CN108947829B - Method for preparing succinic acid diester - Google Patents
Method for preparing succinic acid diester Download PDFInfo
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- CN108947829B CN108947829B CN201710351341.7A CN201710351341A CN108947829B CN 108947829 B CN108947829 B CN 108947829B CN 201710351341 A CN201710351341 A CN 201710351341A CN 108947829 B CN108947829 B CN 108947829B
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/39—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester
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Abstract
A method for preparing succinic acid diester uses molecular oxygen as an oxygen source, glucose, fructose, cellobiose and microcrystalline cellulose as raw materials, and obtains the succinic acid diester through a catalytic selective oxidation process. The raw materials used in the invention can be obtained from biomass resources such as starch, cellulose, agricultural and forestry wastes and the like, the catalyst composition is simple, the reaction condition is mild, the target product succinic acid diester has high selectivity, and the method has an important application prospect.
Description
Technical Field
The invention relates to a method for preparing succinic acid diester, which specifically comprises the following steps: a simple non-noble metal molybdenum-based compound is used as a catalyst to catalyze molecular oxygen to oxidize glucose, fructose, fiber two-pond and microcrystalline cellulose to obtain succinic acid diester.
Background
The succinic acid diester is widely applied to the industries of spices, coatings, foods, rubber, medicines, plastics and the like, and is an important fine chemical intermediate; it can also be used for the production of fine chemicals such as tetrahydrofuran, 1, 4-butanediol, N-methylpyrrolidone, gamma-butyrolactone, etc.; in addition, the polybutylene succinate (PBS) material with good biodegradability can also be polymerized by taking dimethyl succinate or diethyl succinate and 1, 4-butanediol as monomers; high application value and wide development prospect.
At present, the production of the succinic acid diester mainly comprises chemical synthesis, a biological conversion method and the like. The chemical synthesis method is mainly used for preparing the succinic acid diester by catalyzing the hydrogenation of maleic anhydride: the substrate maleic anhydride in the process needs to be obtained by gas-phase catalytic oxidation of benzene or butane and other raw materials, and the key C4 hydrocarbon or benzene is from non-renewable fossil resources. The biotransformation method can isothermally convert the saccharides into succinic acid, and the succinic acid diester is obtained by esterification. However, the biotransformation process is faced with problems such as the microorganisms are greatly influenced by pH value, are easy to survive, and the product separation cost is high. Therefore, the development of a new method for preparing the succinic acid diester has important research significance and application background.
Glucose, fructose and the like are widely available, cheap and easily available (can be obtained by hydrolyzing starch, cellulose, sucrose and the like), and are important biomass-based compounds. So far, there are few reports on the production of succinic acid or succinic acid diester from glucose, fructose or cellobiose, microcrystalline cellulose, and the like. Coman and Garcia et al report Ru @ MNP catalyzed glucose wet oxidation to prepare succinic acid (180 ℃, 1.0MPa O)2) The yield of the succinic acid in the product can reach 87.5 percent; however, the reaction system adopts a noble metal catalyst, and n-butylamine is required to be added as a basic additive. A method for preparing succinic acid or succinic acid diester by using levulinic acid or levulinic acid ester as a raw material is reported before a group of our subjects (Chinese patents: 201210237579.4, 201310148566.4, 201410729795.X, 201410729760.6 and 201610389269.2; PCT patent: PCT/CN 2012/087089). The invention provides a method for preparing succinic acid diester by using glucose, fructose, cellobiose or microcrystalline cellulose as raw materials and performing molecular oxygen oxidation. The adopted catalytic system is simple and green; the reaction condition is mild, the selectivity of the succinic acid diester in the product is high, and the application prospect is good.
Disclosure of Invention
The invention aims to provide a method for preparing succinic acid diester by using simple non-noble metal molybdenum-based compound as a catalyst and oxidizing glucose, fructose, cellobiose and microcrystalline cellulose by molecular oxygen. The catalytic system is simple, the reaction condition is mild, and the selectivity of the target product, namely the succinic acid diester, can reach more than 80%.
The raw materials adopted by the invention comprise glucose, fructose, cellobiose and microcrystalline cellulose, and the raw materials can be obtained from renewable biomass such as starch, cellulose and the like, and are cheap and easy to obtain.
The non-noble metal molybdenum-based compound adopted by the invention comprises molybdenum disulfide, ammonium molybdate, molybdenum trioxide, acetylacetonato molybdenum oxide and molybdenum pentachloride; the amount of the catalyst is 0.5-20 mol%, preferably 2-10 mol% of the raw material.
The invention provides a method for preparing succinic acid diester by catalyzing glucose, fructose, cellobiose and microcrystalline cellulose in a micromolecular alcohol solvent to be oxidized by using molecular oxygen as an oxygen source, which comprises the following steps: the dosage of the catalyst is 0.5-20 mol%, preferably 2-10 mol% of the raw material feeding amount; the reaction temperature is 20-200 ℃, preferably 80-150 ℃; the oxygen partial pressure in the oxidation reaction is 0.1-2.0MPa, preferably 0.2-1.0 MPa; the reaction time is 2-20h, preferably 2-12 h; the conversion rate of the raw materials is 50-90%, and the selectivity of the succinic acid diester can reach more than 80%;
compared with the prior art, the method for preparing the succinic acid diester by the non-noble metal molybdenum-based compound through the catalytic oxidation process has the advantages that the raw material source is wide, the price is low, and the raw material is easy to obtain; the catalytic system is simple and green; the oxidation reaction condition is mild; the product succinic acid diester has high selectivity and obvious technical advantages.
Detailed Description
The invention is further illustrated by the following specific examples.
Example 1:
glucose (0.45g), molybdenum acetylacetonate (10 mol% relative to glucose), and 2.5mL of methanol were sequentially added to a 35mL reaction vessel containing magnetons. Oxygen is replaced by 3 times, then the mixture is oxygenated to 1.0MPa, and the mixture is heated and stirred for 6 hours at 120 ℃. After the reaction is finished, the reaction product is quickly cooled to room temperature, and all liquid phase products are transferred for qualitative and quantitative analysis. The conversion of the starting material and the selectivity of the product were calculated using gas chromatography analysis using the internal standard method. The specific calculation formulas of the conversion rate of glucose and the selectivity of dimethyl succinate are as follows:
conversion [ mol% ]]＝(A0-A)/A0×100％
Selectivity [ mol%]＝B/(A0-A)×100％
In the formula, A0The amount of glucose added [ mol ] before the reaction]And A is the amount of glucose after the reaction [ mol ]]And B is the amount of a substance which generates dimethyl succinate during the reaction [ mol]。
The calculated conversion of glucose was 89% and the selectivity to dimethyl succinate was 87%.
Example 2:
microcrystalline cellulose (0.45g), ammonium molybdate (5 mol% relative to glucose having the same mass as the raw material microcrystalline cellulose), and 2.5mL of methanol were sequentially added to a 35mL reaction vessel containing magnetons. Oxygen is replaced by 3 times, then the oxygen is oxygenated to 0.6MPa, and the mixture is heated and stirred for 10 hours at 80 ℃. After the reaction is finished, the reaction product is quickly cooled to room temperature, and all liquid phase products are transferred for qualitative and quantitative analysis. The calculated conversion of microcrystalline cellulose was 59% and selectivity to dimethyl succinate was 89%.
Example 3:
glucose (0.45g), molybdenum acetylacetonate (5 mol% relative to glucose), and 2.5mL of ethanol were sequentially added to a 35mL reaction vessel containing magnetons. After 3 times of oxygen replacement, the mixture is oxygenated to 1.0MPa and heated and stirred for 12 hours at 100 ℃. After the reaction is finished, the reaction product is quickly cooled to room temperature, and all liquid phase products are transferred for qualitative and quantitative analysis. The calculated conversion of glucose was 83% and the selectivity of diethyl succinate was 85%.
Example 4:
cellobiose (0.45g), molybdenum trioxide (15 mol% based on cellobiose), and 2.5mL of n-propanol were sequentially added to a 35mL reaction vessel containing magnetons. Oxygen is replaced by 3 times, then the mixture is oxygenated to 0.5MPa, and the mixture is heated and stirred for 6 hours at 150 ℃. After the reaction is finished, the reaction product is quickly cooled to room temperature, and all liquid phase products are transferred for qualitative and quantitative analysis. The calculated conversion of cellobiose was 51% and the selectivity of dipropyl succinate was 87%.
Example 5:
glucose (0.45g), molybdenum trioxide (15 mol% based on cellobiose), and 2.5mL of ethanol were sequentially added to a 35mL reaction vessel containing magnetons. Oxygen is replaced by 3 times, then the oxygen is oxygenated to 0.8MPa, and the mixture is heated and stirred for 12 hours at 120 ℃. After the reaction is finished, the reaction product is quickly cooled to room temperature, and all liquid phase products are transferred for qualitative and quantitative analysis. The calculated conversion of glucose was 69% and the selectivity of diethyl succinate was 80%.
Example 6:
cellobiose (0.45g), ammonium molybdate (15 mol% relative to cellobiose), and 2.5mL of methanol were sequentially added to a 35mL reaction vessel containing magnetons. After 3 times of oxygen replacement, the mixture is oxygenated to 1.0MPa and heated and stirred for 6 hours at 140 ℃. After the reaction is finished, the reaction product is quickly cooled to room temperature, and all liquid phase products are transferred for qualitative and quantitative analysis. The calculated conversion of cellobiose was 61% and the selectivity of dimethyl succinate was 82%.
Claims (7)
1. A method for preparing succinic acid diester is characterized in that: the method takes molecular oxygen as an oxygen source, takes one or more than two of glucose, fructose, cellobiose and microcrystalline cellulose as raw materials, takes a molybdenum compound as a catalyst, and obtains succinic acid diester through a catalytic oxidation process in an alcohol solvent; the molybdenum compound is one or more than two of ammonium molybdate, molybdenum trioxide, acetylacetonato molybdenum and molybdenum pentachloride.
2. The method of claim 1, wherein: the dosage of the catalyst is 0.5-20 mol% of the raw material.
3. A method according to claim 1 or 2, characterized in that: the dosage of the catalyst is 2-10 mol% of the raw material.
4. The method of claim 1, wherein: in the oxidation reaction, molecular oxygen is oxygen or oxygen-containing gas, and the partial pressure of oxygen in the reaction system is 0.1-2.0 MPa; the reaction temperature is 20-200oC; the reaction time is 2-20 h.
5. The method of claim 1 or 4, wherein: in the oxidation reaction, molecular oxygen is oxygen or oxygen-containing gas, and the partial pressure of oxygen in the reaction system is 0.2-1.0 MPa; the reaction temperature is 80-150 DEG CoC; the reaction time is 2-12 h.
6. The method of claim 1, wherein: the alcohol solvent used in the reaction system is one or more than two of methanol, ethanol and n-propanol micromolecule alcohol.
7. The method of claim 1, wherein: in the oxidation reaction, the conversion rate of the raw materials is 50-90%, and the selectivity of the succinic acid diester is more than 80%.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539665A (en) * | 2012-07-10 | 2014-01-29 | 中国科学院大连化学物理研究所 | Succinic acid diester preparation method |
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103539665A (en) * | 2012-07-10 | 2014-01-29 | 中国科学院大连化学物理研究所 | Succinic acid diester preparation method |
| CN105646223A (en) * | 2014-12-04 | 2016-06-08 | 中国科学院大连化学物理研究所 | Method used for preparing succinic acid diester via catalytic oxidation esterification of levulinic acid |
Non-Patent Citations (2)
| Title |
|---|
| Unprecedented Catalytic Wet Oxidation of Glucose to Succinic Acid Induced by the Addition of n-Butylamine to a RuIII Catalyst;Iunia Podolean 等;《ChemSusChem》;20160811(第9期);2307-2311 * |
| 催化氧化制备生物基有机二元酸研究进展;刘俊霞 等;《中国科学 化学》;20150520;第45卷(第5期);526-532 * |
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