CN104250256B - A kind of method preparing isosorbide ether - Google Patents
A kind of method preparing isosorbide ether Download PDFInfo
- Publication number
- CN104250256B CN104250256B CN201310273317.8A CN201310273317A CN104250256B CN 104250256 B CN104250256 B CN 104250256B CN 201310273317 A CN201310273317 A CN 201310273317A CN 104250256 B CN104250256 B CN 104250256B
- Authority
- CN
- China
- Prior art keywords
- isosorbide
- ethanol
- acid
- accordance
- etherification reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/04—Ortho-condensed systems
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
Abstract
The present invention relates to a kind of isosorbide and method that ethanol directly etherificate prepares isosorbide ether.Directly being etherified synthesis 2 ethyoxyl isosorbide (2 MEI), 5 ethyoxyl isosorbide (5 MEI) and isosorbide diethyl ether (DEI) with isosorbide and ethanol under acidic catalyst effect for raw material, gained isosorbide ether total recovery is up to more than 65%.The present invention uses the method that environmentally friendly acidic catalyst catalysis isosorbide is directly etherified with ethanol, avoid introducing and the generation of a large amount of halide salt by-product of high toxicity halogenated hydrocarbons, avoid the corrosion problems caused by strong acid, highly basic, it is provided that a kind of green synthesis method efficiently preparing isosorbide, diethyl ether.
Description
Technical field
The present invention relates to a kind of method preparing isosorbide ether, specifically acidic catalyst catalysis isosorbide
Preparation 2-ethyoxyl isosorbide (2-MEI), 5-ethyoxyl isosorbide (5-MEI) and isosorbide directly it is etherified with ethanol
Diethyl ether (DEI).
Background technology
Fossil resource is that the survival and development of human society provide the necessary energy and chemicals guarantee.Along with fossil provides
What day by day exhausted, the greenhouse gases in source endangered highlights further, seeks Renewable resource and substitutes fossil resource to obtain fuel and change
The research of product more and more receives significant attention.Biomass can convert as renewable organic carbonaceous resource prepares fuel and chemistry
Product, provide a sustainable route for social development.
Isosorbide is a kind of important biomass-based compound, and it can be by the hydrogenation products sorbitol of glucose through two steps
Dehydration obtains.Isosorbide is an asymmetric diatomic alcohol compounds in " V " type structure, specifically comprises two tetrahydrochysenes condensed
Furan nucleus and be respectively at (C in face2), (C outside face5) secondary hydroxyl.Wherein, it is positioned at C5The hydroxyl of position and adjacent oxolane
The oxygen atom of ring can form intramolecular hydrogen bond, and is positioned at C2The hydroxyl of position then can not be formed, and causes the reactivity of two hydroxyls
There are differences.In view of the characteristic of its molecular structure, isosorbide derivatives is in green solvent, chiral liquid crystal material, surface activity
The fields such as agent, medicine, polymer and liquid fuel have broad application prospects.
It is worth noting, the etherification derivative of isosorbide because of green solvent, fuel, chiral auxiliary, cosolvent and
The potential application of the aspects such as polymer and enjoy researcher favor (see Palkovits etc., ChemSusChem, 2012,5,
167).Wherein, isosorbide dimethyl ether realizes commercially producing as green high boiling organic solvent.
At present, isosorbide etherate preparation method concentrates on the selection of etherifying reagent and the exploitation of catalyst, can conclude
For following several synthetic methods.(1) isosorbide and halogenated hydrocarbons occur williamson to react under highly basic effect.Loupy etc.
Under strongly alkaline conditions, utilize Microwave-assisted firing, use phase transfer catalyst efficient catalytic isosorbide to convert with bromooctane
Generate isosorbide dioctyl ether, yield up to 90%(Loupy etc., Tetrahedron Lett., 2000,41,3367).Gao Zhengsong
Deng elaborating in CN101445508 with low molecular polyether as solvent, phase transfer catalyst efficient catalytic isosorbide and chlorine
Methane is etherified, and gained isosorbide dimethyl ether yield is up to 95%.But, the high toxicity of halogenated hydrocarbons and a large amount of by-product halogenation
The generation of salt all limits the application of the method.(2) there is etherification reaction in isosorbide and dimethyl carbonate in the presence of highly basic.
Tundo etc., in the presence of Feldalat NM, utilize green solvent dimethyl carbonate for etherifying reagent, and high selectivity prepares isosorbide two
Methyl ether, yield is up to 98%(Tundo etc., ChemSusChem, 2010, and 3,566).(3) isosorbide and alkene occur etherificate anti-
Should.Sauthier etc. report catalyst Pd-TPPTS efficient catalytic isosorbide and 1,3-butadiene telomerisation, wherein, different
Sorbitol converts completely, and isosorbide monoether selectivity reaches 94%.But the multiformity of isosorbide ether substituent structure causes different
Sorbitol etherification product kind is complicated, and the method can not the synthesis of alkyl carbon number isosorbide ether less than 8 (Sauthier etc.,
ChemSusChem, 2011,4,1104).Afterwards, Palkovits etc. use acid-exchange resin Amberlyst-15 catalysis
Isosorbide is etherified with isobutene., it is thus achieved that total recovery is the tertiary butyl ether of isosorbide of 97%, and wherein, diether yield reaches 55%
(Palkovis etc., Catal.Sci.Technol., 2013,3,938).(4) isosorbide and alcohol are direct under acid catalysis
Etherificate.Recently, Decampo etc. are found that Lewis acid Bi (OTf)3Directly it is etherified to have with butanol to isosorbide and preferably urges
Changing activity, isosorbide butyl ether yield is 44%(Decampo etc., Green Chem., 2013,15,901).The same year,
Palkovits etc. use Amberlyst-15 catalysis isosorbide to be directly etherified with the tert-butyl alcohol, and gained isosorbide etherificate is derivative
Thing yield is less than 40%.This is because the reversibility of etherification reaction constrains the degree of etherification reaction under acidic catalysis conditions.Combine
On, the preparation process of isosorbide etherification derivative exists with high toxicity halogenated hydrocarbons as etherifying reagent, or uses deep-etching
Property acid, alkali be catalyst, or by-product is more, or the problems such as etherification product yield is low, limits isosorbide ether
The development of compound and application, therefore seek efficient, green etherification method and have important scientific meaning and application prospect.Based on
This, the green syt route that acid catalysis isosorbide and ethanol are directly etherified can effectively solve the problems referred to above.The present invention is with source
The most biomass-based ethanol is etherifying reagent, achieves acidic catalyst catalysis isosorbide first and is directly etherified system with ethanol
Standby 2-ethyoxyl isosorbide (2-MEI), 5-ethyoxyl isosorbide (5-MEI) and isosorbide diethyl ether (DEI).
Summary of the invention
It is an object of the invention to provide one and prepared isosorbide, diethyl ether by isosorbide and ethanol directly etherificate
Green synthesis method, to avoid the introducing of high toxicity halogenated hydrocarbons, the generation of a large amount of by-product halide salt and strong acid, highly basic institute
The corrosion problems caused, it is possible to efficient catalytic isosorbide and ethanol etherificate prepare isosorbide ether.
For achieving the above object, the technical solution used in the present invention is:
A kind of method preparing isosorbide ether, with isosorbide and ethanol as raw material, under acidic catalyst effect,
Directly etherificate preparation 2-ethyoxyl isosorbide (2-MEI), 5-ethyoxyl isosorbide (5-MEI) and isosorbide diethyl ether
(DEI).
According to the present invention, the acidic catalyst that etherification reaction uses is selected from heteropoly acid, ion exchange resin, zeolite, solid
The one of super acids.In some specific embodiment, the preferred phosphorus heteropoly tungstic acid of heteropoly acid, phosphato-molybdic heteropolyacid, silicotungstic heteropolyacid,
Silicon-molybdenum heteropoly acid, germanium heteropoly tungstic acid, germanomolybdate, boron heteropoly tungstic acid or cobalt heteropoly tungstic acid；In some specific embodiment,
Select ion exchange resin be sulfonic acid ion exchange resin, preferably Amberylst-15, Amberlyst-35,
Amberlyst-70 or Nafion-H；In some specific embodiment, zeolite solid acid divides selected from H-β, H-Y or H-ZSM-5
Son sieve；In some specific embodiment, solid super-strong acid preferably sulfuric acid zirconium oxide, sulfated alumina, sulphation aoxidize
Titanium.
According to the present invention, acidic catalyst consumption is the 0.2～50% of isosorbide quality, preferably 2～40%, more preferably 5
～30%.When catalyst amount is less than 0.2%, reactant molecule contacts with catalyst and the most fully causes isosorbide conversion ratio
Low；When catalyst amount is higher than 50%, its catalytic result and catalyst amount are that the result of 50% is without significant difference.
According to the present invention, preparation process is to carry out in closed reactor, acid catalysis isosorbide and ethanol etherification reaction
It is at self-generated pressure or to be pre-charged with under 0.5～3MPa condition of nitrogen gas carrying out.
According to the present invention, isosorbide and ethanol etherification reaction temperature are 120～260 ° of C, and preferably 130～240 ° C are more excellent
Select 140～220 ° of C.When reaction temperature is less than 120 ° of C, the energy that low temperature provides is far below isosorbide and ethanol etherification reaction
Activation energy, therefore etherification reaction can not be carried out；When reaction temperature is higher than 260 ° of C, side reaction aggravates, and generates the most black in reaction system
Color insoluble matter, reduces the effective rate of utilization of isosorbide.
According to the present invention, isosorbide and ethanol etherification reaction time are 0.25～24 hour, preferably 0.5～20 hour,
More preferably 1～15 hour.After response time was more than 24 hours, owing to isosorbide and ethanol etherification reaction are balancing response, continue
Long response time that renews is unhelpful to etherification reaction result, can aggravate the generation of side reaction on the contrary, cause etherification product yield to reduce.
And, the response time affects the distribution of isosorbide etherification product.
According to the present invention, ethanol is 0.25～100:1 with the mol ratio of isosorbide, preferably 0.5～70:1, more preferably 1
～50:1.When ethanol is less than 0.25:1 with isosorbide ratio, the atom utilization of isosorbide substantially reduces, economic benefit
Low；When the molar ratio of ethanol and isosorbide is higher than 100:1, acidic catalyst is reduced by ethanol dilution, acid strength, causes different
Sorbitol conversion ratio reduces.
According to the present invention, in etherification reaction system in addition to raw material without or be added with the one in etherificate solvent or two kinds
Above；Described etherificate solvent selected from dimethyl sulfoxide, sulfolane, oxolane, 1,4-dioxane, benzene, toluene or hexamethylene
The mixture of one or two or more kinds of alkane.Above-mentioned solvent plays dissolving reactant and catalyst, dispersion reaction system and promotion
Isosorbide conversions etc. act on.Etherification reaction solvent load is 0.1～50 times of isosorbide quality, preferably 0.5～40 times, more
Preferably 1.5～30 times.When reaction dissolvent consumption is less than 0.1 times of isosorbide quality, reaction system excessively thickness, it is unfavorable for anti-
Answer the dispersion of thing；When reaction dissolvent consumption is higher than 50 times of isosorbide quality, substrate and catalyst, by excess dilution, are unfavorable for
Isosorbide etherification reaction is carried out.The consumption of etherification reaction solvent is 0.1～50 times of isosorbide quality, preferably 0.5～40
Times, more preferably 1.5～30 times.
The present invention is that a kind of acid catalysis isosorbide prepares isosorbide, the green syt side of diethyl ether with ethanol etherificate
Method, solves isosorbide and ethanol and is directly etherified the problems such as the isosorbide ether yield of existence is low, catalyst activity is low.
Present invention have the advantage that
1. compared with the method for isosorbide and halohydrocarbons reaction ether, the advantage that isosorbide and ethanol are directly etherified
It is that raw material sources are in Renewable resource.Wherein, isosorbide and ethanol are biomass derivatives, wide material sources, and mainly
Etherificate by-product be water, therefore acid catalysis isosorbide and ethanol directly etherificate prepare the conjunction that isosorbide ether is a kind of green
One-tenth method.
2., with the acid catalysis isosorbide mentioned in document compared with etherified method, the present invention achieves acid first and urges
Change isosorbide and ethanol be directly etherified preparation 5-ethyoxyl isosorbide (5-MEI), 2-ethyoxyl isosorbide (2-MEI) and
Isosorbide diethyl ether (DEI), gained isosorbide ether total recovery is up to more than 65%, and this yield is much larger than document report
Result.
3. the present invention uses environmentally friendly acidic catalyst catalysis isosorbide and ethanol to be directly etherified, the acid used
Property catalyst be catalyst amount, slight to the corrosivity of equipment, it is achieved that green, efficient catalytic isosorbide is etherified with ethanol
Preparation 5-ethyoxyl isosorbide (5-MEI), 2-ethyoxyl isosorbide (2-MEI) and isosorbide diethyl ether (DEI).
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but protection scope of the present invention is not limited in
This.
Embodiment 1
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 50:1, and the phosphorus tungsta adding isosorbide quality 5% is many
Acid, with sulfolane for etherification reaction solvent (5 times of isosorbide quality), is pre-charged with 3MPa nitrogen, closed reactor, in
200 ° of C magnetic agitation are reacted 2 hours.Question response device is cooled to room temperature, extracts reaction solution with gas chromatographic analysis, raw material isosorbide
Conversion ratio and etherification product yield are pressed gas chromatogram fixative and are calculated.Gained isosorbide etherification product has the different Pyrusussuriensis of 5-ethyoxyl
Alcohol (5-MEI), 2-ethyoxyl isosorbide (2-MEI) and isosorbide diethyl ether (DEI).Embodiment 2
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 50:1, and the phosphorus tungsta adding isosorbide quality 30% is many
Acid, with sulfolane for etherification reaction solvent (5 times of isosorbide quality), is pre-charged with 3MPa nitrogen, closed reactor, in
200 ° of C magnetic agitation are reacted 2 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 3
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 50:1, and the phosphorus tungsta adding isosorbide quality 50% is many
Acid, with sulfolane for etherification reaction solvent (5 times of isosorbide quality), is pre-charged with 3MPa nitrogen, closed reactor, in
200 ° of C magnetic agitation are reacted 2 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 4
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 0.25:1, adds the Nafion-of isosorbide quality 30%
H, with Isosorbide-5-Nitrae-dioxane for etherification reaction solvent (10 times of isosorbide quality), closed reactor, at 180 ° of C self-generated pressures
Under the conditions of, magnetic agitation is reacted 5 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 5
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 30:1, adds the Nafion-H of isosorbide quality 30%,
With Isosorbide-5-Nitrae-dioxane for etherification reaction solvent (10 times of isosorbide quality), closed reactor, at 180 ° of C self-generated pressure bars
Under part, magnetic agitation is reacted 5 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 6
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 70:1, adds the Nafion-H of isosorbide quality 30%,
With Isosorbide-5-Nitrae-dioxane for etherification reaction solvent (10 times of isosorbide quality), closed reactor, at 180 ° of C self-generated pressure bars
Under part, magnetic agitation is reacted 5 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 7
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 30:1, and the phosphorus molybda adding isosorbide quality 30% is many
Acid, with benzene for etherification reaction solvent (0.5 times of isosorbide quality), closed reactor, under the conditions of 160 ° of C self-generated pressures,
Magnetic agitation is reacted 12 hours.Raw material isosorbide conversion ratio and etherification product yield are calculated by gas chromatogram fixative.
Embodiment 8
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 30:1, and the phosphorus molybda adding isosorbide quality 30% is many
Acid, with benzene for etherification reaction solvent (5 times of isosorbide quality), closed reactor, under the conditions of 160 ° of C self-generated pressures, magnetic
Power stirring reaction 12 hours.Raw material isosorbide conversion ratio and etherification product yield are calculated by gas chromatogram fixative.
Embodiment 9
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 30:1, and the phosphorus molybda adding isosorbide quality 30% is many
Acid, with benzene for etherification reaction solvent (50 times of isosorbide quality), closed reactor, under the conditions of 160 ° of C self-generated pressures, magnetic
Power stirring reaction 12 hours.Raw material isosorbide conversion ratio and etherification product yield are calculated by gas chromatogram fixative.
Embodiment 10
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 100:1, adds the H-Y molecule of isosorbide quality 20%
Sieve, is pre-charged with 3MPa nitrogen, closed reactor, reacts 2 hours in 180 ° of C magnetic agitation.Raw material isosorbide conversion ratio and
Etherification product yield is calculated by gas chromatogram fixative.
Embodiment 11
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 100:1, adds the H-Y molecule of isosorbide quality 20%
Sieve, is pre-charged with 3MPa nitrogen, closed reactor, reacts 2 hours in 200 ° of C magnetic agitation.Raw material isosorbide conversion ratio and
Etherification product yield is calculated by gas chromatogram fixative.
Embodiment 12
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 100:1, adds the H-Y molecule of isosorbide quality 20%
Sieve, is pre-charged with 3MPa nitrogen, closed reactor, reacts 2 hours in 220 ° of C magnetic agitation.Raw material isosorbide conversion ratio and
Etherification product yield is calculated by gas chromatogram fixative.
Embodiment 13
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 30:1, adds the sulphation oxygen of isosorbide quality 30%
Changing zirconium, with hexamethylene for etherification reaction solvent (20 times of isosorbide quality), closed reactor, at 200 ° of C self-generated pressure bars
Under part, magnetic agitation is reacted 0.5 hour.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 14
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 30:1, adds the sulphation oxygen of isosorbide quality 30%
Changing zirconium, with hexamethylene for etherification reaction solvent (20 times of isosorbide quality), closed reactor, at 200 ° of C self-generated pressure bars
Under part, magnetic agitation is reacted 2 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 15
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 30:1, adds the sulphation oxygen of isosorbide quality 30%
Changing zirconium, with hexamethylene for etherification reaction solvent (20 times of isosorbide quality), closed reactor, at 200 ° of C self-generated pressure bars
Under part, magnetic agitation is reacted 6 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 16
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 20:1, and the silicon tungsta adding isosorbide quality 30% is many
Acid, is etherification reaction solvent (15 times of isosorbide quality) with dimethyl sulfoxide (5 times of isosorbide quality) and hexamethylene,
Closed reactor, is pre-charged with 3MPa nitrogen, reacts 10 hours in 170 ° of C magnetic agitation.Raw material isosorbide conversion ratio and ether
Change product yield to be calculated by gas chromatogram fixative.
Embodiment 17
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 20:1, and the germanium tungsta adding isosorbide quality 30% is many
Acid, with toluene for etherification reaction solvent (0.1 times of isosorbide quality), closed reactor, is pre-charged with 3MPa nitrogen, in
200 ° of C magnetic agitation are reacted 4 hours.Raw material isosorbide conversion ratio and etherification product yield are by gas chromatogram fixative meter
Calculate.
Embodiment 18
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 5:1, adds the Amberlyst-of isosorbide quality 30%
15, with oxolane for etherification reaction solvent (3 times of isosorbide quality), closed reactor, it is pre-charged with 0.5MPa nitrogen,
React 24 hours in 120 ° of C magnetic agitation.Raw material isosorbide conversion ratio and etherification product yield pass through gas chromatogram fixative
Calculate.
Embodiment 19
In typical preparation, isosorbide and ethanol etherification reaction are to carry out in closed reactor.By ethanol and different
Sorbitol is put in stainless steel cauldron according to the ratio of mol ratio 50:1, adds the H-ZSM-5 of isosorbide quality 0.2%
Molecular sieve, closed reactor, under 260 ° of C self-generated pressures, magnetic agitation is reacted 0.25 hour.Raw material isosorbide conversion ratio and
Etherification product yield is calculated by gas chromatogram fixative.
Use the method described in embodiment 1～19, the reaction result that acidic catalyst catalysis isosorbide is etherified with ethanol
It is listed in table 1.
Table 1:
Above-described embodiment 1～19 result shows the acidic catalysts such as heteropoly acid, ion exchange resin, zeolite, solid super-strong acid
Isosorbide and ethanol are directly etherified by agent has more excellent catalytic performance, and adds suitable etherificate solvent and can remarkably promote
Isosorbide converts, and increases etherification product yield.
Embodiment 1～3 result shows with phosphotungstic acid as catalyst, when fixing other reaction conditions, increases catalysis of phosphotungstic acid
Agent consumption, isosorbide conversion ratio and isosorbide ether total recovery increase therewith.When catalyst amount increases to isosorbide matter
Amount 50% time, isosorbide ether total recovery increases slowly, and isosorbide diethyl ether (DEI) yield substantially increases.
Embodiment 4～6 result shows with sulfonic acid ion exchange resin Nafion-H as catalyst, fixes other reactions
During condition, when using the mol ratio of relatively low ethanol and isosorbide, primary product is isosorbide ether products (5-MEI, 2-
MEI), when improving ratio, two ether products DEI yields dramatically increase, but isosorbide conversion ratio slightly reduces.
Embodiment 7～9 result shows with phosphomolybdic acid as catalyst, and benzene is etherification reaction solvent, fixes other reaction conditions
Time, increasing etherification reaction solvent load, isosorbide conversion ratio and etherification product total recovery thereof increase therewith.
Embodiment 10～12 result shows with H-Y molecular sieve as catalyst, when fixing other reaction conditions, and reaction temperature liter
High beneficially isosorbide converts and DEI generates, and higher than after uniform temperature, isosorbide ether total recovery increase trend is relatively
Slow.
Embodiment 13～15 result shows with sulfated zirconia as catalyst, when fixing other reaction conditions, along with instead
Prolongation between Ying Shi, isosorbide conversion ratio is gradually increased, 2-MEI and DEI yield is in increasing trend, and 5-MEI yield first increases
Reduce after adding, show that the response time affects the distribution of isosorbide etherification product.
Claims (13)
1. the method preparing isosorbide ether, it is characterised in that: described preparation process is carried out in closed reactor,
With isosorbide and ethanol as raw material, the most directly etherificate preparation 2-ethyoxyl isosorbide (2-MEI),
5-ethyoxyl isosorbide (5-MEI) and isosorbide diethyl ether (DEI)；
Etherification reaction system is added with in addition to raw material one or two or more kinds in etherificate solvent；
Described etherificate solvent is selected from dimethyl sulfoxide, sulfolane, oxolane, 1,4-dioxane, benzene, toluene or hexamethylene
The mixture of one or two or more kinds.
The most in accordance with the method for claim 1, it is characterised in that: described urges with the acidity that ethanol is etherified for isosorbide
Agent one in heteropoly acid, ion exchange resin, zeolite, solid super-strong acid.
The most in accordance with the method for claim 1, it is characterised in that: the preferred phosphorus heteropoly tungstic acid of described heteropoly acid, phosphorus molybda are many
One in acid, silicotungstic heteropolyacid, silicon-molybdenum heteropoly acid, germanium heteropoly tungstic acid, germanomolybdate, boron heteropoly tungstic acid or cobalt heteropoly tungstic acid
Or more than two kinds.
The most in accordance with the method for claim 1, it is characterised in that: described ion exchange resin is sulfonic acid type cation exchange
Resin.
The most in accordance with the method for claim 4, it is characterised in that: the preferred Amberlyst-15 of described ion exchange resin,
One or two or more kinds in Amberlyst-35, Amberlyst-70 or Nafion-H.
The most in accordance with the method for claim 1, it is characterised in that: described zeolite preferred H-β, H-Y or H-ZSM-5 molecular sieve
In one or two or more kinds；
Described solid super-strong acid preferably sulfuric acid zirconium oxide, sulfated alumina, the one of sulphation titanium oxide or two kinds with
Upper combination.
The most in accordance with the method for claim 1, it is characterised in that: acidic catalyst consumption be isosorbide quality 0.2～
50%.
The most in accordance with the method for claim 1, it is characterised in that: acid catalysis isosorbide and ethanol etherification reaction are spontaneous
Pressure or be pre-charged with under 0.5～3MPa condition of nitrogen gas carrying out.
The most in accordance with the method for claim 1, it is characterised in that: etherification reaction temperature is 120～260 DEG C.
The most in accordance with the method for claim 9, it is characterised in that: etherification reaction temperature preferably 140～200 DEG C.
11. in accordance with the method for claim 1, it is characterised in that: the etherification reaction time is 0.25～24 hour.
12. in accordance with the method for claim 1, it is characterised in that: ethanol is 0.25～100 with the mol ratio of isosorbide:
1。
13. in accordance with the method for claim 1, it is characterised in that:
The consumption of etherification reaction solvent is 0.1～50 times of isosorbide quality.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310273317.8A CN104250256B (en) | 2013-06-28 | 2013-06-28 | A kind of method preparing isosorbide ether |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310273317.8A CN104250256B (en) | 2013-06-28 | 2013-06-28 | A kind of method preparing isosorbide ether |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104250256A CN104250256A (en) | 2014-12-31 |
| CN104250256B true CN104250256B (en) | 2016-12-28 |
Family
ID=52185535
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310273317.8A Active CN104250256B (en) | 2013-06-28 | 2013-06-28 | A kind of method preparing isosorbide ether |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104250256B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR2994183B1 (en) * | 2012-08-06 | 2015-07-31 | Roquette Freres | PROCESS FOR PREPARING DIALKYLOXYDIANHYDROHEXITOLS BY ETHERIFYING DIANHYDROHEXITOLS WITH LIGHT ALCOHOL IN THE PRESENCE OF AN ACIDIC CATALYST |
| CN104888859A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Silicon dioxide loaded fluorapatite composite solid acid catalyst and preparation method thereof |
| CN104888861A (en) * | 2015-05-13 | 2015-09-09 | 安徽金邦医药化工有限公司 | Aluminum oxide loaded polyamide short fiber composite solid acid catalyst, and preparation method thereof |
| EP3728389B1 (en) | 2017-12-21 | 2021-11-17 | Elantas Europe Srl | New use of isosorbide |
| CN108569956A (en) * | 2018-06-06 | 2018-09-25 | 江苏创拓新材料有限公司 | The green separation process of Williamson's reaction product system |
| KR102531524B1 (en) * | 2020-10-26 | 2023-05-15 | 주식회사 삼양사 | Method for preparing diether of anhydrosugar alcohol with improved purity |
| CN114621246B (en) * | 2020-12-10 | 2023-08-25 | 中国科学院大连化学物理研究所 | Method for preparing isoidide diacetate |
| CN114621247A (en) * | 2020-12-11 | 2022-06-14 | 中国科学院大连化学物理研究所 | Method for preparing/synthesizing isosorbide methyl ether |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104822683A (en) * | 2012-08-06 | 2015-08-05 | 罗盖特公司 | Method for preparing dialkyloxydianhyrohexitol by etherification of dianhydrohexitol using light alcohol, in presence of acidic catalyst |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BRPI0803522A2 (en) * | 2008-09-17 | 2010-06-15 | Petroleo Brasileiro Sa | diesel cycle fuel compositions containing dianhydrohexitols and derivatives |
| CN101445508B (en) * | 2008-11-21 | 2011-08-31 | 南京威尔化工有限公司 | Method for synthesizing isosorbide dimethyl ether |
-
2013
- 2013-06-28 CN CN201310273317.8A patent/CN104250256B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104822683A (en) * | 2012-08-06 | 2015-08-05 | 罗盖特公司 | Method for preparing dialkyloxydianhyrohexitol by etherification of dianhydrohexitol using light alcohol, in presence of acidic catalyst |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104250256A (en) | 2014-12-31 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104250256B (en) | A kind of method preparing isosorbide ether | |
| Hou et al. | An ionic liquid–organic solvent biphasic system for efficient production of 5-hydroxymethylfurfural from carbohydrates at high concentrations | |
| Ordomsky et al. | Biphasic single-reactor process for dehydration of xylose and hydrogenation of produced furfural | |
| CN103172517B (en) | Methyl methoxyacetate preparation method | |
| CN102040488B (en) | Method for synthesizing PODE (polyformaldehyde dimethyl ether) | |
| CN104829560A (en) | Method of synthesizing 5-hydroxymethyl furfural | |
| CN102212046A (en) | Catalytic system for synthesizing 5-hydroxymethylfurfural by dehydration of sugar or polysaccharide | |
| Yang et al. | Transetherification of guaiacol to o-ethoxyphenol with gamma Al2O3 as a catalyst in supercritical ethanol | |
| CN106866331B (en) | Method for preparing cyclopentadiene or dicyclopentadiene from furfuryl alcohol | |
| CN111995602A (en) | Method for synthesizing 5-hydroxymethylfurfural by utilizing acidic resin to catalyze fructose | |
| Li et al. | Efficient one-pot hydrogenolysis of biomass-derived xylitol into ethylene glycol and 1, 2-propylene glycol over Cu–Ni–ZrO2 catalyst without solid bases | |
| EA036494B1 (en) | Method for directly preparing glycol dimethyl ether and co-producing ethylene glycol from ethylene glycol monomethyl ether | |
| CN103739454B (en) | The technique that after utilizing ether, the C 4 fraction in liquefied gas prepares MTBE | |
| CN105646514B (en) | One kind synthesis 1,4：The method of 3,6 pairs of dewatering hexitol methyl ethers | |
| Li et al. | One pot cascade conversion of furfural to alkyl levulinate over Lu (OTf) 3 without external H2 | |
| CN104725225A (en) | Method for preparing polyoxymethylene dimethyl ether carboxylate and methyl methoxy acetate | |
| CN103420817A (en) | Method for synthesizing polyformaldehyde dimethyl ether from methylal and paraformaldehyde | |
| CN106588596B (en) | The method for purifying polyoxymethylene dimethyl ethers | |
| CN103570485A (en) | Method for preparation of propylene, ethylene, glyoxylic acid, propyl alcohol, ethyl alcohol, propylene glycol, malonic ester and the like by reductive coupling reaction of CO2 or CO | |
| CN109134485B (en) | Method for preparing isosorbide | |
| CN102372561B (en) | Method for preparing ethylene by using ethanol | |
| CN105272810A (en) | Method for separating ethylene/propylene mixed gas | |
| CN103772175B (en) | Combined technique for synthesizing iso-propylidene acetone and sec-butyl alcohol | |
| CN101538195A (en) | Acrylaldehyde preparation method by glycerin dehydration under inert gas dilution | |
| CN111253350A (en) | Method for preparing 5-hydroxymethylfurfural by using chlorohydrin to promote dehydration of saccharide compounds |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |