CN109912549A - A kind of 5 hydroxymethyl furfural selective oxidation prepares the new method of 5-HMFA - Google Patents
A kind of 5 hydroxymethyl furfural selective oxidation prepares the new method of 5-HMFA Download PDFInfo
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Abstract
The present invention is a kind of method for preparing 5-HMFA by 5 hydroxymethyl furfural selective oxidation, comprising: is added in reaction unit, and is passed through oxygen 5 hydroxymethyl furfural, alkali, catalyst, solvent, form reaction system；It is 0-100 DEG C in temperature, carries out oxidation reaction, can be prepared by the 5-HMFA product of higher yields.Advantage: the disadvantages of by-product in the prior art is more, and selectivity is not high, and catalyst is expensive are overcome.This catalyst does not use noble metal, has the characteristics that efficient, green, environmentally friendly, by-product is few, easily separated recycling, can be recycled, and the yield of 5-HMFA is higher.
Description
Technical field
The present invention relates to a kind of method for preparing 5-HMFA by 5 hydroxymethyl furfural selective oxidation, belonging to
Work reaction technology field.
Background technique
Currently, fossil resources are increasingly reduced, the chemicals such as how effectively developed renewable resources with sustainable mode
The problem of becoming urgent need to resolve with fuel.Unlike other renewable resources, biomass is unique wide in addition to fossil resource
The general carbon source used.5 hydroxymethyl furfural (HMF) is a kind of important plateform molecules, is the pass for developing a variety of important substances
Key intermediate, such as natural drug, antifungal compound and polymer.Some furan compounds can pass through the selectivity of HMF
Oxidation be made, such as 2,5- dimethyl furan (DFF), 5-HMFA (HMFCA), -2 furancarboxylic acid of 5- formoxyl (FFCA) and
2,5- furan dicarboxylic acids (FDCA).Wherein, HMFCA's is widely used, is the presoma of the monomers of various polyester, anti-tumor drug
And the building module of interleukin inhibitor.For a long time, people are a lot of to the study on the synthesis of FDCA and DFF, and to HMFCA
Study on the synthesis it is limited, the reason is that hydroxyl is extremely oxidized easily and can not selective oxidation aldehyde radical in oxidation process.
The report for having had some related 5 hydroxymethyl furfurals to prepare 5-HMFA both at home and abroad: Krystof etc. is utilized
Lipase-catalyzed HMF oxidative synthesis HMFCA generates about 20% by-product second although the substrate transformation rate almost reaches to 100%
Acid esters or butyrate, selectivity are bad.(ChemSusChem, 2013,6,826)
Cannizzaro reaction in recent years also be used to prepare 5-HMFA.Ionic liquid is used in anhydrous conditions
Cannizzaro reaction occurs as reusable solvent and generates 5-HMFA.In the process, although it is environmentally friendly, behaviour
Make simply, but the yield of 5-HMFA is lower and will cause the waste of highly basic.(J.Ind.Eng.Chem., 2012,
18,174.)
Zehui Zhang et al., for carrier loaded Mo, prepares heterogeneous catalysis K-10 clay-Mo catalysis with montmorillonite
HMF oxidative synthesis HMFCA, it is 86.9% that using toluene as solvent, after reaction 3h, conversion ratio, which reaches 100%, HMFCA yield, turn
Though rate and yield are higher, the toxic solvent used, environment is polluted.(Green Chem., 2014,16,2762)
Summary of the invention
Proposed by the present invention is a kind of method for preparing 5-HMFA by 5 hydroxymethyl furfural selective oxidation, and reaction turns
Rate and yield are higher, do not need addition organic solvent, and reaction dissolvent is water, simple and easy to get, environmentally protective.React following institute
Show.Its purpose is intended to overcome drawbacks described above present in the prior art, prepares 5-HMFA using loaded catalyst, tool
There is the features such as synthesis process is simple, easy post-processing, and manufacturing cost is low.
A kind of technical solution of the invention: side preparing 5-HMFA by 5 hydroxymethyl furfural selective oxidation
Method comprises the technical steps that:
(1) by 5 hydroxymethyl furfural, alkali, solvent, catalyst, be added in reaction unit, and be passed through oxygen, form reaction system,
The mass ratio of the 5 hydroxymethyl furfural and solvent is 0.01-1000, and the mass ratio of catalyst and 5 hydroxymethyl furfural is
The mass ratio of 0.01-100, alkali and 5 hydroxymethyl furfural is 0.01-100；
(2) in the case where temperature is 0-100 DEG C, oxidation reaction 0.01-200h is carried out, can be prepared by 5-HMFA.
The invention has the following advantages that
1) without using the solvent of difficult separation and recovery, this technology has the advantages that environmentally protective；
2) using 5 hydroxymethyl furfural as raw material, water is solvent, and loaded catalyst prepares 5- hydroxyl first under oxygen and alkaline condition
Base furancarboxylic acid；The effect of addition stabilizer PVP, PAP be in order to prevent metal nanoparticle occur concentration effect generate big particle into
And active sites are reduced, to reduce catalyst activity.This reaction can change gold by changing the molar ratio of PVP and metallic
The size of metal nano-particle.Improve the conversion ratio of 5 hydroxymethyl furfural and the yield of 5-HMFA.This reaction is simple and efficient,
Low in cost, environmental-friendly, safe operation is able to satisfy the requirement of Technological Economy, has good industrial prospect；
3) loaded catalyst can be catalyzed 5 hydroxymethyl furfural selective oxidation preparation 5- methylol chaff efficiently, with high selectivity
Acid, and can be easy to separate from product, realize recycling for catalyst；
4) under suitable condition, 5 hydroxymethyl furfural conversion ratio is 100% for reaction, and the yield of product 5-HMFA is
99%, selectivity is 99%.
Specific embodiment
A method of 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation, is comprised the technical steps that:
(1) 5 hydroxymethyl furfural, alkali, solvent, catalyst are added in reaction unit, form reaction system, the 5- hydroxyl first
The mass ratio of base furfural and solvent is 0.01-1000, and the mass ratio of catalyst and 5 hydroxymethyl furfural is 0.01-100, alkali and 5-
The mass ratio of hydroxymethylfurfural is 0.01-100；
(2) it is 0-100 DEG C in temperature, carries out oxidation reaction 0.01-200h, can be prepared by 5-HMFA；
(3) for product using the content of high performance liquid chromatography measurement 5-HMFA, 5 hydroxymethyl furfural conversion ratio is 100%,
The yield of 5-HMFA is 99%, and selectivity is 99%.
The solvent is water, organic solvent, one ORGANIC SOLVENT MIXTURES of water.
The organic solvent is methanol, ethyl alcohol, ethylene glycol, tetrahydrofuran, methylene chloride, acetone, ethyl acetate, benzene, first
Benzene, n,N-Dimethylformamide.
The aqueous slkali is sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium hydroxide.
The catalyst is loaded catalyst；The metal of the catalyst load is the one of Ag, Co, Ni, Cu, Fe
Kind or two kinds, two kinds of its mass ratioes are 0.001-1000.
The catalyst carrier is active carbon, hydrotalcite, titanium dioxide, zirconium dioxide, silica, aluminium oxide, four oxygen
Change three-iron.
The stabilizer is PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), mole with metal load content
Than for 0.01-100.
Embodiment 1
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2(Ag: PVP=1: 0.5 (molar ratio), 2.5% is negative for catalyst
Carry), 0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, and oxygen flow is 60 mL/min, in temperature
It is reacted at 20 DEG C of degree, real time sample, product measures containing for 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography
Amount.When reacting 12h, the conversion ratio of 5 hydroxymethyl furfural is 99%, and the yield of 5-HMFA is 99%, is selectively
100%.
Embodiment 2
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2(Ag: PVP=1: 1 (molar ratio), 2.5% is negative for catalyst
Carrying) 0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, and oxygen flow is 60 mL/min, in temperature
It is reacted at 20 DEG C of degree, real time sample, product measures containing for 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography
Amount.When reacting 4h, the conversion ratio of 5 hydroxymethyl furfural is 100%, and the yield of 5-HMFA is 99%, is selectively
99%.
Embodiment 3
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2(Ag: PVP=1: 2 (molar ratios), 2.5% is negative for catalyst
Carry), 0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, and oxygen flow is 60 mL/min, in temperature
It is reacted at 20 DEG C of degree, real time sample, product measures containing for 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography
Amount.When reacting 6h, the conversion ratio of 5 hydroxymethyl furfural is 100%, and the yield of 5-HMFA is 95%, is selectively
95%.
Embodiment 4
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2(Ag: PVP=1: 1 (molar ratio), 2.5% is negative for catalyst
Carry), 0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, and oxygen flow is 60 mL/min, in temperature
It is reacted at 40 DEG C of degree, real time sample, product measures containing for 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography
Amount.When reacting 4h, the conversion ratio of 5 hydroxymethyl furfural is 100%, and the yield of 5-HMFA is 99%, is selectively
99%.
Embodiment 5
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2(Ag: PVP=1: 1 (molar ratio), 2.5% is negative for catalyst
Carry), 0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, and oxygen flow is 60 mL/min, in temperature
It is reacted at 60 DEG C of degree, real time sample, product measures containing for 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography
Amount.When reacting 12h, the conversion ratio of 5 hydroxymethyl furfural is 99.84%, and the yield of 5-HMFA is 92.01%, selectivity
It is 92.16%.
Embodiment 6
By 0) 2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2(Ag: PVP=1: 1 (molar ratio), 2.5% is negative for catalyst
Carry), 0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, and oxygen flow is 30 mL/min, in temperature
It is reacted at 20 DEG C of degree, real time sample, product measures containing for 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography
Amount.When reacting 12h, the conversion ratio of 5 hydroxymethyl furfural is 100%, and the yield of 5-HMFA is 98.84%, is selectively
98.84%.
Embodiment 7
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2(Ag: PVP=1: 1 (molar ratio), 2.5% is negative for catalyst
Carry), 0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, and oxygen flow is 120 mL/min,
It is reacted at 20 DEG C of temperature, real time sample, product uses high performance liquid chromatography measurement 5 hydroxymethyl furfural and 5-HMFA
Content.When reacting 9h, the conversion ratio of 5 hydroxymethyl furfural is 100%, and the yield of 5-HMFA is 99%, is selectively
99%.
Embodiment 8
By 0.2g 5 hydroxymethyl furfural, 0.05gAg-PVP/ZrO2Catalyst (Ag: PVP=1: 1 (molar ratio), 1% load),
0.126gNaOH, 50mL water are added in 150mL three-neck flask, and are passed through oxygen, oxygen flow 60mL/min, at 20 DEG C of temperature
Lower reaction, real time sample, product measure the content of 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography.Reaction
When 12h, the conversion ratio of 5 hydroxymethyl furfural is 96.69%, and the yield of 5-HMFA is 96%, and selectivity is 99.29%.
Embodiment 9
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag-PVP/ZrO2Catalyst (Ag: PVP=1: 1 (molar ratio), 5% load),
0.126g NaOH, 50mL water is added in 150mL three-neck flask, and is passed through oxygen, oxygen flow 60mL/min, in temperature 20
It is reacted at DEG C, real time sample, product measures the content of 5 hydroxymethyl furfural and 5-HMFA using high performance liquid chromatography.Instead
When answering 12h, the conversion ratio of 5 hydroxymethyl furfural is 96.02%, and the yield of 5-HMFA is 95%, and selectivity is 99%.
Embodiment 10
By 0.2g 5 hydroxymethyl furfural, 0.05g Ag/ZrO2Catalyst (2.5% load), 0.126g NaOH, 50mL water is added
In 150mL three-neck flask, and it is passed through oxygen, oxygen flow 60mL/min reacts, real time sample, product at 20 DEG C of temperature
Use the content of high performance liquid chromatography measurement 5 hydroxymethyl furfural and 5-HMFA.When reacting 12h, 5 hydroxymethyl furfural
Conversion ratio be 76.04%, the yield of 5-HMFA is 76%, and selectivity is 99.9%.
Embodiment 11
By 0.5g 5 hydroxymethyl furfural, 0.125g Ag-PVP/ZrO2(Ag: PVP=1: 1 (molar ratio), 2.5% is negative for catalyst
Carry), 0.165g NaOH, 10mL water is added in 50mL three-neck flask, and is passed through oxygen, and oxygen flow is 60 mL/min, in temperature
It is reacted at 20 DEG C of degree, real time sample, product contains using high performance liquid chromatography measurement 5 hydroxymethyl furfural and 5- methylol are sour
Amount.When reacting 4h, the conversion ratio of 5 hydroxymethyl furfural is 99%, and the yield of 5-HMFA is 87.8%, is selectively
88.7%.
Claims (9)
1. a kind of method for preparing 5-HMFA by 5 hydroxymethyl furfural selective oxidation, feature includes following technique step
It is rapid:
(1) 5 hydroxymethyl furfural, alkali, catalyst, solvent are added in reaction unit, and are passed through oxygen, form reaction system, institute
The mass ratio of the 5 hydroxymethyl furfural and solvent stated is 0.01-1000, and the mass ratio of catalyst and 5 hydroxymethyl furfural is 0.01-
100, the mass ratio of alkali and 5 hydroxymethyl furfural is 0.01-100；
(2) at 0-100 DEG C of temperature, oxidation reaction 0.01-200h is carried out, 5-HMFA is made.
2. a kind of method that 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation according to claim 1,
It is characterized in that the 5 hydroxymethyl furfural is prepared by glucose, fructose, jerusalem artichoke, sucrose, cellulose or lignocellulosic material.
3. a kind of method that 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation according to claim 1,
It is characterized in that the solvent is water, organic solvent, water-ORGANIC SOLVENT MIXTURES.
4. a kind of method that 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation according to claim 3,
Be characterized in the organic solvent be methanol, ethyl alcohol, ethylene glycol, tetrahydrofuran, methylene chloride, acetone, ethyl acetate, benzene, toluene,
N,N-Dimethylformamide.
5. a kind of method that 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation according to claim 1,
It is characterized in that the aqueous slkali is sodium hydroxide, sodium carbonate, sodium bicarbonate, ammonium hydroxide.
6. a kind of method that 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation according to claim 1,
It is characterized in that the catalyst is loaded catalyst.
7. a kind of method that 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation according to claim 6,
The metal for being characterized in the catalyst load is the one or two of Ag, Co, Ni, Cu, Fe, and two kinds of its mass ratioes are 0.001-
1000。
8. a kind of method for preparing 5 methyl furfural by 5 hydroxymethyl furfural selective oxidation according to claim 6, special
Sign is that the catalyst carrier is active carbon, hydrotalcite, titanium dioxide, zirconium dioxide, silica, aluminium oxide or four oxidations three
Iron.
9. a kind of method that 5-HMFA is prepared by 5 hydroxymethyl furfural selective oxidation according to claim 6,
It is characterized in that the stabilizer is PVP (polyvinylpyrrolidone), PVA (polyvinyl alcohol), the molar ratio with metal load content
For 0.01-100.
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