A kind of method of being prepared furyl dimethyl carbinol dialkyl ether by sugar
Technical field
The present invention relates to a kind of method of being prepared furyl dimethyl carbinol dialkyl ether by sugar, under an acidic catalyst and the simultaneous condition of hydrogenation catalyst, adopt single stage method to complete sugared dehydration, hydrogenation, etherificate specifically, prepare corresponding furyl ethers product.
Background technology
Along with not day by day consumption of renewable resource such as oil; in the urgent need to finding fuel and the Essential Chemistry product of energy petroleum replacing; utilize biomass to replace that oil is prepared chemical and fuel is one of feasible program solving world energy sources crisis, from the general chemical of reproducible biomass resource preparation, become the study hotspot of domestic and international resource and energy field.Wherein, take biomass sugar source can prepare Important Platform compound 5 hydroxymethyl furfural (HMF) as raw material, in HMF molecule, contain aldehyde radical and methylol, its structure less stable, be easy to polymerization, and boiling point is higher, so HMF itself do not have larger purposes, but HMF can synthetic fuel additive dimethyl furan as a kind of important chemical intermediate and the high valuable chemicals such as polymer monomer furandicarboxylic acid, furans dicarbaldehyde, furyl dimethyl carbinol.On the other hand, ethers molecule is widely used as vehicle fuel or additive, methyl tertiary butyl ether (MTBE), tert pentyl methyl ether (TAME), diisopropyl ether (DIPE) and Ethyl Tertisry Butyl Ether (ETBE), dme are all used as petrol and diesel oil octane promoter, and MTBE is because environmental protection reason is forbidden gradually by states such as America and Europes.Therefore from HMF, the petrol and diesel oil octane promoter furyl dimethyl carbinol dialkyl ether of Development of Novel will have boundless market outlook.Same methyl tertiary butyl ether (MTBE), tert pentyl methyl ether (TAME), diisopropyl ether (DIPE), Ethyl Tertisry Butyl Ether (ETBE), dme etc. are compared, furyl dimethyl carbinol dialkyl ether has higher oxygen level, is more suitable for as petrol and diesel oil octane promoter.
With dimethyl furan, compare, from the synthetic furyl dimethyl carbinol dialkyl ether of HMF, only need to consume a part hydrogen, retained 95% of HMF molecular weight, from HMF synthesization of dimethyl furans, need to consume three molecular hydrogens, retained 76% of HMF molecular weight, the economic attractiveness of this process is poor.
Although the people such as Gruter have reported 5 hydroxymethyl furfural or 5-alkoxymethylfurfural and can be converted into furyl dimethyl carbinol dialkyl ether under hydrogenation catalyst and the simultaneous conditions of an acidic catalyst in its patent (EP2008/007423), but 5 hydroxymethyl furfural and 5-alkoxymethylfurfural are expensive, obtaining of raw material is very difficult.The people such as Gruter point out in its patent (200880106056.8, EP2008/007428), raw material containing C5 and C6 sugar reacts and can generate furfural and 5-alkoxymethylfurfural under an acidic catalyst exists with alcohol, the aldehyde radical of furfural and 5-alkoxymethylfurfural can change alkoxyl-methyl group into after hydrogenation etherificate, but he does not propose the concrete method for transformation of aldehyde radical, and this reaction process is to set up sugar to be converted in advance on the basis of furfural and 5-alkoxymethylfurfural, step is various, complex process, energy consumption is high.One kettle way from sugar to furyl dimethyl carbinol dialkyl ether transforms and there is no at present bibliographical information.
Summary of the invention
The object of the invention is to provide a kind of method of being prepared furyl dimethyl carbinol dialkyl ether by sugar.
For achieving the above object, the technical solution used in the present invention is:
A kind of method of being prepared furyl dimethyl carbinol dialkyl ether by sugar, after sugar is dissolved with alcohol, add again hydrogenation catalyst, an acidic catalyst, and pass into hydrogen under 0.1MPa~10MPa pressure, when temperature reaches 40 ℃~200 ℃ hydrogenation etherification reactions 0.1~24 hour, obtain furyl dimethyl carbinol dialkyl ether.
After sugar is dissolved with alcohol, then add hydrogenation catalyst, an acidic catalyst, and pass into hydrogen under 0.1MPa~10MPa pressure, when temperature reaches 40 ℃~200 ℃ hydrogenation etherification reactions 0.1~24 hour, obtain furyl dimethyl carbinol dialkyl ether; Described hydrogen catalyst and sugared mass ratio are 1: 0.0001~10; An acidic catalyst and sugared mass ratio are 1: 0.0001~10.
The described concentration with sugar soln after alcohol dissolving can be 0.001g/mL~1g/mL.Described sugar is glucose, fructose, inulin, sucrose, inulin, cellobiose or starch.Described hydrogenation catalyst is comprised of active constituent and carrier, the mass ratio of active constituent and carrier is 1: 0.005~0.5, active constituent is simple substance or its compound of Pt, Rh, Ir, Ru, Pd, Ni, Cu, Co, W, Mo element, or the combination of above-mentioned two or more element of simple substance; Carrier is solid acid carrier.Described solid acid carrier is Al
2o
3, SiO
2, ZrO
2, diatomite, molecular sieve or gac.The described solvent for dissolving sugar is one or more of methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol.Described an acidic catalyst is solid acid catalyst.Described solid acid catalyst is ZSM-5, ZSM-12, ZSM-23, ZSM-48, acidic beta molecular sieve, mordenite, ferrierite or acidic ion exchange resin; Described acidic ion exchange resin is as Amberlyst-15, Amberlyst-70 etc.
The advantage that the present invention has is: it is raw material that the present invention has selected sugar cheap and easy to get, only need single step reaction just sugar can be converted into furyl dimethyl carbinol dialkyl ether, technique is simple, reaction conditions is gentleer, avoided the corrosion of liquid acid to equipment, energy consumption is low, catalyzer, the easily separated purification of product, catalyzer and solvent can repeatedly recycle, and greatly reduce the production cost of furyl dimethyl carbinol dialkyl ether.
Attached body explanation
Fig. 1 prepares the high resolution mass spectrum figure of furyl dimethyl carbinol dme for what the embodiment of the present invention provided by sugar.
Fig. 2 prepares the mass spectrum of furyl dimethyl carbinol dme for what the embodiment of the present invention provided by sugar.
The nmr spectrum of preparing furyl dimethyl carbinol dme by sugar that Fig. 3 provides for the embodiment of the present invention (wherein
1h NMR (a) and
13c NMR (b)).
Fig. 4 prepares the nmr spectrum of furyl dimethyl carbinol diethyl ether for what the embodiment of the present invention provided by sugar.
Fig. 5 prepares the nmr spectrum of furyl dimethyl carbinol dipropyl ether for what the embodiment of the present invention provided by sugar.
Fig. 6 prepares the nmr spectrum of furyl dimethyl carbinol dibutyl ether for what the embodiment of the present invention provided by sugar.
Embodiment
The method of being prepared furyl dimethyl carbinol dialkyl ether by sugar: after sugar is dissolved with alcohol, pour in autoclave, and add hydrogenation catalyst, an acidic catalyst in reactor, with hydrogen, wash still three times, be filled with the hydrogen of certain pressure, after temperature reaches established temperature, open to stir and carry out hydrogenation etherification reaction, after finishing, reaction removes by filter hydrogenation catalyst, an acidic catalyst, underpressure distillation evaporates alcohol, further improves the temperature of underpressure distillation, steams furyl dimethyl carbinol dialkyl ether.
Reaction formula is,
Embodiment 1
The preparation of furyl dimethyl carbinol dme
After 5g fructose is dissolved in to 50mL methyl alcohol, pour in autoclave, add afterwards 0.5gNi/Al
2o
3hydrogenation catalyst and 0.5g ZSM-5 acidic molecular sieve (Si/Al=25), be filled with 2.5MPaH
2, when temperature reaches 120 ℃, open to stir and react, after reaction 6h, treat that temperature drops to room temperature, remove by filter catalyzer, the methanol solution underpressure distillation of product is removed after methyl alcohol, further improves the temperature of underpressure distillation, steam furyl dimethyl carbinol dme, productive rate 35%.
The furyl dimethyl carbinol dme obtaining records its boiling point at 166~168 ℃, density 1.062g/mL; Miscible with arbitrary proportion with octane, (referring to Fig. 1,2 and 3) completely do not dissolve each other with n-hexadecane.
The preparation of embodiment 2 furyl dimethyl carbinol diethyl ether:
After 5g fructose is dissolved in to 50mL ethanol, pour in autoclave, add afterwards 0.5gNi/Al
2o
3hydrogenation catalyst and 0.5g ZSM-5 acidic molecular sieve (Si/Al=25), be filled with 2.5MPa H
2, when temperature reaches 120 ℃, open to stir and react, after reaction 8h, treat that temperature drops to room temperature, remove by filter catalyzer, the ethanolic soln underpressure distillation of product is removed after ethanol, further improves the temperature of underpressure distillation, steam furyl dimethyl carbinol diethyl ether, productive rate 30%.
The furyl dimethyl carbinol diethyl ether (referring to Fig. 4) steaming
The preparation of embodiment 3 furyl dimethyl carbinol dipropyl ether
After 5g glucose is dissolved in to 50mL propyl alcohol, pour in autoclave, add afterwards 0.5g Pt/C hydrogenation catalyst and 0.5g Amberlyst-15, be filled with 2.5MPa H
2, when temperature reaches 120 ℃, open to stir and react, after reaction 10h, treat that temperature drops to room temperature, remove by filter catalyzer, the propanol solution underpressure distillation of product is removed after propyl alcohol, further improves the temperature of underpressure distillation, steam furyl dimethyl carbinol dipropyl ether, productive rate 32%.The furyl dimethyl carbinol dipropyl ether (referring to Fig. 5) steaming
The preparation of embodiment 4 furyl dimethyl carbinol dibutyl ethers
5g sucrose dissolved is poured in autoclave after 50mL butanols, added afterwards 0.5g Pd/C hydrogenation catalyst and 0.5g Amberlyst-15, be filled with 2.5MPa H
2, when temperature reaches 120 ℃, open to stir and react, after reaction 12h, treat that temperature drops to room temperature, remove by filter catalyzer, the butanol solution underpressure distillation of product is removed after butanols, further improves the temperature of underpressure distillation, steam furyl dimethyl carbinol dibutyl ether, productive rate 34%.The furyl dimethyl carbinol dibutyl ether (referring to Fig. 6) steaming
The preparation of embodiment 5 furyl dimethyl carbinol diisobutyl ethers
After 5g inulin is dissolved in to 50mL isopropylcarbinol, pour in autoclave, add afterwards 0.5g Ru/C hydrogenation catalyst and 0.5g Amberlyst-15, be filled with 2.5MPa H
2, when temperature reaches 140 ℃, open to stir and react, after reaction 16h, treat that temperature drops to room temperature, remove by filter catalyzer, the isobutanol solution underpressure distillation of product is removed after isopropylcarbinol, further improves the temperature of underpressure distillation, steam furyl dimethyl carbinol diisobutyl ether, productive rate 33%.