CN105712870A - Method for preparing butanedioic acid through catalytic oxidation cracking of acetylpropionic acid - Google Patents
Method for preparing butanedioic acid through catalytic oxidation cracking of acetylpropionic acid Download PDFInfo
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Abstract
A method for preparing butanedioic acid through catalytic oxidation cracking of acetylpropionic acid is provided; according to the method, a manganese-containing composite oxide material modified by a hydrophobic group is used as a catalyst, molecular oxygen is used as an oxygen source, and acetylpropionic acid is oxidized into butanedioic acid under a solvent-free condition. The hydrophobic properties of the catalyst can inhibit adsorption of oxidation by-product water on the catalyst surface, and the catalyst stability is improved; at the same time, through control of adsorption of raw materials and products on the catalyst surface, the selectivity of the target product butanedioic acid is improved.
Description
Technical field
The invention belongs to nano material application in catalytic oxidation, specifically hydrophobic type nanometer complex oxide material containing manganese is applied to levulic acid oxidation and prepares in succinic acid reaction, improve catalyst stability and selectivity of product.
Background technology
Succinic acid is a kind of important fine-chemical intermediate, can be used for producing BDO, oxolane, gamma-butyrolacton and N-Methyl pyrrolidone etc., is widely used at food, spice, medicine, coating, rubber and plastic industry.Succinic acid and BDO can be grouped to poly butylene succinate as monomer, and this material has good biological degradability, has important using value and vast potential for future development.
The production method of current succinic acid, mainly with benzene or butane etc. for raw material, first passes through catalytic gas phase oxidation and obtains maleic anhydride, then selects hydrogenation to obtain succinic acid.The critical materials C4 hydro carbons of this method or benzene are from non-renewable fossil resource, and the price by fossil resource is bigger.The biomass such as starch, glucose, fructose can be converted into succinic acid by biotechnology in a mild condition, but biotransformation needs problems such as overcoming the degeneration of microorganism, microorganism adaptation pH value range narrow, and extracts succinic acid from the mixed fermentation liquid of composition complexity and be faced with the challenges such as cost, energy consumption and material consumption.Therefore, development is prepared the new method of succinic acid and is had great importance and application background.
Levulic acid (levulinicacid) is one of primary product of the polyol dehydration such as cellulose, glucose degraded, it it is considered as a kind of important bio-based platform chemicals, raw material sources prepared by levulic acid are widely, can produce from having the hemicellulose of C5 construction unit, xylose etc., it is also possible to from having the preparations such as the cellulose of C6 biomass unit, starch, glucose, fructose；The forestry waste such as the agricultural wastes such as straw, wood flour, fallen leaves, paper-making industry and domestic refuse etc. also can obtain levulic acid under acid catalysis.In the molecular structure of levulic acid, there is the construction unit similar to succinic acid, levulic acid can be converted into succinic acid by C-C key oxidation scission.
Up to the present, only have minority bibliographical information and prepare succinic acid with levulic acid for raw material, as US Patent No. 2676186 reports with V2O5Being converted into succinic acid for catalyst gas phase catalysis levulic acid, the method reacts in gas phase, and reaction temperature is higher；Ponsford etc. report with mantoquita for catalyst H2O2Acetyloxide propanoic acid obtains succinic acid (Biochem.J., 1934,28,892-897).Applicant in patent (application number 201210237579.4) with levulic acid or levulinate for raw material, molecular oxygen is oxygen source, manganese compound is as catalyst, under liquid phase temperate condition, prepare succinate, but catalyst used is homogeneous manganese compound or common Mn oxide.With molecular oxygen for the oxidation reaction of oxygen source, water would generally generate as by-product.Homogeneous manganese compound easily meets water inactivation in the oxidation reaction, and Mn oxide surface can be adsorbed water and be caused that its catalysis activity significantly reduces, and therefore in previously research, catalyst can not recycle or the selectivity of product succinic acid is relatively low.For these problems, the present invention is by introducing hydrophobic organic group, surface containing manganese composite oxide material is modified, construct the catalyst with hydrophobic surface, suppression water contacts with Mn oxide, improve the stability of catalyst, regulate the absorption at catalyst surface of levulic acid and succinic acid simultaneously, improve the selectivity of succinic acid.
Summary of the invention
In order to construct the catalyst with hydrophobic surface, it is achieved the regulation and control that water, levulic acid, succinic acid are adsorbed by catalyst surface, it is necessary to invention body contains manganese metal, surface hydrophobic nano composite oxide material connecting organic group and preparation method thereof mutually；It is based upon under the effect of catalyst, with the method that molecular oxygen prepares succinic acid for oxygen source acetyloxide propanoic acid.
The preparation method of this hydrophobic type catalyst, is specifically with SiO2Nano-particle is substrate, its body mutually in be embedded with inorganic manganese oxide, connect organic group in its surface；It can adopt formula Og-Mn-SiO2Representing, Og is the abbreviation of organic group Organicgroup；Wherein said organic group is one or two or more kinds in methyl, ethyl, propyl group, phenyl, naphthyl, trifluoro propyl, ten trifluoro octyl groups, 17 fluorine decyls, phenyl-monofluoride base and pentafluorophenyl group.Og-Mn-SiO2Material particle size is 20-150nm；Mn oxide is with the form of composite oxides in body phase, and mass content is 0.5-30%；Organic group mass content is 2-40%, and all the other components are SiO2。
The preparation of described hydrophobic nano composite oxide material can operate as follows:
1) by surfactant, the ammonia of mass concentration 25-28%, organic facies and cosurfactant mixing composition reverse micro emulsion A；The aqueous solution of soluble manganese salt or or the ammonia complexing solution of manganese be B；
2) tetraethyl orthosilicate and alkyl triethoxysilane are silicon source, are mixed and made into solution C；
3) mixed solution A and B obtain solution D；When stirring, solution C is added in solution D, and aging 2-48h；The mass ratio of the final mixed solution of gained is (0-8) surfactant: (1-4) water: (5-9) organic facies: (0-6) cosurfactant: (1) tetraethyl orthosilicate: (0.05-1.5) alkyl triethoxysilane: (0.01-1) manganese slaine；In ammonia, ammonia precipitates required amount completely with added manganese ion and measures.Step 1) in ammonia complexing solution be used in the aqueous solution of manganese soluble-salt drip mass concentration 25-28% ammonia prepare；In described ammonia complexing solution, ammonia is generally 2-8 with the mol ratio of manganese ion；
4) add the acetone breakdown of emulsion of 5-10 times of tetraethyl orthosilicate quality, after centrifugal, take out solid；With this solid of washing with alcohol more than 5 times to remove surfactant, 80-150 DEG C of vacuum drying, finally obtain the nano material of a kind of even particle size；
Surfactant used in said method can be anion surfactant such as sodium n-alkylbenzenesulfonate and α-sodium olefin sulfonate, can also be the organic primary amine of nonionic surfactant such as long-chain, Np series and TWEEN Series surfactant, it is also possible to be cationic surfactant such as CTAB etc..Organic facies is ethanol, hexamethylene, normal hexane or toluene, and cosurfactant is hexanol, isobutanol or n-octyl alcohol.
Described manganese soluble-salt is manganese acetate, manganese nitrate, manganese chloride or manganese sulfate；Mn oxide is with the form of composite oxides in body phase, and mass content is 0.5-30%；Alkyl in described alkyl triethoxysilane is one or two or more kinds in methyl, ethyl, propyl group, phenyl, trifluoro propyl, ten trifluoro octyl groups, 17 fluorine decyls, phenyl-monofluoride base and pentafluorophenyl group.According to the present invention, the amount of hydrophobic group can affect catalyst surface hydrophobicity and nano-particle pattern, and content too much can make nano silicon spheres irregular, and the hydrophobic performance on the too low then surface of content improves deficiency.Therefore hydrophobic group mass content 0.5-40% in the catalyst in the present invention.
Materials application provided by the invention is prepared in succinic acid reaction in levulic acid catalytic oxidation, with molecular oxygen for oxygen source, carries out under solvent-free liquid-phase condition.Catalyst amount is the 5-40% of levulic acid quality, and reaction temperature is 100-160 DEG C；Molecular oxygen is one or more in oxygen and air, and wherein in oxidation reaction, oxygen partial pressure is 0.1-2.0MPa；Response time is 5-20h；Levulic acid conversion ratio is 50-90%, and succinic acid selectivity reaches more than 85%；Reaction need not add solvent, and as added atent solvent (such as acetonitrile, ethyl acetate etc.), reaction still can carry out, but can improve cost, reduces reaction rate.When temperature improves, catalyst amount increases, the response time can shorten, but cost improves.Oxygen pressure increases the raising being conducive to reaction rate, but the requirement of equipment and production safety is also greatly improved.
Catalyst can recycle more than 5 times.The employing following methods of reusing of catalyst carries out: after reaction terminates, adds ethanol etc. and dissolves reacted organic mixture, adopt centrifugal method by catalyst separation out, fully wash final vacuum with ethanol and dry.Gained solid catalyst can repeatedly use in this way.
Beneficial effects of the present invention
The present invention obtains hydrophobicity Mn oxide material by the organic decoration design on surface, is applied in the solvent-free oxidation reaction of levulic acid, owing to this material shows hydrophobic property, can suppress the water adverse effect to catalytic reaction.Compared with prior art, the method that succinic acid prepared by heterogeneous catalytic oxidation levulic acid provided by the invention, adopt solvent-free liquid phase reactor, catalyst can repeatedly be recycled, and the selectivity of target product succinic acid is also obviously improved.
Detailed description of the invention
First the present invention configures the microemulsion of certain volume, then allows manganese metal saline solution, silester and alkyl triethoxysilane react in the water core of microemulsion simultaneously, last breakdown of emulsion, centrifugal, get rid of surfactant again, dry.
By a certain proportion of surfactant, ammonia, organic facies and cosurfactant mixing composition reverse micro emulsion A；The chloride of manganese, acetate, nitrate, sulfate or isopropoxide are manganese source metal, solution B of making soluble in water, and tetraethyl orthosilicate and alkyl triethoxysilane are silicon source, are mixed and made into solution C；Mixed solution A and B obtain solution D；When stirring, solution C is added in solution D, and aging 2-48h；Add acetone breakdown of emulsion, be centrifuged to obtain solid；Ethanol repeatedly washs this solid and removes surfactant, dries to obtain final nano material for 80-150 DEG C.The mass ratio of the final mixed solution of gained is (0-8) surfactant: (1-4) water: (2-9) organic facies: (0-6) cosurfactant: (1) tetraethyl orthosilicate: (0.05-1.5) alkyl triethoxysilane: (0.01-1) manganese salt.Similar with the material synthesis method containing manganese composite oxide that hydrophobic group is modified, it is different in that in the kind of manganese source metal or organosilan, the kind of the concrete manganese source metal adopted and organosilan is in Table 1.
Table 1
| Material number | Manganese source metal | Organosilan |
| 1 | Manganese acetate | Methltriethoxysilone |
| 2 | Manganese sulfate | Phenyl-monofluoride ethyl triethoxy silicane alkane |
| 3 | Manganese nitrate | Pentafluorophenyl group triethoxysilane |
| 4 | Manganese chloride | Phenyltriethoxysilane |
| 5 | Manganese acetate | Phenyltriethoxysilane |
| 6 | Manganese acetate | Pentafluorophenyl group triethoxysilane |
| 7 | Manganese acetate | One propyl-triethoxysilicane |
| 8 | Manganese acetate | One ethyl triethoxysilane |
| 9 | Manganese acetate | One VTES |
| 10 | Manganese acetate | Chloroallyl triethoxysilane |
Embodiment 1:
Material M (MnPh-SiO2) preparation
Take 15g dodecylbenzene sodium sulfonate, 35g normal hexane, 6g hexanol and 0.5g ammonia and be mixed to get solution A；0.02g manganese acetate is dissolved in 3g deionized water and obtains solution B；1g tetraethyl orthosilicate and 0.4g phenyltriethoxysilane are mixed to get solution C；Solution B and solution C are added in solution A when stirring, aging 20h；Add 15mL acetone, stir 20min, after centrifugal, take solid；In this solid, add 80mL ethanol, heated and stirred 20min, be centrifuged；Repeat this step repeatedly, until removal of surfactant is clean；100 DEG C of vacuum dryings obtain nano material MnPh-SiO2。
Levulic acid aoxidizes:
By 5g levulic acid, 5wt% (relative to levulic acid) MnPh-SiO2Join in 50mL reactor, be filled with oxygen to 1.0MPa, be stirred continuously down and be warming up to 150 DEG C, and keep 10h.Then room temperature it is cooled to.Add the abundant dissolved organic matter of methanol, after centrifugal, filter solid catalyst, use liquid-phase chromatographic analysis to obtain the conversion ratio of raw material and the selectivity of product succinic acid.Calculate the conversion ratio of levulic acid and the selectivity of succinic acid according to the following formula.
Conversion ratio [mol%]=(A0-A)/A0× 100%, selectivity [mol%]=B/ (A0-A) × 100%
In formula, A0For adding the amount of substance [mol] of levulic acid before reacting, A is the amount of substance [mol] remaining levulic acid after reaction, and B is the amount of substance [mol] generating succinic acid in course of reaction.
The conversion ratio of the levulic acid calculated is 83%, and the selectivity of succinic acid is 85%, and other Main By products include oxalic acid, acetic acid, formic acid, carbon dioxide etc..
Embodiment 2: take 20gNp-10,25g hexamethylene and 3g n-octyl alcohol is mixed to get solution A；0.02g manganese chloride is dissolved in 3g deionized water, and adds 0.5g ammonia, obtains solution B；1g tetraethyl orthosilicate and 0.2g 17 fluorine decyl triethoxysilane are mixed to get solution C；Solution B is poured into solution A obtains solution D, with vigorous stirring solution C is added in solution D, aging 8h；Then, add 10mL acetone, stir 30min, after centrifugal, take out solid；In this solid, add 30mL ethanol, heated and stirred 10min, be centrifuged；Repeat this step repeatedly, until removal of surfactant is clean；80 DEG C of nano material HF-Mn-SiO drying finally2。
Levulic acid aoxidizes:
By 5g levulic acid, 5wt% (relative to levulic acid) HF-Mn-SiO2Join in 50mL reactor, be filled with oxygen to 0.5MPa, be stirred continuously down and be warming up to 150 DEG C, and keep 5h.Then room temperature it is cooled to.Add the abundant dissolved organic matter of methanol, after centrifugal, filter solid catalyst, use liquid-phase chromatographic analysis to obtain the conversion ratio of raw material and the selectivity of product succinic acid.The conversion ratio of the levulic acid calculated is 40%, and the selectivity of succinic acid is 92%, and other Main By products include oxalic acid, acetic acid, formic acid, carbon dioxide etc..
Embodiment 3: take 20g ethanol and 0.9g ammonia is mixed to get solution A；0.03g manganese sulfate is dissolved in 5g deionized water and obtains solution B；1g tetraethyl orthosilicate and 0.g mono-propyl-triethoxysilicane are mixed to get solution C；Solution B and solution C are added in solution A when stirring, aging 20h；Solid is taken after centrifugal；In this solid, add 60mL ethanol, heated and stirred 15min, be centrifuged；100 DEG C of drying, obtain final nano material Pr-Mn-SiO2。
Levulic acid aoxidizes:
By 5g levulic acid, 10wt% (relative to levulic acid) Pr-Mn-SiO2Join in 50mL reactor, be filled with oxygen to 1.5MPa, be stirred continuously down and be warming up to 120 DEG C, and keep 15h.Then room temperature it is cooled to.Add the abundant dissolved organic matter of methanol, after centrifugal, filter solid catalyst, use liquid-phase chromatographic analysis to obtain the conversion ratio of raw material and the selectivity of product succinic acid.The conversion ratio of the levulic acid calculated is 78%, and the selectivity of succinic acid is 87%, and other Main By products include oxalic acid, acetic acid, formic acid, carbon dioxide etc..
Claims (5)
1. the method that a levulic acid catalytic oxidative cracking prepares succinic acid, it is characterised in that: the method with hydrophobic type containing manganese nanometer complex oxide material for catalyst；With molecular oxygen for oxygen source, under condition of no solvent, succinic acid prepared by catalytic oxidation levulic acid, and this catalyst is with SiO2Microsphere is substrate, and its body embeds Mn oxide with composite oxides form, and its surface connects hydrophobic organic groups with Si-C key-like formula；Catalyst surface has hydrophobicity.
2. in accordance with the method for claim 1, it is characterised in that: organic group is one or two or more kinds in methyl, ethyl, propyl group, phenyl, naphthyl, trifluoro propyl, ten trifluoro octyl groups, 17 fluorine decyls, phenyl-monofluoride base or pentafluorophenyl group.
3. the method described in claim 1 or 2, it is characterised in that: described hydrophobic type adopts formula Og-Mn-SiO containing manganese nanometer complex oxide material2Representing, Og is the abbreviation of organic group Organicgroup；Og-Mn-SiO2Material particle size is 20-150nm；Mn oxide is with the form of composite oxides in body phase, and mass content is 0.5-30%；Organic group mass content is 2-40%, and all the other components are SiO2。
4. the method described in claim 1 or 2, it is characterised in that: described levulic acid oxidation is prepared the reaction of succinic acid and is carried out under solvent-free liquid-phase condition, and catalyst amount is the 5-40% of levulic acid quality, and reaction temperature is 100-160 DEG C；Molecular oxygen is one or both in oxygen and air, and wherein in oxidation reaction, oxygen partial pressure is 0.1-2.0MPa；Response time is 5-20h.
5. the method described in claim 1 or 4, it is characterised in that: levulic acid conversion ratio is 50-90%, and succinic acid selectivity reaches more than 85%；Catalyst can recycle more than 5 times.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573450A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by catalyzing levulinic acid with MnCeOx |
| CN114835572A (en) * | 2022-06-07 | 2022-08-02 | 南昌大学 | Synthesis method of metal-free 2-hydroxy-2-methylsuccinic 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 |
| CN101597437A (en) * | 2008-06-04 | 2009-12-09 | 中国科学院大连化学物理研究所 | A kind of nanometer complex oxide material of organic decoration and preparation thereof |
| 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 |
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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 |
| CN101597437A (en) * | 2008-06-04 | 2009-12-09 | 中国科学院大连化学物理研究所 | A kind of nanometer complex oxide material of organic decoration and preparation thereof |
| 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 |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114573450A (en) * | 2020-12-01 | 2022-06-03 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by catalyzing levulinic acid with MnCeOx |
| CN114573450B (en) * | 2020-12-01 | 2023-05-30 | 中国科学院大连化学物理研究所 | Method for preparing acetic acid by catalyzing levulinic acid through MnCeOx |
| CN114835572A (en) * | 2022-06-07 | 2022-08-02 | 南昌大学 | Synthesis method of metal-free 2-hydroxy-2-methylsuccinic acid |
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