CN104119224A - Method for catalytic oxidation conversion of levulinic acid and levulinic acid ester - Google Patents
Method for catalytic oxidation conversion of levulinic acid and levulinic acid ester Download PDFInfo
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- CN104119224A CN104119224A CN201310148566.4A CN201310148566A CN104119224A CN 104119224 A CN104119224 A CN 104119224A CN 201310148566 A CN201310148566 A CN 201310148566A CN 104119224 A CN104119224 A CN 104119224A
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- 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
- C07C67/42—Preparation of carboxylic acid esters by oxidation of groups which are precursors for the acid moiety of the ester by oxidation of secondary alcohols or ketones
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Abstract
The invention relates to a method for catalytic oxidation conversion of levulinic acid and levulinic acid ester. The method adopts air or oxygen as the oxidant, and a bivalent manganese compound and nitric acid, nitrate or nitrous acid, nitrite are employed as a composite catalyst to catalyze levulinic acid or levulinic acid ester liquid phase selective oxidation and esterification reaction under mild conditions, thus obtaining succinic acid diester. The method has the characteristics of high catalytic oxidation efficiency and mild reaction condition, the bivalent manganese compound and nitric acid, nitrate or nitrous acid, nitrite involved in the composite catalyst are cheap and easily available, and the product is easy to separate and purify, so that the method has very good practicability and broad application prospects.
Description
Technical field
The present invention relates to the method for transformation of a kind of levulinic acid and levulinate, relate in particular to a kind of with manganous compound and nitric acid, nitrate or nitrous acid, nitrite for being complex as catalyzer, catalysis biomass based platform compound levulinic acid or levulinate are converted into the method for succinate, the method be take air or oxygen as oxygenant, manganous compound and nitric acid, nitrate or nitrous acid, nitrite are composite catalyst, by liquid-phase selective oxidation and esterification, levulinic acid or levulinate are converted into product succinate.
Background technology
Succinate is a kind of important fine chemical material and intermediate.By succinate, can produce many fine chemicals, comprise succinic acid, BDO, tetrahydrofuran (THF), gamma-butyrolactone, butyrolactam and N-Methyl pyrrolidone etc.; Therefore, succinate is widely used in the industries such as food, spices, medicine, coating, rubber and plastics at present.By succinate, through hydrolysis, can obtain succinic acid, through hydrogenating reduction, obtain 1,4-butyleneglycol (CN1286142A), succinic acid and 1,4-butyleneglycol can be grouped to degradation material---poly butylene succinate, this material has good biological degradability, has important using value and vast potential for future development.
Traditional preparation method of succinate mainly contains two kinds.(1) carbohydrate such as glucose obtains succinic acid by fermentation, and then succinic acid obtains succinate (US5723322, US5143834, US5143833, US5168055, US5573931) with corresponding alcohol esterification under acid catalysis.Although succinic acid can be by biomass in the method, but the method still faces a lot of difficulties, first the culture medium cost of fermentative Production succinic acid is higher, secondly fermenting process requires strict to pH value, and product more complicated in the succinic acid reaction solution that fermentation method obtains, there is very large difficulty in the separating-purifying of succinic acid.(2) C
4hydro carbons or benzene oxidation obtain maleic anhydride, and then maleic anhydride obtains succinate (EP844231, EP728731, CN102070448A, CN101824627A, CN101343210A) through esterification, hydrogenation.This method critical materials C
4hydro carbons or benzene rely on fossil resource.Our seminar has reported a kind of novel method (Chinese Patent Application No.: 201210237579.4 of preparing succinate; PCT application number: PCT/CN2012/087089), it is raw material that the method be take levulinic acid or levulinate, and molecular oxygen is oxygenant, under manganic compound katalysis, by liquid-phase catalysis selective oxidation and esterification, obtains succinate.The present invention is on the existing working foundation of seminar, further reported that take manganous compound and nitric acid, nitrate or nitrous acid, nitrite is composite catalyst, oxygen or air are oxygenant, under milder condition, by liquid-phase catalysis selective oxidation and esterification, levulinic acid and levulinate are converted into succinate.
Summary of the invention
The object of the present invention is to provide a kind of with manganous compound and nitric acid, nitrate, nitrous acid, or nitrite is composite catalyst, oxygen or air are oxygenant, the method of being prepared succinate by levulinic acid or levulinate, it is raw material that the method be take levulinic acid or levulinate, manganous compound and nitric acid, nitrate, nitrous acid, or nitrite is composite catalyst, oxygen or air are oxygenant, by liquid-phase catalysis selective oxidation, again through esterification, obtain succinate (primary product that the invention provides method distributes as shown in Figure 1).
In the method, used catalyst is one or two or more kinds composite catalyst for composition in manganous compound and nitric acid, nitrate, nitrous acid or nitrite, and wherein manganous compound comprises one or two or more kinds in manganous sulfate, manganous carbonate, manganous acetate (II), Manganous chloride tetrahydrate, manganese sulfide, manganese monoxide, manganous oxalate, manganese acetylacetonate (II); The consumption of manganous compound is the 0.05-5mol% of raw material levulinic acid or levulinate, and better consumption is 0.05-2mol%, and optimum amount is 0.1-1mol%; Another component of composite catalyst is nitric acid, nitrate, nitrous acid or nitrite, wherein nitrate comprises one or two or more kinds in saltpetre, SODIUMNITRATE, magnesium nitrate, aluminum nitrate, zinc nitrate, iron nitrate, cupric nitrate, and nitrite is one or two or more kinds in potassium nitrite, Sodium Nitrite; One or two or more kinds consumption in nitric acid, nitrate, nitrous acid or nitrite is the 0.05-5mol% of raw material levulinic acid or levulinate, and better consumption is 0.05-2mol%, and optimum amount is 0.1-1mol%.
Wherein, the mol ratio of nitric acid, nitrate, nitrous acid or nitrite consumption and manganous compound is 1:1.
The method reaction raw materials used is a kind of in levulinic acid, methyl ester levulinate, ethyl levulinate, levulinic acid n-propyl, levulinic acid isopropyl ester, the positive butyl ester of levulinic acid, levulinic acid isobutyl ester or more than two kinds, structure is as follows:
R is the alkyl of hydrogen atom or C1-C4.
Oxidizing reaction solvent for use of the present invention is a kind of in acetic acid, acetonitrile, methyl acetate, ethyl acetate, diacetyl oxide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, Isosorbide-5-Nitrae-dioxane; Or a kind of in the alcohol of 1-4 carbon atom; The mol ratio of solvent and raw material levulinic acid or levulinate is 5-100.
This oxidizing reaction is carried out in pressure reactor, and oxygenant is oxygen or air, and in oxidizing reaction, oxygen partial pressure is 0.1-0.5MPa, and better oxygen partial pressure is 0.1-0.3MPa; Temperature of reaction is 40-100 ° of C, and optimal reaction temperature is 40-80 ° of C; Reaction times is 2-10h, and optimum reacting time is 2-4h.
Oxidizing reaction finishes to add excessive alcohol and esterifying catalyst to obtain target product succinate in backward reaction solution.According to the kind of target product succinate, determine the kind (as dimethyl succinate, just add methyl alcohol, diethyl succinate, just adds ethanol) that adds alcohol, the mol ratio of alcohol and raw material is 50-500.Esterification used catalyst can be hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, boron trifluoride diethyl etherate etc., can be also one or more of the heteropolyacids such as phospho-molybdic acid, phospho-wolframic acid, silicotungstic acid, silicomolybdic acid and solid super-strong acid.The add-on of esterification esterifying catalyst used is the 0.5-10.0mol% of substrate, and better consumption is 1.0-10.0mol%, and optimum amount is 2-5mol%, and reaction time of esterification 4-10h all can.Because esterification is a reversible reaction, the kind of esterifying catalyst and consumption, esterification reaction temperature and reaction time of esterification all can have impact to the ultimate yield of succinate, the rule of this esterification meets the feature of conventional esterification,, within the scope of claim of the present invention, the present invention does not repeat no more.
The example that is prepared as with diethyl succinate, typical preparation process is: a certain amount of ethyl levulinate and solvent are joined in reactor, under manganous compound and nitric acid, nitrate or nitrous acid, the effect of nitrite composite catalyst, carry out oxidizing reaction.After oxidizing reaction finishes, add excessive dehydrated alcohol and esterifying catalyst to carry out esterification, sampling analysis, esterification obtains product dimethyl succinate by underpressure distillation separation after approaching completely.
Compare with traditional route, variation route provided by the invention has following characteristics:
1. the present invention has realized that to take manganous compound and nitric acid, nitrate or nitrous acid, nitrite be composite catalyst, take molecular oxygen as oxygenant, more under mild conditions, levulinic acid or levulinate is being converted into succinate.
2. a kind of novel method (Chinese Patent Application No.: 201210237579.4 of preparing succinate of Yu Ben of the present invention seminar report; PCT application number: PCT/CN2012/087089) compare, under the prerequisite not declining in feed stock conversion and target product selectivity, reaction efficiency further improves, and reaction conditions is gentleer.
Accompanying drawing explanation
The primary product that Fig. 1 the invention provides method distributes;
Fig. 2 embodiment 1(is left) and the embodiment 2(right side) the original GC figure of reaction solution.
With embodiment in detail the present invention is described in detail below.
Embodiment
Embodiment 1: by 0.33g methyl ester levulinate, 0.5mol%(is with respect to methyl ester levulinate) manganous acetate (II) and 0.5mol% cupric nitrate, join in 35mL reactor, add 2mL glacial acetic acid, close still, being filled with oxygen pressure is 0.1MPa, under stirring, be warming up to 60 ° of C, and keep 4h.Then cool to room temperature, carefully reduces pressure and arrives normal pressure.Whole products are transferred in 50mL round-bottomed flask, add 20mL anhydrous methanol and 100mg boron trifluoride diethyl etherate, reflux 4h, cool to room temperature, is all transferred to 25mL volumetric flask by liquid, adds mark TMB(durol in 2mL) rear constant volume, use the gas chromatography retention time of GC-MS and reference material qualitative to primary product, then gas chromatographic analysis (GC, Fig. 2 is left) is used in sampling, and interior scalar quantity method obtains the selectivity of transformation efficiency and the product succinate of raw material.According to formula below:
The transformation efficiency that calculates methyl ester levulinate is 98.3%, and the selectivity of dimethyl succinate is 83.5%.
Embodiment 2: by 0.29g levulinic acid, 0.1mol%(is with respect to levulinic acid) manganese acetylacetonate (II) and 0.1mol% Sodium Nitrite, join in 35mL reactor, add 2mL methyl acetate, close still, being filled with oxygen pressure is 0.2MPa, under stirring, be warming up to 70 ° of C, and keep 2h.Then cool to room temperature, carefully reduces pressure and arrives normal pressure.Total overall reaction liquid is transferred to 50mL round-bottomed flask, add 20mL anhydrous methanol and the 120mg vitriol oil, backflow 6h, cool to room temperature, whole products are transferred to 25mL volumetric flask, add mark TMB(durol in 2mL) rear by methanol constant volume, it is qualitative to primary product that then the gas chromatography retention time of GC-MS and reference material is used in sampling.Quantitatively, interior scalar quantity method obtains the selectivity of transformation efficiency and the product dimethyl succinate of raw material levulinic acid to use gas chromatographic analysis (GC, Fig. 2 is right).According to the methods analyst product in embodiment 1, the transformation efficiency that obtains levulinic acid is 96.2%, and the selectivity of dimethyl succinate is 82.1%.
Embodiment 3: by 3.3g ethyl levulinate, 0.8mol%(is with respect to ethyl levulinate) manganous sulfate and 0.8mol% aluminum nitrate, join in 150mL reactor, add 20mL ethyl acetate, close still, being filled with oxygen pressure is 0.1MPa, under stirring, be warming up to 50 ° of C, and keep 2h.Then cool to room temperature, carefully reduces pressure and arrives normal pressure.Whole products are transferred in 100mL round-bottomed flask, added 20mL dehydrated alcohol and 100mg phospho-molybdic acid, reflux 2h, cool to room temperature.According to the methods analyst product in embodiment 1, the transformation efficiency that obtains ethyl levulinate is 90.5%, and the selectivity of diethyl succinate is 81.1%.
Embodiment 4: by 29.0g levulinic acid, 0.5mol%(is with respect to levulinic acid) manganous carbonate and 0.5mol% nitric acid, join in 1000mL reactor, add 200mL tetramethylene sulfone, close still, being filled with oxygen pressure is 0.1MPa, under stirring, be warming up to 80 ° of C, and keep 4h.Then cool to room temperature, carefully reduces pressure and arrives normal pressure.Whole products are transferred in 5000mL round-bottomed flask, added 500mL anhydrous methanol and 500mg silicotungstic acid, reflux 6h, cool to room temperature.According to the methods analyst product in embodiment 1, the transformation efficiency that obtains levulinic acid is 89.5%, and the selectivity of dimethyl succinate is 70.3%.
The above; it is only the present invention's specific embodiment partly; but protection scope of the present invention is not limited in this; also not because the precedence of each embodiment causes any restriction to the present invention; anyly be familiar with person skilled in the art of the present invention in the technical scope of the present invention report; can expect easily changing or replacing, within all should being encompassed in protection scope of the present invention.Therefore, protection scope of the present invention is not limited only to above embodiment, should be as the criterion with the protection domain of claim.
Claims (7)
1. the method that a levulinic acid and levulinate catalyzed oxidation transform, it is characterized in that: take air or oxygen as oxygenant, one or two or more kinds in manganous compound and nitric acid, nitrate, nitrous acid or nitrite is composite catalyst, catalysis levulinic acid or levulinate liquid-phase selective oxidation, through esterification, obtain product succinate again.
2. in accordance with the method for claim 1, it is characterized in that: in the method, used catalyst is one or two or more kinds composite catalyst for composition in manganous compound and nitric acid, nitrate, nitrous acid or nitrite, and wherein manganous compound comprises one or two or more kinds in manganous sulfate, manganous carbonate, manganous acetate (II), Manganous chloride tetrahydrate, manganese sulfide, manganese monoxide, manganous oxalate, manganese acetylacetonate (II); The consumption of manganous compound is that the better consumption of the 0.05-5mol%(of raw material levulinic acid or levulinate is 0.05-2mol%, and optimum amount is 0.1-1mol%); Another component of composite catalyst is nitric acid, nitrate, nitrous acid or nitrite, wherein nitrate comprises one or two or more kinds in saltpetre, SODIUMNITRATE, magnesium nitrate, aluminum nitrate, zinc nitrate, iron nitrate, cupric nitrate, and nitrite is one or two or more kinds in potassium nitrite, Sodium Nitrite; One or two or more kinds consumption in nitric acid, nitrate, nitrous acid or nitrite is that the better consumption of 0.05-5mol%(of raw material levulinic acid or levulinate is 0.05-2mol%, and optimum amount is 0.1-1mol%).
3. it is characterized in that in accordance with the method for claim 1: the mol ratio of nitric acid, nitrate, nitrous acid or nitrite consumption and manganous compound is 1:1.
4. in accordance with the method for claim 1, it is characterized in that: reaction raw materials is a kind of in levulinic acid, methyl ester levulinate, ethyl levulinate, levulinic acid n-propyl, levulinic acid isopropyl ester, the positive butyl ester of levulinic acid, levulinic acid isobutyl ester or more than two kinds, structure is as follows:
R is the alkyl of hydrogen atom or C1-C4.
5. it is characterized in that in accordance with the method for claim 1: oxidizing reaction solvent for use is a kind of in acetic acid, acetonitrile, methyl acetate, ethyl acetate, diacetyl oxide, dimethyl sulfoxide (DMSO), tetramethylene sulfone, Isosorbide-5-Nitrae-dioxane; Or a kind of in the alcohol of 1-4 carbon atom; The mol ratio of solvent and raw material levulinic acid or levulinate is 5-100.
6. in accordance with the method for claim 1, it is characterized in that: oxygenant is oxygen or air, in oxidizing reaction, oxygen partial pressure is that the better oxygen partial pressure of 0.1-0.5MPa(is 0.1-0.3MPa, temperature of reaction is 40-100 ° of C), optimal reaction temperature is that 40-80 ° of C(reaction times is 2-10h, and optimum reacting time is 2-4h).
7. in accordance with the method for claim 1, it is characterized in that: after oxidizing reaction finishes, according to the kind of target product succinate, determine the kind that adds alcohol, in reaction solution, add excessive corresponding alcohol and esterifying catalyst, by esterification, obtain product succinate.
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| CN201310148566.4A CN104119224B (en) | 2013-04-26 | 2013-04-26 | A kind of method that levulic acid and levulinate catalytic oxidation transform |
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| CN201310148566.4A CN104119224B (en) | 2013-04-26 | 2013-04-26 | A kind of method that levulic acid and levulinate catalytic oxidation transform |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN107459454A (en) * | 2016-06-02 | 2017-12-12 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation levulinate prepares succinate |
| CN109761799A (en) * | 2017-11-09 | 2019-05-17 | 中国科学院大连化学物理研究所 | A method of catalysis glucose selective oxidation |
| CN109761783A (en) * | 2017-11-09 | 2019-05-17 | 中国科学院大连化学物理研究所 | A kind of preparation method of gluconic acid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2676186A (en) * | 1952-04-18 | 1954-04-20 | Quaker Oats Co | Preparation of succinic acid |
| US5371229A (en) * | 1992-10-28 | 1994-12-06 | American Cyanamid Company | Method for the preparation of 2,3-pyridine-dicarboxylic acids and derivatives thereof |
| CN101323566A (en) * | 2007-06-11 | 2008-12-17 | 深圳市飞扬实业有限公司 | Preparation method of diethyl succinate |
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2013
- 2013-04-26 CN CN201310148566.4A patent/CN104119224B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2676186A (en) * | 1952-04-18 | 1954-04-20 | Quaker Oats Co | Preparation of succinic acid |
| US5371229A (en) * | 1992-10-28 | 1994-12-06 | American Cyanamid Company | Method for the preparation of 2,3-pyridine-dicarboxylic acids and derivatives thereof |
| CN101323566A (en) * | 2007-06-11 | 2008-12-17 | 深圳市飞扬实业有限公司 | Preparation method of diethyl succinate |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN105646223B (en) * | 2014-12-04 | 2017-12-26 | 中国科学院大连化学物理研究所 | A kind of method that levulic acid catalysis oxidation esterification prepares succinate |
| CN107459454A (en) * | 2016-06-02 | 2017-12-12 | 中国科学院大连化学物理研究所 | A kind of method that catalysis oxidation levulinate prepares succinate |
| CN109761799A (en) * | 2017-11-09 | 2019-05-17 | 中国科学院大连化学物理研究所 | A method of catalysis glucose selective oxidation |
| CN109761783A (en) * | 2017-11-09 | 2019-05-17 | 中国科学院大连化学物理研究所 | A kind of preparation method of gluconic acid |
| CN109761783B (en) * | 2017-11-09 | 2021-06-22 | 中国科学院大连化学物理研究所 | Preparation method of gluconic acid |
| CN109761799B (en) * | 2017-11-09 | 2021-08-06 | 中国科学院大连化学物理研究所 | Method for catalyzing selective oxidation of glucose |
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