Method by Dextrose production Fructose
Technical field
The present invention relates to monosaccharide isomerization, in particular it relates to the method by Dextrose production Fructose.
Background technology
Glucose, as a kind of monosaccharide of paramount importance in nature, abundance, is widely present in cellulose family plant
In, such as Semen Maydiss, Radix Betae, yam etc., these plants produce glucose by photosynthesis.It is industrial that to produce glucose mainly sharp
With amylase and saccharifying enzymatic degradation of starch or cellulose.Inexpensive glucose is converted into the fine chemicals of higher value
Prospect is very wide, such as Fructose.The using value of Fructose is high, can be used for fructose syrup preparation, food service industry and energy combustion
The fields such as material precursor.
At present, industrial produce that Fructose is main to obtain the mixed solution of Fructose and glucose from biological enzymolysis sucrose,
Separated purification finally obtains the crystalline solid of Fructose.Meanwhile, it is sugar source using glucose, in the work using glucose isomer enzyme
With under, glucose can be converted into Fructose through isomery.Both modes obtain the activity depending on enzyme for the production efficiency of Fructose,
Meanwhile, glucose and Fructose are affected by reversible reaction during the course of the reaction, lead to glucose transformation efficiency relatively low.Merit attention
, enzyme stability during the course of the reaction is notable on the impact of sugared transformation efficiency, need under certain sour environment these
Enzyme just can be survived, and the control to reaction key parameter is extremely strict, and the production cost of these enzyme is very simultaneously
Height is so that Fructose is somewhat limited on its synthesis technique.
Produce technical problem present in Fructose technique for solving biological enzyme, make glucose isomerization using catalysis technique
Cause concern.In aqueous phase system, mg-al brucite and mixing base catalyst etc. are proved glucose isomerase is had certain
Facilitation, but actual production effect has much room for improvement.In recent years, some organic faciess such as dimethyl sulfoxide (dmso), dimethyl methyl
Amide (dmf) etc. is used for glucose isomerase, and the conversion ratio of glucose makes moderate progress.Liu etc. (acs catalysis, 2014,
4:4295-4298) report, in the reaction medium of triethylamine, the highest yield of Fructose reaches 32%.(the journal such as yang
Of catalysis, 2015,330:474 484) report, have studied the reaction medium in 1,5,7- tri- azabicyclic decyl- 5- alkene
Middle Dextrose production Fructose, using a kind of organic alkali catalyst containing iron-base magnetic, after 120 DEG C of reaction 2h, Fructose highest yield
Reach 27%.Due to the use of these organic amines or nitrogen class solvent, consersion unit is required higher, and environment is caused necessarily
Pollution so that a large amount of productions of this technique receive obvious restriction.
Content of the invention
It is an object of the invention to provide a kind of method by Dextrose production Fructose, the method mild condition, operation are simple
And transformation efficiency is high.
To achieve these goals, the invention provides a kind of method by Dextrose production Fructose, the method is: in acid
In the presence of catalyst and organic solvent, glucose is carried out in high-pressure sealed environment isomerization reaction so that Fructose is obtained;Its
In, acid catalyst is selected from one or more of tungsten salt, aluminium salt, chromic salts, phosphotungstic acid and silico-tungstic acid.
By technique scheme, it is reaction medium that one aspect of the present invention passes through adopted low-carbon alcohols (alcohol of c1-c6),
Be conducive to regulating and controlling the reversible balance between glucose and Fructose molecule, improve glucose transformation efficiency and Fructose generates;The opposing party
Adopted acid catalyst (need not be carrier loaded) is passed through in face, may advantageously facilitate h in glucose molecule and translates into Fructose, significantly carries
High reaction efficiency (yield of Fructose may be up to 39.0%) and the selectivity of Fructose.Meanwhile, the isomerization method that the present invention provides
Reaction condition gentle, easy to operate, be conducive to simplifying Fructose production technology, and then make the method have higher economic effect
Beneficial and wide application prospect.
Other features and advantages of the present invention will be described in detail in subsequent specific embodiment part.
Brief description
Accompanying drawing is used to provide a further understanding of the present invention, and constitutes the part of description, with following tool
Body embodiment is used for explaining the present invention together, but is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is high-efficient liquid phase chromatogram in embodiment 1.
Specific embodiment
Hereinafter the specific embodiment of the present invention is described in detail.It should be appreciated that it is described herein concrete
Embodiment is merely to illustrate and explains the present invention, is not limited to the present invention.
The invention provides a kind of method by Dextrose production Fructose, the method is: in acid catalyst and low-carbon alcohols
In the presence of, glucose is carried out in high-pressure sealed environment isomerization reaction so that Fructose is obtained;Wherein, acid catalyst is selected from tungsten
One or more of salt, aluminium salt, chromic salts, phosphotungstic acid and silico-tungstic acid.
In the present invention, the concrete species of low-carbon alcohols can select in wide scope, but in order to improve Portugal further
The conversion ratio of grape sugar is it is preferable that low-carbon alcohols can be selected from the alcohol of c1-c4, such as a kind of or many in methanol, ethanol or propanol
Kind.
In the present invention, the consumption of raw material can select in wide scope, but in order to improve glucose further
Conversion ratio it is preferable that with respect to 100 weight portions glucose, the consumption of acid catalyst is 1-20 weight portion, the use of organic solvent
Measure as 300-2500 weight portion;It is highly preferred that with respect to the glucose of 100 weight portions, the consumption of acid catalyst is 1-10 weight
Part, the consumption of organic solvent is 400-2000 weight portion.
Meanwhile, the reaction condition of the present invention can select in wide scope, but in order to improve glucose further
Conversion ratio is it is preferable that isomerization reaction at least meets following condition: reaction temperature is 80-120 DEG C, and the response time is 0.5-
20h;It is highly preferred that the response time is 0.5-12h.
Additionally, the concrete species of tungsten salt can select in wide scope, but in order to improve turning of glucose further
Rate is it is preferable that tungsten salt is selected from tungsten chloride.
In the same manner, the concrete species of aluminium salt can select in wide scope, but in order to improve glucose further
Conversion ratio is it is preferable that aluminium salt is selected from one or more of aluminum chloride, aluminum sulfate, aluminium oxide, aluminum nitrate, aluminium fluoride;More preferably
Ground, aluminium salt is aluminum chloride.
In the same manner, the concrete species of chromic salts can select in wide scope, but in order to improve turning of glucose further
Rate is it is preferable that chromic salts is selected from Chlorizate chromium.
Hereinafter will be described the present invention by embodiment.
Embodiment 1
3g glucose, 0.15g tungsten chloride and 60g ethanol are placed in intermittent high-pressure reactor, then closed reactor
And reaction temperature is controlled to reaction 0.5h at 100 DEG C, after reaction terminates, reactant liquor is cooled down and adopts high performance liquid chromatography to divide
Analysis (high-efficient liquid phase chromatogram is shown in Fig. 1), result shows, the yield of Fructose is 37.2%.
Embodiment 2
Method according to embodiment 1 is carried out, and the yield of Fructose is 37.6%, except for the difference that the response time will extend to 2h.
Embodiment 3
Method according to embodiment 2 is carried out, and the yield of Fructose is 32.3%, except for the difference that reaction temperature is changed to 80 DEG C.
Embodiment 4
Method according to embodiment 2 is carried out, and the yield of Fructose is 26.8%, except for the difference that tungsten chloride is replaced by chlorination
Chromium.
Embodiment 5
Method according to embodiment 2 is carried out, and the yield of Fructose is 29.1%, except for the difference that tungsten chloride is replaced by chlorination
Aluminum.
Embodiment 6
Method according to embodiment 2 is carried out, and the yield of Fructose is 33.2%, except for the difference that tungsten chloride is replaced by phosphorus tungsten
Acid.
Embodiment 7
Method according to embodiment 2 is carried out, and the yield of Fructose is 25.0%, except for the difference that tungsten chloride is replaced by silicon tungsten
Acid.
Embodiment 8
Method according to embodiment 2 is carried out, and the yield of Fructose is 38.6%, except for the difference that ethanol is replaced by methanol.
Embodiment 9
Method according to embodiment 2 is carried out, and the yield of Fructose is 34.4%, except for the difference that ethanol is replaced by propanol.
Embodiment 10
Method according to embodiment 2 is carried out, and the yield of Fructose is 21.7%, except for the difference that reaction temperature is changed to 120 DEG C.
Embodiment 11
Method according to embodiment 2 is carried out, and the yield of Fructose is 39.0%, except for the difference that by the weight of tungsten chloride by
0.15g changes as 0.6g.
Embodiment 12
Method according to embodiment 2 is carried out, and the yield of Fructose is 31.9%, is except for the difference that changed the weight of glucose by 3g
It is changed to 15g.
Comparative example 1
Method according to embodiment 2 is carried out, and in product, no Fructose generates, and ethanol is except for the difference that all replaced by water.
Comparative example 2
Method according to embodiment 2 is carried out, and the yield of Fructose is 7.1%, except for the difference that 60g ethanol is replaced by 30g water
With 30g ethanol.
Comparative example 3
Method according to embodiment 2 is carried out, and the yield of Fructose is 6.4%, except for the difference that not using acid catalyst.
Indirectly demonstrated by above-described embodiment and comparative example: passing through adopted alcohol is reaction medium, can be favourable
Reversible balance between regulation and control glucose and Fructose molecule, improves glucose transformation efficiency and Fructose generates;Acid catalyst is (no
Need carrier loaded), h in glucose molecule can be may advantageously facilitate and translate into Fructose, greatly improve the choosing of reaction efficiency and Fructose
Selecting property.
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited in above-mentioned embodiment
Detail, in the range of the technology design of the present invention, multiple simple variant can be carried out to technical scheme, this
A little simple variant belong to protection scope of the present invention.
It is further to note that each particular technique feature described in above-mentioned specific embodiment, in not lance
In the case of shield, can be combined by any suitable means, in order to avoid unnecessary repetition, the present invention to various can
The compound mode of energy no longer separately illustrates.
Additionally, combination in any can also be carried out between the various different embodiment of the present invention, as long as it is without prejudice to this
The thought of invention, it equally should be considered as content disclosed in this invention.