reaction products by using nuclear magnetism; accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The evaluation results of the metal solid acid dual-function catalyst are shown in Table 3.
TABLE 3 results of different solid acid supported metal catalyzed malic acid dehydration and hydrogenation reactions
aOthers include the formation of polymerization products and unknown by-products, among others.
EXAMPLE 4 Effect of catalyst dosage on malic acid dehydration and hydrogenation reactions
This example studies the effect of different Ru/HY dosages on the dehydration and hydrogenation reaction results of malic acid. The analytical method of example 1 was used to determine the nature and quantity of the reaction products.
2.68g of malic acid and 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 20 wt%) are added into an autoclave with a polytetrafluoroethylene lining, a certain amount of Ru/HY catalyst is added (the amount of Ru/HY and the molar amount of the initial charge of the malic acid are shown in Table 4), hydrogen replacement is carried out for 5 times, the initial hydrogen pressure is 10bar, the temperature is raised to 140 ℃ by adopting an electric heating mode, and the reaction is carried out for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and centrifugally filtering the reaction liquid to remove a reaction medium; washing the mixture of the catalyst and the reaction sample with cyclohexane for several times; dissolving the reaction sample completely with anhydrous methanol, filtering to obtain catalyst, evaporating the filtrate to remove solvent, vacuum drying at 50 deg.C overnight to obtain total mass m of the sampletotalWeighing a certain amount of 0.10g of sample in a nuclear magnetic tube, and using deuterated dimethyl sulfoxide (DMSO-d)6) Dissolving, and carrying out qualitative analysis on reaction products by using nuclear magnetism; accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results for different amounts of Ru/HY are shown in Table 4.
TABLE 4 dehydration and hydrogenation of malic acid at different Ru/HY loadings
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 5 Effect of reaction temperature on dehydration and hydrogenation of malic acid
This example studies the effect of reaction temperature on the results of dehydration and hydrogenation reactions of malic acid. The analytical method of example 1 was used to determine the nature and quantity of the reaction products.
Adding 2.68g of malic acid and 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 20 wt%) into an autoclave with a polytetrafluoroethylene lining, and adding a Ru/HY catalyst (the amount of active metal Ru is equal to that of the apple)The molar weight ratio of the initial feeding of the fruit acid is 4%), replacing with hydrogen for 5 times, increasing the initial hydrogen pressure to 10bar, heating to the specified temperature by adopting an electric heating mode, and reacting for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and centrifugally filtering the reaction liquid to remove a reaction medium; washing the mixture of the catalyst and the reaction sample with cyclohexane for several times; dissolving the reaction sample completely with anhydrous methanol, filtering to obtain catalyst, evaporating the filtrate to remove solvent, vacuum drying at 50 deg.C overnight to obtain total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and treated with deuterated dimethyl sulfoxide (DMSO-d)6) Dissolving, and carrying out qualitative analysis on reaction products by using nuclear magnetism; accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results at different reaction temperatures are shown in Table 5.
TABLE 5 results of dehydration and hydrogenation of malic acid at different reaction temperatures
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 6 Effect of Hydrogen initial pressure on malic acid dehydration and hydrogenation reactions
This example studies the effect of hydrogen initial pressure on the results of dehydration and hydrogenation reactions of malic acid. The analytical method of example 1 was used to determine the nature and quantity of the reaction products.
Adding 2.68g of malic acid and 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 20 wt%) into an autoclave with a polytetrafluoroethylene lining, and adding Ru/HY catalyst (the amount of active metal Ru and the initial amount of the malic acid)The molar ratio of the initial feeding is 4%), replacing 5 times with hydrogen, charging hydrogen with certain pressure, heating to 180 ℃ by adopting an electric heating mode, and reacting for 2 hours under the magnetic stirring of 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and centrifugally filtering the reaction liquid to remove a reaction medium; washing the mixture of the catalyst and the reaction sample with cyclohexane for several times; dissolving the reaction sample completely with anhydrous methanol, filtering to obtain catalyst, evaporating the filtrate to remove solvent, vacuum drying at 50 deg.C overnight to obtain total mass m of the sampletotal0.10g of sample is weighed into a nuclear magnetic tube and treated with deuterated dimethyl sulfoxide (DMSO-d)6) Dissolving, and carrying out qualitative analysis on reaction products by using nuclear magnetism; accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results for the different initial hydrogen pressures are shown in table 5.
TABLE 6 results of malic acid dehydration and hydrogenation reactions at different initial hydrogen pressures
aOthers include the formation of polymerization products and unknown by-products, among others.
Example 7 Effect of reaction time on dehydration and hydrogenation of malic acid
This example investigated the effect of reaction time on dehydration and hydrogenation of malic acid. The product was qualitatively and quantitatively analyzed by the analytical method in example 1.
Adding 2.68g of malic acid and 13.4g of n-octane medium (the mass ratio of the malic acid to the reaction medium is 20 wt%) into an autoclave with a polytetrafluoroethylene lining, adding a Ru/HY catalyst (the molar ratio of the active metal Ru to the initial charge of the malic acid is 4%), replacing for 5 times with hydrogen, wherein the initial hydrogen pressure is 10bar, heating to 180 ℃ by adopting an electric heating mode, and reacting for a certain time under magnetic stirring at 1000 rpm. Stopping stirring, naturally cooling the reaction kettle to room temperature, and reactingCentrifuging the reaction solution and filtering to remove the reaction medium; washing the mixture of the catalyst and the reaction sample with cyclohexane for several times; dissolving the reaction sample completely with anhydrous methanol, filtering to obtain catalyst, evaporating the filtrate to remove solvent, vacuum drying at 50 deg.C overnight to obtain total mass m of the sampletotalWeighing 0.10g of sample in a nuclear magnetic tube, dissolving the sample by using deuterated chloroform, and qualitatively analyzing a reaction product by using nuclear magnetism; accurately measure 0.20g of the reaction sample (denoted as m)sample) In a 25mL volumetric flask, the reaction sample was dissolved with the mobile phase, diluted, and subjected to volume fixing for quantitative analysis by HPLC. The conversion rate of malic acid and the selectivity of the product were calculated using the formula of example 1. The results of the different reaction times are shown in Table 7.
TABLE 7 results of dehydration and hydrogenation of malic acid at different reaction times
aOthers include the formation of polymerization products and unknown by-products, among others.
From the above examples, it can be seen that the preparation method of succinic acid provided by the present invention uses malic acid as a raw material, uses nonpolar aromatic hydrocarbons and aliphatic hydrocarbons as solvents, and under the action of a metal-solid acid bifunctional catalyst, the malic acid is subjected to dehydration and hydrogenation coupling reaction to prepare succinic acid with high selectivity. When the conversion rate of malic acid is more than 99%, the selectivity of succinic acid is more than 96%.
Although the present application has been described with reference to a few embodiments, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the application as defined by the appended claims.
Claims (10)
1. The preparation method of succinic acid is characterized in that malic acid is used as a raw material, and the malic acid is reacted in one step in a hydrogen atmosphere in the presence or absence of a nonpolar medium and under the action of a metal-solid acid bifunctional catalyst to obtain succinic acid.
2. The preparation method of claim 1, wherein the metal-solid acid bifunctional catalyst catalyzes malic acid to perform a one-step reaction coupling dehydration and hydrogenation.
3. The production method according to claim 2, wherein the metal-solid acid bifunctional catalyst comprises an acidic support and a metal element supported on the acidic support;
the metal elements comprise at least one of non-noble metal elements and noble metal elements;
the non-noble metal element comprises at least one of nickel, copper, iron, cobalt, molybdenum and manganese;
the noble metal element comprises at least one of ruthenium, rhodium, palladium, platinum, iridium and gold;
the acidic carrier is molecular sieve or acidic metal oxide.
4. The production method according to claim 3,
the molecular sieve comprises at least one of protonated Y-type molecular sieve, beta-molecular sieve, mordenite, ZSM-5, ZSM-23, SAPO-34, SBA-15 and MCM-41;
the acidic metal oxide comprises gamma-Al2O3、ZnO、CeO2、ZrO2、La2O3、ZnO-Al2O3Solid solution, ZnO-ZrO2Solid solution, CeO2-ZrO2At least one of solid solutions.
5. The method of any one of claims 1 to 4, wherein the metal-solid acid bifunctional catalyst comprises Ni/HY, Ni/Hbeta, Ni/ZSM-5, Ni/SAPO-34, Ni/SBA-15, Ni/MCM-41, Ni/gamma-Al2O3、Ni/ZnO、Ni/CeO2、Ni/ZrO2、Ni/La2O3、Ni/ZnO-Al2O3、Ni/ZnO-ZrO2、Ni/CeO2-ZrO2、Ru/γ-Al2O3、Ru/ZrO2At least one of Ru/HY, Pd/HY and Pt/HY.
6. The method of claim 1, wherein the non-polar medium comprises aliphatic hydrocarbons and aromatic hydrocarbons,
the aliphatic hydrocarbon comprises C5～C9N-alkanes, C5～C9At least one of branched isomers of n-alkanes;
said C is5～C9The n-alkane comprises any one of n-pentane, n-hexane, n-heptane, n-octane and n-nonane;
the aromatic hydrocarbon includes at least one of toluene, ethylbenzene, ortho-xylene, meta-xylene, and para-xylene.
7. The preparation method according to claim 1, wherein the malic acid dosage is 0.5-50% of the mass of the reaction medium in percentage by mass;
preferably, the feed amount of the malic acid is 1-40% of the mass of the reaction medium;
more preferably, the feed amount of the malic acid is 5-30% of the mass of the reaction medium;
wherein the reaction medium is a non-polar medium.
8. The preparation method according to claim 1, wherein in the metal-solid acid bifunctional catalyst, the molar ratio of the usage amount of the metal element to the initial charge of the malic acid is 0.01-20%;
preferably, the molar ratio of the usage amount of the metal elements to the initial charging amount of the malic acid is 0.1-10%;
more preferably, the ratio of the usage amount of the metal element to the molar amount of the malic acid initial feeding is 0.5-5%.
9. The method according to claim 1, wherein the reaction temperature is 20 to 300 ℃;
preferably, the reaction temperature is 50-220 ℃;
more preferably, the reaction temperature is 80 to 200 ℃.
10. The method according to claim 1, wherein the reaction time is 0.1 to 24 hours;
preferably, the reaction time is 0.5-10 hours;
more preferably, the reaction time is 1 to 6 hours.
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