CN104119224B - A kind of method that levulic acid and levulinate catalytic oxidation transform - Google Patents
A kind of method that levulic acid and levulinate catalytic oxidation transform Download PDFInfo
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- CN104119224B CN104119224B CN201310148566.4A CN201310148566A CN104119224B CN 104119224 B CN104119224 B CN 104119224B CN 201310148566 A CN201310148566 A CN 201310148566A CN 104119224 B CN104119224 B CN 104119224B
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- 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
A kind of method that levulic acid and levulinate catalytic oxidation transform, the method is taking air or oxygen as oxidant, manganous compound and nitric acid, nitrate or nitrous acid, nitrite are composite catalyst, and under temperate condition, catalysis levulic acid or levulinate liquid phase selective oxidation and esterification prepare succinate. The method catalytic oxidation efficiency is high, reaction condition gentleness, and composite catalyst manganous compound used and nitric acid, nitrate or nitrous acid, nitrite are cheap and easy to get, and product is easy to separate and purify, and have extraordinary practicality and broad prospect of application.
Description
Technical field
The present invention relates to the method for transformation of a kind of levulic acid and levulinate, relate in particular to a kind of with divalenceManganese compound and nitric acid, nitrate or nitrous acid, nitrite be for being complex as catalyst, catalysis biomass baseHardware and software platform compound levulic acid or levulinate are converted into the method for succinate, the method with air orOxygen is oxidant, and manganous compound and nitric acid, nitrate or nitrous acid, nitrite are composite catalyzingAgent, is converted into product succinic acid by liquid-phase selective oxidation and esterification by levulic acid or levulinateDiester.
Background technology
Succinate is a kind of important fine chemical material and intermediate. Can produce and be permitted by succinateMany fine chemicals, comprise succinic acid, BDO, oxolane, gamma-butyrolacton, γ-Ding Nei acylAmine and 1-METHYLPYRROLIDONE etc.; Therefore, at present succinate be widely used in food, spices, medicine,The industries such as coating, rubber and plastics. Can obtain succinic acid by succinate through hydrolysis, through hydrogenating reductionObtain BDO (CN1286142A), succinic acid and BDO can be grouped to degradation material---Poly butylene succinate, this material has good biological degradability, has important using value and wideWealthy development prospect.
Traditional preparation method of succinate mainly contains two kinds. (1) carbohydrate such as glucose is by sending outFerment obtains succinic acid, and then succinic acid obtains succinate (US with corresponding alcohol esterification under acid catalysis5723322, US5143834, US5143833, US5168055, US5573931). Although the methodMiddle succinic acid can be by living beings, but the method still faces a lot of difficulties, first fermentation method production fourthSecondly the culture medium cost of diacid is higher, and sweat requires strictly pH value, and the fourth that obtains of fermentation methodProduct more complicated in diacid reactant liquid, there is very large difficulty in the separating-purifying of succinic acid. (2) C4Hydro carbons or benzeneOxidation obtains maleic anhydride, and then maleic anhydride obtains succinate (EP844231, EP through esterification, hydrogenation728731, CN102070448A, CN101824627A, CN101343210A). This method keyRaw material C4Hydro carbons or benzene rely on fossil resource. Our seminar has reported a kind of new side who prepares succinateMethod (Chinese Patent Application No.: 201210237579.4; PCT application number: PCT/CN2012/087089), shouldMethod is taking levulic acid or levulinate as raw material, and molecular oxygen is oxidant, in manganese compound catalytic actionUnder, by liquid-phase catalysis selective oxidation and esterification, obtain succinate. The present invention in seminarOn some working foundations, further report with manganous compound and nitric acid, nitrate or nitrous acid, AsiaNitrate is composite catalyst, and oxygen or air are oxidant, under milder condition, pass through liquid-phase catalysisLevulic acid and levulinate are converted into succinate by selective oxidation and esterification.
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 orNitrite is composite catalyst, and oxygen or air are oxidant, are prepared by levulic acid or levulinateThe method of succinate, the method is taking levulic acid or levulinate as raw material, manganous compound withNitric acid, nitrate, nitrous acid or nitrite are composite catalyst, and oxygen or air are oxidant, logicalCross liquid-phase catalysis selective oxidation, then through esterification, obtain succinate and (the invention provides the master of methodWant product to distribute as shown in Figure 1).
In the method, used catalyst is manganous compound and nitric acid, nitrate, nitrous acid or nitriteIn one or two or more kinds for composition composite catalyst, wherein manganous compound comprises manganese sulfate, carbonAcid manganese, manganese acetate (II), manganese chloride, manganese sulfide, manganese monoxide, manganese oxalate, manganese acetylacetonate (II)In one or two or more kinds; The consumption of manganous compound is raw material levulic acid or levulinate0.05-5mol%, better consumption is 0.05-2mol%, optimum amount is 0.1-1mol%; Composite catalyzingAnother component of agent is nitric acid, nitrate, nitrous acid or nitrite, wherein nitrate comprise potassium nitrate,One or two or more kinds in sodium nitrate, magnesium nitrate, aluminum nitrate, zinc nitrate, ferric nitrate, copper nitrate, AsiaNitrate is one or two or more kinds in potassium nitrite, natrium nitrosum; Nitric acid, nitrate, nitrous acid or AsiaOne or two or more kinds consumption in nitrate is the 0.05-5 of raw material levulic acid or levulinateMol%, better consumption is 0.05-2mol%, optimum amount is 0.1-1mol%.
Wherein, the mol ratio of nitric acid, nitrate, nitrous acid or nitrite consumption and manganous compound is1:1。
The method reaction raw materials used is levulic acid, methyl ester levulinate, ethyl levulinate, levulinicA kind of in acid n-propyl, levulic acid isopropyl ester, the positive butyl ester of levulic acid, levulic acid isobutyl ester orMore than two kinds, structure is as follows:
R is the alkyl of hydrogen atom or C1-C4.
Oxidation reaction solvent for use of the present invention be acetic acid, acetonitrile, methyl acetate, ethyl acetate, acetic anhydride,One in dimethyl sulfoxide (DMSO), sulfolane, Isosorbide-5-Nitrae-dioxane; Or one in the alcohol of 1-4 carbon atom;The mol ratio of solvent and raw material levulic acid or levulinate is 5-100.
This oxidation reaction is carried out in pressure reactor, and oxidant is oxygen or air, oxygen in oxidation reactionDividing potential drop is 0.1-0.5MPa, and better oxygen partial pressure is 0.1-0.3MPa; Reaction temperature is 40-100 ° of C,Optimal reaction temperature is 40-80 ° of C; Reaction time is 2-10h, and optimum reacting time is 2-4h.
Oxidation reaction finishes to add excessive alcohol and esterification catalyst to obtain target product fourth in backward reactant liquorTwo acid diesters. Determine and add the kind of alcohol (as succinic acid diformazan according to the kind of target product succinateEster, just adds methyl alcohol, and diethyl succinate just adds ethanol), the mol ratio of alcohol and raw material is 50-500.Esterification used catalyst can be hydrochloric acid, sulfuric acid, phosphoric acid, boric acid, BFEE etc., also canTo be one or more of the heteropoly acids such as phosphomolybdic acid, phosphotungstic acid, silico-tungstic acid, silicomolybdic acid and solid super-strong acid.The addition of esterification esterification catalyst used is the 0.5-10.0mol% of substrate, and better consumption is1.0-10.0mol%, optimum amount is 2-5mol%, reaction time of esterification 4-10h all can. Due to esterificationReaction is a reversible reaction, when the kind of esterification catalyst and consumption, esterification reaction temperature and esterificationBetween all can have impact to the ultimate yield of succinate, it is anti-that the rule of this esterification meets conventional esterificationThe feature of answering,, within the scope of claim of the present invention, the present invention does not repeat no more.
With the example that is prepared as of diethyl succinate, typical preparation process is: by a certain amount of ethyl levulinateJoin in reactor with solvent, at manganous compound and nitric acid, nitrate or nitrous acid, nitriteUnder composite catalyst effect, carry out oxidation reaction. After oxidation reaction finishes, add excessive absolute ethyl alcohol and esterChange catalyst and carry out esterification, sample analysis, esterification separates by decompression distillation after approaching completelyObtain product dimethyl succinate.
Compared with traditional route, variation route provided by the invention has following characteristics:
1. the present invention has realized taking manganous compound and nitric acid, nitrate or nitrous acid, nitrite as multipleClose catalyst, taking molecular oxygen as oxidant, under temperate condition more by levulic acid or levulinicAcid esters is converted into succinate.
2. a kind of new method (Chinese patent application of preparing succinate of the present invention and this seminar reportNumber: 201210237579.4; PCT application number: PCT/CN2012/087089) compare, at raw materialUnder the prerequisite that conversion ratio and target product selectivity do not decline, reaction efficiency further improves, reactionCondition is gentleer.
Brief description of the drawings
The primary product that Fig. 1 the invention provides method distributes;
Fig. 2 embodiment 1(left side) and the embodiment 2(right side) the original GC figure of reactant liquor.
With embodiment in detail the present invention is described in detail below.
Detailed description of the invention
Embodiment 1: by 0.33g methyl ester levulinate, 0.5mol%(is with respect to methyl ester levulinate) secondAcid manganese (II) and 0.5mol% copper nitrate, join in 35mL reactor, adds 2mL glacial acetic acid,Close still, being filled with oxygen pressure is 0.1MPa, is warming up to 60 ° of C, and keeps 4h under stirring. Then coolingTo room temperature, careful decompression is to normal pressure. Whole products are transferred in 50mL round-bottomed flask, added 20mLAbsolute methanol and 100mg BFEE, add hot reflux 4h, and cool to room temperature, all turns liquidMove to 25mL volumetric flask, add mark TMB(durol in 2mL) rear constant volume, use GC-MS and markThe gas chromatography retention time of accurate material is qualitative to primary product, then sampling use gas chromatographic analysis (GC,Fig. 2 left side), interior scalar quantity method obtains the selective of the conversion ratio of raw material and product succinate. According underFace formula:
Calculating the conversion ratio of methyl ester levulinate is 98.3%, dimethyl succinate be selectively 83.5%.
Embodiment 2: by 0.29g levulic acid, 0.1mol%(is with respect to levulic acid) manganese acetylacetonate(II) and 0.1mol% natrium nitrosum, join in 35mL reactor, adds 2mL methyl acetate,Close still, being filled with oxygen pressure is 0.2MPa, is warming up to 70 ° of C, and keeps 2h under stirring. Then coolingTo room temperature, careful decompression is to normal pressure. Total overall reaction liquid is transferred to 50mL round-bottomed flask, adds 20mLAbsolute methanol and the 120mg concentrated sulfuric acid, backflow 6h, cool to room temperature, transfers to 25mL by whole productsVolumetric flask, adds mark TMB(durol in 2mL) rear by methanol constant volume, then sampling is used GC-MSQualitative to primary product with the gas chromatography retention time of standard substance. Use gas chromatographic analysis (GC, Fig. 2Right) quantitatively, interior scalar quantity method obtains the selection of conversion ratio and the product dimethyl succinate of raw material levulic acidProperty. According to the methods analyst product in embodiment 1, the conversion ratio that obtains levulic acid is 96.2%, fourth twoDimethyl phthalate be selectively 82.1%.
Embodiment 3: by 3.3g ethyl levulinate, 0.8mol%(is with respect to ethyl levulinate) sulphurAcid manganese and 0.8mol% aluminum nitrate, join in 150mL reactor, adds 20mL ethyl acetate, closesStill, being filled with oxygen pressure is 0.1MPa, is warming up to 50 ° of C, and keeps 2h under stirring. Then be cooled toRoom temperature, careful decompression is to normal pressure. Whole products are transferred in 100mL round-bottomed flask, added 20mLAbsolute ethyl alcohol and 100mg phosphomolybdic acid, add hot reflux 2h, cool to room temperature. According in embodiment 1Methods analyst product, the conversion ratio that obtains ethyl levulinate is 90.5%, diethyl succinate selectiveBe 81.1%.
Embodiment 4: by 29.0g levulic acid, 0.5mol%(is with respect to levulic acid) manganese carbonate and0.5mol% nitric acid, joins in 1000mL reactor, adds 200mL sulfolane, closes still, is filled withOxygen pressure is 0.1MPa, is warming up to 80 ° of C, and keeps 4h under stirring. Then cool to room temperature is littleThe heart normal pressure that reduces pressure. Whole products are transferred in 5000mL round-bottomed flask, added 500mL without water beetleAlcohol and 500mg silico-tungstic acid, add hot reflux 6h, cool to room temperature. Divide according to the method in embodiment 1Division thing, the conversion ratio that obtains levulic acid is 89.5%, dimethyl succinate be selectively 70.3%.
The above be only the specific embodiment of part of the present invention, but protection scope of the present invention also not onlyBe limited to this, also not because the precedence of each embodiment causes any restriction to the present invention, be anyly familiar with the present inventionThose skilled in the art, in the technical scope of the present invention's report, can expect changing or replacing, easilyWithin should being encompassed in protection scope of the present invention. Therefore, protection scope of the present invention is not limited only to above enforcementExample, should be as the criterion with the protection domain of claim.
Claims (10)
1. the method that levulic acid and levulinate catalytic oxidation transform, is characterized in that: with air orOxygen is oxidant, the one or two in manganous compound and nitric acid, nitrate, nitrous acid or nitriteMore than kind, be composite catalyst, catalysis levulic acid or levulinate liquid-phase selective oxidation, then through esterification, obtain product succinate.
2. it is characterized in that in accordance with the method for claim 1: in the method, used catalyst is divalenceOne or two or more kinds in manganese compound and nitric acid, nitrate, nitrous acid or nitrite answered for compositionClose catalyst, wherein manganous compound comprises manganese sulfate, manganese carbonate, manganese acetate (II), manganese chloride, sulphurChange one or two or more kinds in manganese, manganese monoxide, manganese oxalate, manganese acetylacetonate (II); Divalence manganeseThe consumption of compound is the 0.05-5mol% of raw material levulic acid or levulinate; Another group of composite catalystPart is nitric acid, nitrate, nitrous acid or nitrite, and wherein nitrate comprises potassium nitrate, sodium nitrate, nitreOne or two or more kinds in acid magnesium, aluminum nitrate, zinc nitrate, ferric nitrate, copper nitrate, nitrite is sub-In potassium nitrate, natrium nitrosum one or two or more kinds; In nitric acid, nitrate, nitrous acid or nitriteOne or two or more kinds consumption is the 0.05-5mol% of raw material levulic acid or levulinate.
3. it is characterized in that in accordance with the method for claim 2: the better consumption of manganous compound is formerThe 0.05-2mol% of material levulic acid or levulinate; In nitric acid, nitrate, nitrous acid or nitriteThe better consumption of one or two or more kinds is the 0.05-2mol% of raw material levulic acid or levulinate.
4. according to the method described in claim 2 or 3, it is characterized in that: the optimum amount of manganous compoundFor the 0.1-1mol% of raw material levulic acid or levulinate; Nitric acid, nitrate, nitrous acid or nitriteIn one or two or more kinds optimum amount be the 0.1-1mol% of raw material levulic acid or levulinate.
5. it is characterized in that in accordance with the method for claim 1: nitric acid, nitrate, nitrous acid or AsiaThe mol ratio of nitrate consumption and manganous compound is 1:1.
6. it is characterized in that in accordance with the method for claim 1: reaction raw materials is levulic acid, acetylMethyl propionate, ethyl levulinate, levulic acid n-propyl, levulic acid isopropyl ester, the positive fourth of levulic acidA kind of in ester, levulic acid isobutyl ester or more than two kinds, structure is as follows:
R is the alkyl of hydrogen atom or C1-C4.
7. it is characterized in that in accordance with the method for claim 1: oxidation reaction solvent for use be acetic acid,In acetonitrile, methyl acetate, ethyl acetate, acetic anhydride, dimethyl sulfoxide (DMSO), sulfolane, Isosorbide-5-Nitrae-dioxaneA kind of; Or one in the alcohol of 1-4 carbon atom; Solvent and raw material levulic acid or levulinate moleThan being 5-100.
8. in accordance with the method for claim 1, it is characterized in that: oxidant is oxygen or air, oxidation is anti-Should middle oxygen partial pressure be 0.1-0.5MPa, reaction temperature be 40-100 DEG C, and the reaction time is 2-10h.
9. according to the method described in claim 1 or 8, it is characterized in that: in oxidation reaction, better oxygen dividesPress as 0.1-0.3MPa, optimal reaction temperature is 40-80 DEG C, and optimum reacting time is 2-4h.
10. in accordance with the method for claim 1, it is characterized in that: after oxidation reaction finishes, according to targetThe kind of product succinate is determined the kind that adds alcohol, in reactant liquor, adds excessive corresponding alcohol and esterificationCatalyst, obtains product succinate by esterification.
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| 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 |
| 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 |
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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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 |
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