CN106336437A - Method for preparing fructose from glucose - Google Patents

Method for preparing fructose from glucose Download PDF

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Publication number
CN106336437A
CN106336437A CN201610681628.1A CN201610681628A CN106336437A CN 106336437 A CN106336437 A CN 106336437A CN 201610681628 A CN201610681628 A CN 201610681628A CN 106336437 A CN106336437 A CN 106336437A
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fructose
glucose
acid
salt
consumption
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CN106336437B (en
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章青
李路微
李兵
沈培友
周双六
商永嘉
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Shandong Tianjiu Biotechnology Co ltd
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Anhui Normal University
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    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00Processes for the preparation of sugar derivatives
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07HSUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H3/00Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
    • C07H3/02Monosaccharides

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
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  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The invention discloses a method for preparing fructose from glucose. According to the method, in the presence of an acid catalyst and low carbon alcohol, glucose undergoes an isomerization reaction in a closed high-pressure environment so as to prepare fructose, wherein the acid catalyst is one or more ingredients selected from a group consisting of tungsten salt, aluminium salt, chromium salt, phosphotungstic acid and silicotungstic acid. The method has advantages of mild condition, simple process and high conversion efficiency.

Description

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.

Claims (9)

1. a kind of method by Dextrose production Fructose is it is characterised in that methods described is: in depositing of acid catalyst and low-carbon alcohols Under, described glucose is carried out in high-pressure sealed environment isomerization reaction be obtained described Fructose;Wherein, described acid catalysiss Agent is selected from one or more of tungsten salt, aluminium salt, chromic salts, phosphotungstic acid and silico-tungstic acid.
2. method according to claim 1, wherein, described low-carbon alcohols are selected from one or more in methanol, ethanol or propanol.
3. method according to claim 1 and 2, wherein, with respect to the described glucose of 100 weight portions, described acid catalysiss The consumption of agent is 1-20 weight portion, and the consumption of described low-carbon alcohols is 300-2500 weight portion.
4. method according to claim 3, wherein, with respect to the described glucose of 100 weight portions, described acid catalyst Consumption is 1-10 weight portion, and the consumption of described low-carbon alcohols is 400-2000 weight portion.
5. method according to claim 3, wherein, described isomerization reaction at least meets following condition: reaction temperature is 80-120 DEG C, the response time is 0.5-20h.
6. the method according to claim 3 or 4, wherein, described tungsten salt is tungsten chloride.
7. the method according to claim 3 or 4, wherein, described aluminium salt is selected from aluminum chloride, aluminum sulfate, aluminium oxide, nitric acid One or more of aluminum, aluminium fluoride.
8. method according to claim 7, wherein, described aluminium salt is aluminum chloride.
9. the method according to claim 3 or 4, wherein, described chromic salts is Chlorizate chromium.
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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100170A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Method for producing fructose through glucose isomerization
CN111841521A (en) * 2020-08-11 2020-10-30 浙江大学 Preparation method and application of cellulose-based hydrothermal carbon-supported aluminum catalyst based on swelling regulation
CN112028949A (en) * 2020-08-31 2020-12-04 安徽师范大学 Method for preparing fructose by glucose catalysis
CN112354563A (en) * 2020-11-27 2021-02-12 广东省科学院生物工程研究所 Carbon catalyst loaded with phosphotungstic acid, and preparation method and application thereof
CN112746136A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Chemical preparation method of fructose

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US3256270A (en) * 1961-11-11 1966-06-14 Boehringer & Soehne Gmbh Process for the manufacture of d-fructose
CN103288887A (en) * 2013-06-04 2013-09-11 北京大学 Method for preparing ketose by utilizing aldose
CN105837643A (en) * 2016-05-04 2016-08-10 南京林业大学 Method for preparing D-fructose through isomerization of D-glucose

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US3256270A (en) * 1961-11-11 1966-06-14 Boehringer & Soehne Gmbh Process for the manufacture of d-fructose
CN103288887A (en) * 2013-06-04 2013-09-11 北京大学 Method for preparing ketose by utilizing aldose
CN105837643A (en) * 2016-05-04 2016-08-10 南京林业大学 Method for preparing D-fructose through isomerization of D-glucose

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111100170A (en) * 2018-10-26 2020-05-05 中国石油化工股份有限公司 Method for producing fructose through glucose isomerization
CN111100170B (en) * 2018-10-26 2021-06-04 中国石油化工股份有限公司 Method for producing fructose through glucose isomerization
CN112746136A (en) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 Chemical preparation method of fructose
CN112746136B (en) * 2019-10-31 2022-03-08 中国石油化工股份有限公司 Chemical preparation method of fructose
CN111841521A (en) * 2020-08-11 2020-10-30 浙江大学 Preparation method and application of cellulose-based hydrothermal carbon-supported aluminum catalyst based on swelling regulation
CN112028949A (en) * 2020-08-31 2020-12-04 安徽师范大学 Method for preparing fructose by glucose catalysis
CN112028949B (en) * 2020-08-31 2021-09-28 安徽师范大学 Method for preparing fructose by glucose catalysis
CN112354563A (en) * 2020-11-27 2021-02-12 广东省科学院生物工程研究所 Carbon catalyst loaded with phosphotungstic acid, and preparation method and application thereof
CN112354563B (en) * 2020-11-27 2023-04-18 广东省科学院生物工程研究所 Carbon catalyst loaded with phosphotungstic acid, and preparation method and application thereof

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Denomination of invention: Method of producing fructose from glucose

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