CN110452197A - A method of synthesis 5 hydroxymethyl furfural - Google Patents
A method of synthesis 5 hydroxymethyl furfural Download PDFInfo
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- CN110452197A CN110452197A CN201910860502.4A CN201910860502A CN110452197A CN 110452197 A CN110452197 A CN 110452197A CN 201910860502 A CN201910860502 A CN 201910860502A CN 110452197 A CN110452197 A CN 110452197A
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- C07—ORGANIC CHEMISTRY
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- C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
- C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
- C07D307/34—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
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Abstract
The present invention provides a kind of method for synthesizing 5 hydroxymethyl furfural, and the raw material of the method is fructose, and reaction system is saturation inorganic salt solution-organic solvent system, and reactor is static mixer, and the flow velocity of solution is 0.1-5m/s in the static mixer；The catalyst of the method is organic acid, inorganic acid, ionic liquid or lewis acid.By flow velocity of the control reaction solution in static mixer, the reaction time is controlled, reaction temperature is preheated in advance, reduces the reaction time substantially, so that residence time of the reactant in system is reduced, by-product is reduced, and the yield of product is up to 99%.
Description
Technical field
The invention belongs to 5 hydroxymethyl furfurals to synthesize field, and in particular to a method of synthesis 5 hydroxymethyl furfural.
Background technique
5 hydroxymethyl furfural (HMF) is a kind of important industrial chemicals, is the original for synthesizing 2,5-furandicarboxylic acid (FDCA)
Material.Although 5 hydroxymethyl furfural has had more than 120 years time now from being found to, do not given birth on a large scale so far
It produces, the main reason is that there is very big difficulties in its preparation and separation process.5 hydroxymethyl furfural mainly passes through grape
The dehydration of the hexoses such as sugar, fructose obtains, and is easy the most wherein obtaining from fructose dehydration, and by other saccharide compounds
Prepare the basis of 5 hydroxymethyl furfural.The method of 5 hydroxymethyl furfural is prepared mainly by following several systems by fructose at present: pure
Aqueous systems, organic system, water phase and an oil phase system, ion liquid system.Although the initial concentration of fructose can be improved in pure aquatic system,
But since with water rehydrated reaction can occur for the 5 hydroxymethyl furfural of generation, levulic acid and formic acid are generated, so that final
5 hydroxymethyl furfural yield is very low.A large amount of experimental study proves, in high boiling organic solvent, 5 hydroxymethyl furfural
Selectivity is higher, such as the selectivity of 5 hydroxymethyl furfural can achieve 99% or more in DMSO.But how from higher boiling
It is an extremely difficult problem that 5 hydroxymethyl furfural is isolated in solvent, even if will also result in using vacuum distillation very big
Product loss.In recent years, ion liquid system is paid close attention to by everybody, can almost be obtained in slave fructose quantitatively in ionic liquid
Obtain 5 hydroxymethyl furfural.But the price of ionic liquid is relatively high, is unfavorable for largely using.And 5- is separated from ionic liquid
Hydroxymethylfurfural is needed using extracting process, and a large amount of low boiling point solvent of using up consumes a large amount of energy.Therefore, water phase and an oil phase
The reaction system of system, especially water and low boiling point organic solvent composition is the body for most holding promise for 5 hydroxymethyl furfural production
System.Dumesic et al. (Science, 2006；Top Catal, 2009) a large amount of research has been done in this respect, it achieves good
Effect, in water-organic solvent system, dehydration occurs in water phase for fructose, then in situ to be extracted in organic phase,
The hydration reaction that 5 hydroxymethyl furfural can effectively be avoided within a certain period of time, improves the selectivity of 5 hydroxymethyl furfural.But
It is if the reaction time is longer, the 5 hydroxymethyl furfural for being extracted to organic layer can be stripped into water phase, and in water phase
Hydration reaction occurs, generating levulic acid and formic acid, the selectivity of 5 hydroxymethyl furfural can also reduce.
Summary of the invention
Based on above background technique, the purpose of the present invention is to provide a kind of sides for efficiently synthesizing 5 hydroxymethyl furfural
Method adopts the following technical scheme that:
The present invention provides a kind of method for synthesizing 5 hydroxymethyl furfural, and the raw material of the method is fructose, and reaction system is
It is saturated inorganic salt solution-organic solvent system, reactor is static mixer, and the flow velocity of solution is in the static mixer
0.1-5m/s；The catalyst of the method is organic acid, inorganic acid, acidic ion liquid or lewis acid.
Based on above technical scheme, it is preferred that the organic solvent is tetrahydrofuran, n-butanol, 2- butanol, butanone, first
Base isobutyl ketone, 2- methyltetrahydrofuran.
Based on above technical scheme, it is preferred that the inorganic salts are potassium chloride, sodium chloride, sodium sulphate, potassium sulfate, bromination
Potassium, sodium bromide, potassium iodide, sodium iodide, lithium chloride.
Based on above technical scheme, it is preferred that the tube length of reaction tube of the static mixer is 10-200m, preferably 60m.
Based on above technical scheme, it is preferred that described method includes following steps:
(1) saturation inorganic salt solution and fructose are mixed to get fructose soln, catalyst is added to the fructose soln
In obtain reaction solution；The mass fraction of fructose is 5-60wt% in the fructose soln；
(2) organic solvent and the reaction solution are injected into static mixer by conveying equipment respectively, is controlled in 160-
It is reacted at 240 DEG C；
(3) the cooling, stratification by the reaction solution effluent of static mixer in step (2), upper layer is organic phase, lower layer
For saturated sodium-chloride water phase, then the organic layer on upper layer is evaporated under reduced pressure to obtain the 5 hydroxymethyl furfural by liquid separation.
Based on above technical scheme, it is preferred that the mass fraction of the catalyst is the 0.1% of the reaction solution；Institute
Stating catalyst is organic acid, inorganic acid, acidic ion liquid or lewis acid.
Based on above technical scheme, it is preferred that the inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid；
The organic acid is formic acid, acetic acid, propionic acid；
The lewis acid is aluminium chloride, iron chloride, aluminum sulfate, aluminum nitrate, ferric nitrate, chromic nitrate, chromium chloride；
The acidic ion liquid is 1- (3- sulfonic group propyl) -3- methylimidazolium hydrogen sulphate salt, 1- (3- sulfonic group third
Base) -3- methylimidazole villaumite, 1- (3- sulfonic group propyl) -3- methylimidazole bromide, 1- (3- sulfonic group propyl) -3- methyl miaow
Azoles acetate, 1- (3- sulfonic group propyl) -3- methylimidazole hexafluorophosphate, 1- (3- sulfonic group propyl) -3- methylimidazole four
Borofluoride, 1- (3- sulfonic group propyl) -3- methylimidazolium nitrate, 1- (3- sulfonic group propyl) -3- methylimidazole di(2-ethylhexyl)phosphate
Hydrogen salt, 1- (4- sulfonic group butyl) -3- methylimidazolium hydrogen sulphate salt, 1- (4- sulfonic group butyl) -3- methylimidazole villaumite, 1-
(4- sulfonic group butyl) -3- methylimidazole bromide, 1- (4- sulfonic group butyl) -3- methylimidazole acetate, 1- (4- sulfonic group fourth
Base) -3- methylimidazole hexafluorophosphate, 1- (4- sulfonic group butyl) -3- methyl imidazolium tetrafluoroborate, 1- (4- sulfonic group fourth
Base) -3- methylimidazolium nitrate, 1- (4- sulfonic group butyl) -3- methylimidazole dihydric phosphate.
Based on above technical scheme, it is preferred that the isometric organic solvent of saturated sodium-chloride water phase in step (3)
(tetrahydrofuran) extraction, organic layer extracted merge vacuum distillation with organic layer described in step (3), obtain the 5-
Hydroxymethylfurfural and recycling organic solvent；Saturated sodium-chloride water layer extracted is recycled after adding fructose.
Based on above technical scheme, it is preferred that the flow velocity of solution is 0.1-5m/s, preferably 1m/s in static mixer.
Based on above technical scheme, it is preferred that the volume ratio of organic solvent described in step (2) and reactant solution is 1:
1-20:1。
Beneficial effect
(1) in synthetic method of the invention, organic phase is first preheated to reaction temperature, then squeezes into reaction together with water phase
Device can play the role of being rapidly heated avoiding during rising to reaction temperature from room temperature so as to shorten the reaction time in this way
The generation of side reaction reduces the hydrolysis of 5 hydroxymethyl furfural, improves the yield of 5 hydroxymethyl furfural.
(2) the extractant toxicity that the present invention uses is smaller, smaller to the harm of environment, uses the saturation inorganic salts of high concentration
Solution so that product organic-aqueous phase distribution coefficient increase, guarantee diphasic system formation while, be conducive to product to
The transfer of organic phase.
(3) present invention uses static mixer, and compared to traditional high-pressure reactor, the present invention is existed by controlling reaction solution
Flow velocity in static mixer controls the reaction time, reduces the reaction time substantially, so that when stop of the reactant in system
Between reduce, by-product is reduced, and the yield of product is 61-99%.Compared with tank reactor, static mixing of the present invention
Device is that raw material can be continuously added from reactor front end, from reactor with quantity-produced reactor in one kind into reactor
Liquid after the continuous output-response in rear end, and liquid and new plus raw material air-teturning mixed phenomenon after will not reacting, do not need yet
By cooling down, opening the processes such as kettle, production efficiency can be improved.
Specific embodiment
Static mixer used in the present invention is general commercially available or commercial static mixer.
Embodiment 1
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.Fructose soln by 200 DEG C of tetrahydrofuran is preheated to and containing catalyst pass through respectively two constant flow pumps of A, B by
According to 1m/s flow injection have been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and
The volume ratio of fructose soln is 3:1, is entered in the fluid reservoir being placed in ice-water bath by reaction solution after static mixer
Cooling layering, upper layer are organic phase, and lower layer is saturated common salt water phase.With isometric tetrahydrofuran extraction saturation food after liquid separation
Brine layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 99%, the tetrahydro furan of recycling
It mutters and is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 2
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal chlorine
Change Al catalysts.Fructose soln by 200 DEG C of tetrahydrofuran is preheated to and containing catalyst passes through two constant flow pumps of A, B respectively
It has been warmed up according to the flow injection of 1m/s into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran
Volume ratio with fructose soln is 3:1, enters a fluid reservoir being placed in ice-water bath by reaction solution after static mixer
Middle cooling layering, upper layer are organic phase, and lower layer is saturated common salt water phase.Saturation is extracted with isometric tetrahydrofuran after liquid separation
Salt water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 79%, the tetrahydro of recycling
Furans is directly recycled, and saturated common salt water layer is recycled after adding raw material.
Embodiment 3
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.Fructose soln by 160 DEG C of tetrahydrofuran is preheated to and containing catalyst pass through respectively two constant flow pumps of A, B by
According to 1m/s flow injection have been warmed up into 160 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and
The volume ratio of fructose soln is 3:1, is entered in the fluid reservoir being placed in ice-water bath by reaction solution after static mixer
Cooling layering, upper layer are organic phase, and lower layer is saturated common salt water phase.With isometric tetrahydrofuran extraction saturation food after liquid separation
Brine layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 75%, the tetrahydro furan of recycling
It mutters and is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 4
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.Fructose soln by 240 DEG C of tetrahydrofuran is preheated to and containing catalyst pass through respectively two constant flow pumps of A, B by
According to 1m/s flow injection have been warmed up into 240 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and
The volume ratio of fructose soln is 3:1, is entered in the fluid reservoir being placed in ice-water bath by reaction solution after static mixer
Cooling layering, upper layer are organic phase, and lower layer is saturated common salt water phase.With isometric tetrahydrofuran extraction saturation food after liquid separation
Brine layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 89%, the tetrahydro furan of recycling
It mutters and is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 5
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal first
Acid catalyst.Fructose soln by 200 DEG C of tetrahydrofuran is preheated to and containing catalyst pass through respectively two constant flow pumps of A, B by
According to 1m/s flow injection have been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and
The volume ratio of fructose soln is 3:1, is entered in the fluid reservoir being placed in ice-water bath by reaction solution after static mixer
Cooling layering, upper layer are organic phase, and lower layer is saturated common salt water phase.With isometric tetrahydrofuran extraction saturation food after liquid separation
Brine layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 70%, the tetrahydro furan of recycling
It mutters and is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 6
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal 1-
(3- sulfonic group propyl) -3- methylimidazolium hydrogen sulphate salt catalyst.200 DEG C of tetrahydrofuran will be preheated to and containing catalyst
Fructose soln passes through two constant flow pumps of A, B respectively and has been warmed up to 200 DEG C of static mixer (instead according to the flow injection of 1m/s
Answering length of tube is 60m) in, wherein the volume ratio of tetrahydrofuran and fructose soln is 3:1, passes through reaction solution after static mixer
Cooling layering in the fluid reservoir being placed in ice-water bath into one, upper layer are organic phase, and lower layer is saturated common salt water phase.Liquid separation with
Saturated common salt water layer is extracted with isometric tetrahydrofuran afterwards, and is evaporated under reduced pressure after merging with upper organic phase, 5- hydroxyl first is obtained
The yield of base furfural is 82%, and the tetrahydrofuran of recycling is directly recycled, and saturated common salt water layer is after adding raw material
It is recycled.
Embodiment 7
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.Fructose soln by 200 DEG C of tetrahydrofuran is preheated to and containing catalyst pass through respectively two constant flow pumps of A, B by
According to 1m/s flow injection have been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and
The volume ratio of fructose soln is 1:1, is entered in the fluid reservoir being placed in ice-water bath by reaction solution after static mixer
Cooling layering, upper layer are organic phase, and lower layer is saturated common salt water phase.With isometric tetrahydrofuran extraction saturation food after liquid separation
Brine layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 72%, the tetrahydro furan of recycling
It mutters and is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 8
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal first
Acid catalyst.Fructose soln by 200 DEG C of tetrahydrofuran is preheated to and containing catalyst pass through respectively two constant flow pumps of A, B by
According to 1m/s flow injection have been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and
The volume ratio of fructose soln is 20:1, is entered in the fluid reservoir being placed in ice-water bath by reaction solution after static mixer
Cooling layering, upper layer are organic phase, and lower layer is saturated common salt water phase.With isometric tetrahydrofuran extraction saturation food after liquid separation
Brine layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 97%, the tetrahydro furan of recycling
It mutters and is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 9
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 1m/s has been warmed up into 240 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 3:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 71%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 10
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 1m/s has been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 3:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 77%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 11
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 1m/s has been warmed up into 160 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 3:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 64%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 12
The fructose soln that mass fraction is 5% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 1m/s has been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 3:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 73%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 13
The fructose soln that mass fraction is 60% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 1m/s has been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 3:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 76%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 14
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 3m/s has been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 3:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 72%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 15
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, 1- (the 3- sulphur that mass fraction is 2% is added
Acidic group propyl) -3- methylimidazolium hydrogen sulphate salt catalyst.By not preheated tetrahydrofuran and contain the fructose soln of catalyst
It is had been warmed up respectively according to the flow injection of 1m/s to 200 DEG C of static mixer (tube length of reaction tube by two constant flow pumps of A, B
For in 60m), wherein the volume ratio of tetrahydrofuran and fructose soln is 3:1, enter one by reaction solution after static mixer
Cooling layering is placed in the fluid reservoir in ice-water bath, and upper layer is organic phase, and lower layer is saturated common salt water phase.The bodies such as use after liquid separation
Long-pending tetrahydrofuran extracts saturated common salt water layer, and is evaporated under reduced pressure after merging with upper organic phase, obtains 5 hydroxymethyl furfural
Yield is 69%, and the tetrahydrofuran of recycling is directly recycled, and saturated common salt water layer is recycled after adding raw material
It uses.
Embodiment 16
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, the formic acid that mass fraction is 5% is added and urges
Agent.Not preheated tetrahydrofuran and the fructose soln containing catalyst are passed through into two constant flow pumps of A, B according to 1m/s respectively
Flow injection have been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fructose are molten
The volume ratio of liquid is 3:1, enters in the fluid reservoir being placed in ice-water bath cooling point by reaction solution after static mixer
Layer, upper layer are organic phase, and lower layer is saturated common salt water phase.Saturated salt solution is extracted with isometric tetrahydrofuran after liquid separation
Layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 61%, and the tetrahydrofuran of recycling is straight
Capable recycling is tapped into, saturated common salt water layer is recycled after adding raw material.
Embodiment 17
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 1m/s has been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 1:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 65%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Embodiment 18
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.By not preheated tetrahydrofuran and the fructose soln containing catalyst pass through respectively two constant flow pumps of A, B according to
The flow injection of 1m/s has been warmed up into 200 DEG C of static mixer (tube length of reaction tube 60m), wherein tetrahydrofuran and fruit
The volume ratio of sugar juice is 20:1, is entered by reaction solution after static mixer cold in the fluid reservoir being placed in ice-water bath
But it is layered, upper layer is organic phase, and lower layer is saturated common salt water phase.Saturated common salt is extracted with isometric tetrahydrofuran after liquid separation
Water layer, and be evaporated under reduced pressure after merging with upper organic phase, the yield for obtaining 5 hydroxymethyl furfural is 76%, the tetrahydrofuran of recycling
It is directly recycled, saturated common salt water layer is recycled after adding raw material.
Comparative example 1
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.Fructose soln by 200 DEG C of tetrahydrofuran is preheated to and containing catalyst is injected into advance by charge pump
In the autoclave of heat to 200 DEG C, wherein the volume ratio of tetrahydrofuran and fructose soln is 3:1, in 200 DEG C of reaction 3min,
The cooling reaction kettle of ice water to room temperature, liquid separation, upper layer is organic phase, and lower layer is saturated common salt water phase, is used in equal volume after liquid separation
Tetrahydrofuran extracts saturated common salt water layer, and is evaporated under reduced pressure after merging with upper organic phase, obtains the yield of 5 hydroxymethyl furfural
It is 58%, the tetrahydrofuran of recycling is directly recycled, and saturated common salt water layer is recycled after adding raw material.
Comparative example 2
The fructose soln that mass fraction is 10% is prepared using saturated salt solution, addition mass fraction is millesimal sulphur
Acid catalyst.Not preheated tetrahydrofuran and fructose soln containing catalyst are injected by charge pump have been warmed up to
In 200 DEG C of autoclave, wherein the volume ratio of tetrahydrofuran and fructose soln is 3:1, in 200 DEG C of reaction 3min, ice water
Cooling reaction kettle to room temperature, liquid separation, upper layer is organic phase, and lower layer is saturated common salt water phase, with isometric tetrahydro after liquid separation
Furans extracts saturated common salt water layer, and is evaporated under reduced pressure after merging with upper organic phase, and the yield for obtaining 5 hydroxymethyl furfural is
51%, the tetrahydrofuran of recycling is directly recycled, and saturated common salt water layer is recycled after adding raw material.
Claims (10)
1. a kind of method for synthesizing 5 hydroxymethyl furfural, which is characterized in that the raw material of the method is fructose, and reaction system is full
With inorganic salt solution-organic solvent system, reactor is static mixer, and the flow velocity of solution is 0.1- in the static mixer
5m/s；The catalyst of the method is organic acid, inorganic acid, acidic ion liquid or lewis acid.
2. the method according to claim 1, wherein the organic solvent is tetrahydrofuran, n-butanol, 2- fourth
Alcohol, butanone, methyl iso-butyl ketone (MIBK), 2- methyltetrahydrofuran.
3. the method according to claim 1, wherein the inorganic salts are potassium chloride, sodium chloride, sodium sulphate, sulphur
Sour potassium, potassium bromide, sodium bromide, potassium iodide, sodium iodide, lithium chloride.
4. the method according to claim 1, wherein the tube length of reaction tube of the static mixer is 10-200m.
5. the method according to claim 1, wherein described method includes following steps:
(1) saturation inorganic salt solution and fructose are mixed to get fructose soln, catalyst is added in the fructose soln and is obtained
To reaction solution；In the fructose soln, the mass fraction of fructose is 5-60wt%；
(2) organic solvent for being preheated to reaction temperature and the reaction solution are passed through into conveying equipment respectively and inject static mixing
Device is controlled at 160-240 DEG C and reacts；
(3) cooling, stratification, liquid separation, then by the organic of upper layer by the reaction solution effluent of static mixer in step (2)
Phase layer is evaporated under reduced pressure to obtain the 5 hydroxymethyl furfural；Upper layer is organic phase, and lower layer is saturation inorganic salts water phase.
6. the method according to claim 1, wherein in the reaction solution, the mass fraction of catalyst is
0.1%-5%.
7. the method according to claim 1, wherein the inorganic acid is sulfuric acid, hydrochloric acid, phosphoric acid, nitric acid；
The organic acid is formic acid, acetic acid, propionic acid；
The lewis acid is aluminium chloride, iron chloride, aluminum sulfate, aluminum nitrate, ferric nitrate, chromic nitrate, chromium chloride；
The acidic ion liquid is 1- (3- sulfonic group propyl) -3- methylimidazolium hydrogen sulphate salt, 1- (3- sulfonic group propyl) -3-
Methylimidazole villaumite, 1- (3- sulfonic group propyl) -3- methylimidazole bromide, 1- (3- sulfonic group propyl) -3- methylimidazole acetic acid
Salt, 1- (3- sulfonic group propyl) -3- methylimidazole hexafluorophosphate, 1- (3- sulfonic group propyl) -3- methylimidazole tetrafluoro boric acid
Salt, 1- (3- sulfonic group propyl) -3- methylimidazolium nitrate, 1- (3- sulfonic group propyl) -3- methylimidazole dihydric phosphate, 1-
(4- sulfonic group butyl) -3- methylimidazolium hydrogen sulphate salt, 1- (4- sulfonic group butyl) -3- methylimidazole villaumite, 1- (4- sulfonic group
Butyl) -3- methylimidazole bromide, 1- (4- sulfonic group butyl) -3- methylimidazole acetate, 1- (4- sulfonic group butyl) -3- first
Base limidazolium hexafluorophosphate, 1- (4- sulfonic group butyl) -3- methyl imidazolium tetrafluoroborate, 1- (4- sulfonic group butyl) -3- first
Base imidazole nitrate, 1- (4- sulfonic group butyl) -3- methylimidazole dihydric phosphate.
8. according to the method described in claim 5, it is characterized in that, the saturation inorganic salts water phase in step (3) is used in equal volume
Organic solvent extraction, organic layer extracted merge vacuum distillation with organic layer described in step (3), obtain the 5- hydroxyl
Methyl furfural and recycling organic solvent；The inorganic brine layer of saturation extracted is recycled after adding fructose.
9. the method according to claim 1, wherein the flow velocity of solution is 1-3m/s in static mixer.
10. according to the method described in claim 5, it is characterized in that, organic solvent described in step (2) and reactant solution
Volume ratio is 1:1-20:1.
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| WO2021046996A1 (en) * | 2019-09-11 | 2021-03-18 | 中国科学院大连化学物理研究所 | Method for improving synthesis efficiency of 5-hydroxymethylfurfural |
| CN112830907A (en) * | 2019-12-20 | 2021-05-25 | 中国科学院宁波材料技术与工程研究所 | Method for preparing 5-hydroxymethylfurfural |
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