CN106632522A - Method for catalyzing glucose isomerism to prepare fructose by using basic ionic liquid - Google Patents
Method for catalyzing glucose isomerism to prepare fructose by using basic ionic liquid Download PDFInfo
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- CN106632522A CN106632522A CN201610836295.5A CN201610836295A CN106632522A CN 106632522 A CN106632522 A CN 106632522A CN 201610836295 A CN201610836295 A CN 201610836295A CN 106632522 A CN106632522 A CN 106632522A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H3/00—Compounds containing only hydrogen atoms and saccharide radicals having only carbon, hydrogen, and oxygen atoms
- C07H3/02—Monosaccharides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
- C07H1/00—Processes for the preparation of sugar derivatives
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
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Abstract
The invention discloses a method for catalyzing glucose isomerism to prepare fructose by using a basic ionic liquid. According to the method, the basic ionic liquid and glucose are taken as raw materials, water is added as a solvent, wherein the concentration of glucose in the system is 0.1-1mol/L; the concentration of the basic ionic liquid catalyst to the glucose is 10-30mol%; the reaction temperature is 70-120 DEG C; the reaction time is 10-60 minutes; the conversion rate of the glucose is 47-59per mill; the fructose yield is 35-37%. The basic ionic liquid catalyst is an alkali functional ionic liquid consisting of cation and anion; the cation is alkyl substituted imidazole, quaternary ammonium or alkyl substituted morpholine; the anion is a carboxylate radical, a hydroxy radical, a carbonic acid radical or proline radical. The basic ionic liquid liquid has 'greenness' and nonvolatility, is capable of achieving circulated testing, and has a remarkable advantage of environmental friendliness.
Description
Technical field
The present invention relates to the preparation method of fructose, more particularly to a kind of alkali ionic liquid catalysis glucose isomerase preparation fruit
The method of sugar, belongs to resource higher value application and technical field of fine chemical production.
Background technology
Fossil energy is increasingly reduced, and adjoint environmental problem becomes increasingly conspicuous, find regenerative resource solve the current energy and
Environmental crisis is extremely urgent.The chemicals that reproducible biomass are converted into liquid energy and high added value is caused into extensively pass
Note.By the saccharide converted important way for being biomass economy for platform chemicals such as 5 hydroxymethyl furfural and levulic acids in biomass
Footpath, these platform chemicals can be further converted to polymer, medicine and liquid fuel, with being extremely widely applied prospect.
Platform chemicals are prepared with fructose or levulan as raw material to be easier, the fructose dehydration 5- hydroxyl first in ionic liquid
Base furfural yield is up to 90%.It is more difficult that glucose or glucan are converted into platform chemicals, and Jing is needed in conversion process
Glucose is gone through to this committed step of fructose isomery, subsequent fructose dehydration prepares platform chemicals.5 hydroxymethyl furfural and acetyl
The platform chemicals such as propionic acid have great industrial application value, and these platform chemical combination can be used for plastics industry, green solvent, profit
The field such as lubrication prescription and the biological substitution energy.Therefore, research glucose isomerization prepares fructose and is converted into platform chemical combination in biomass
It is most important in the research of thing.
Alkaline ionic liquid catalyst has following advantage：(1) alkali ionic liquid easily mixes with reaction system, mass transfer without
Boundary, catalysis activity and selective all high；(2) vapour pressure of alkali ionic liquid is extremely low and molten between some molecular solvents
Solution property is adjustable, thus, by the method such as decompression or extraction, it is possible to achieve product is separated with solvent；(3) alkali ion can be built
Liquid catalyst and reactant dissolve each other system, and alkali ionic liquid catalysis can carry out technique and dock with traditional base catalysis.It is comprehensive with
Upper advantage, with alkali ionic liquid replace traditional inorganic base and organic base catalytic glucose isomerization prepare fructose have it is larger
Development prospect.
The content of the invention
Present invention aim at providing a kind of to be capable of achieving the ionic liquid-catalyzed glucose of reusable high activity alkalescence
The method that isomery prepares fructose, up to 1.0mol/L, catalytic process is provided simultaneously with higher glucose conversion to glucose treating capacity
Rate (47-59%) and fructose yield (35-37%).
The present invention is designed one kind and is efficiently catalyzed using " green chemical " and the reusable performance of ionic liquid
Glucose isomerase catalyst.The catalyst to the treating capacity of glucose up to 0.1-1mol/L, can obtain within a short period of time compared with
High inversion rate of glucose and fructose yield.Further, since the stable physical and chemical performance of ionic liquid and fixedness, this is urged
Agent is capable of achieving to reuse.
The purpose of the present invention is realized by following technical proposals：
A kind of method that alkali ionic liquid catalysis glucose isomerase prepares fructose：It is with alkali ionic liquid and glucose
Raw material, addition water is solvent；Glucose concentration in system is 0.1-1mol/L；Ionic-liquid catalyst is to concentration of glucose
10-30mol%；Reaction temperature is 70-120 DEG C；Reaction time is 10-60min；
The ionic-liquid catalyst is the basic functionalized ionic liquid being made up of cation and anion；It is described sun from
Son is alkyl substituted imidazole, quaternary ammonium or alkyl replace morpholine；Anion is carboxylate radical, hydroxyl, carbonate or proline root.
Further to realize the object of the invention, it is preferable that the ionic-liquid catalyst is with following structural formula
It is a kind of：
Preferably, the glucose initial reaction concentration is 0.1-1mol/L.
Preferably, the ionic liquid is 10-20mol% relative to the concentration of glucose.
Preferably, the reaction temperature is 80-100 DEG C.
Preferably, the reaction time is 20-50min.
Relative to prior art, the present invention just has the following advantages：
1) present invention utilizes the premium properties of " green medium " ionic liquid, and with basic functionalized ionic liquid tradition is replaced
Base catalyst realizes that glucose efficient catalytic prepares fructose.Gained inversion rate of glucose is 47-59%, and fructose yield is 35-
37%, higher than the present art.
2) ionic liquid of present invention report can be separated and recovered using aqueous two-phase, realize the recycling and reuse of catalyst.
3) catalyst successfully avoid the high volatility of organic alkali catalyst presence, and corrosivity is big to wait not enough, is a kind of
Eco-friendly glucose isomerase catalyst.
4) base catalyst that the present invention is provided possesses good recycling performance.
Description of the drawings
Fig. 1 is the gained glucose of embodiment 1 and fructose liquid chromatogram.
Specific embodiment
To more fully understand the present invention, with reference to embodiment, the present invention will be further described, but the reality of the present invention
Apply mode not limited to this.
Embodiment 1
10mL ultra-pure waters are taken, 0.9g glucose (0.5mol/L), 0.356g tetrabutyls proline ammonium (20mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 100 DEG C 30min is reacted.
After reaction terminates, gained liquid (containing unreacted glucose and isomerized products fructose) is diluted into 100 times, using efficient liquid phase
Chromatogram (dilute sulfuric acid with 5mmol/L as mobile phase, refractive power Composition distribution, HPX-87 chromatographic columns, column temperature is 65 DEG C), by with
The mode of standard substance control carries out qualitative analysis (Fig. 1) to its component, and their content is quantitatively divided by external standard method
Analysis.Result of study shows：With this understanding inversion rate of glucose is 55%, and fructose yield is 37%.The fruit that the present invention is obtained
Sugared yield reports technical merit higher than contemporary literature, and ionic-liquid catalyst is much smaller than traditional base catalysis to the corrosivity of equipment
Agent, and be capable of achieving to reuse.Therefore, compared with prior art, the technology of the present invention has significant advantage.
Embodiment 2
10mL ultra-pure waters are taken, 0.18g glucose (0.1mol/L), 0.071g tetrabutyls proline ammonium (20mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 80 DEG C 30min is reacted.
It is 50% to obtain inversion rate of glucose, and fructose yield is 37%.Method of testing and test condition are same as Example 1.
Embodiment 3
10mL ultra-pure waters are taken, 1.8g glucose (1.0mol/L), 0.712g tetrabutyls proline ammonium (20mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 80 DEG C 30min is reacted.
It is 50% to obtain inversion rate of glucose, and fructose yield is 35%.Method of testing and test condition are same as Example 1.
Embodiment 4
10mL ultra-pure waters are taken, 0.9g glucose (0.5mol/L), 0.356g tetrabutyls proline ammonium (20mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 120 DEG C 10min is reacted.
It is 56% to obtain inversion rate of glucose, and fructose yield is 36%.Method of testing and test condition are same as Example 1.
Embodiment 5
10mL ultra-pure waters are taken, 1.08g glucose (0.6mol/L), 0.356g tetrabutyls proline ammonium (20mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 70 DEG C 60min is reacted.
It is 47% to obtain inversion rate of glucose, and fructose yield is 37%.Method of testing and test condition are same as Example 1.
Embodiment 4 and 5 shows the reaction time in 10-60min, the reaction time between 70-120 DEG C under the conditions of fructose yield
Still can reach 35-37%.
Embodiment 6
Take 10mL ultra-pure waters, 0.9g glucose (0.5mol/L), 0.226g 1- ethyl-3-methylimidazole proline salts
(20mol%) in, being added to 100mL autoclaves, reactor Jing after nitrogen displacement three times, holding pressure be 1.0MPa, 100
30min is reacted at DEG C.It is 57% to obtain inversion rate of glucose, and fructose yield is 36%.Method of testing and test condition and enforcement
Example 1 is identical.
Embodiment 7
Take 10mL ultra-pure waters, 1.44g glucose (0.8mol/L), 0.240g 1- propyl group -3- methylimidazole proline salts
(20mol%) in, being added to 100mL autoclaves, reactor Jing after nitrogen displacement three times, holding pressure be 1.0MPa, 100
30min is reacted at DEG C.It is 56% to obtain inversion rate of glucose, and fructose yield is 36%.Method of testing and test condition and enforcement
Example 1 is identical.
Embodiment 8
10mL ultra-pure waters are taken, 0.9g glucose (0.5mol/L), 0.356g tetrabutyls proline ammonium (20mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 80 DEG C 30min is reacted.
It is 50% to obtain inversion rate of glucose, and fructose yield is 37%.Method of testing and test condition are same as Example 1.
Embodiment 9
10mL ultra-pure waters are taken, 0.9g glucose (0.5mol/L), 0.178g tetrabutyls proline ammonium (10mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 100 DEG C 30min is reacted.
It is 52% to obtain inversion rate of glucose, and fructose yield is 36%.Method of testing and test condition are same as Example 1.
Embodiment 10
10mL ultra-pure waters are taken, 0.9g glucose (0.5mol/L), 0.534g tetrabutyls proline ammonium (30mol%) is added
To in 100mL autoclaves, Jing after nitrogen displacement three times, holding pressure is 1.0MPa to reactor, and at 80 DEG C 30min is reacted.
It is 59% to obtain inversion rate of glucose, and fructose yield is 36%.Method of testing and test condition are same as Example 1.
Embodiment 9 and 10 is it can be seen that catalyst dosage is between 10-30mol%.
Embodiment 11
Experimental procedure will add potassium phosphate solid with embodiment 8 in reacted liquid, aqueous two-phase occur, phase in recovery
Rich tetrabutyl proline ammonium phase, with ether washing a small amount of potassium phosphate is separated out, and ether is removed in vacuum drying, the ionic liquid after recovery
For circulation experiment, catalyst weight reusability is investigated, as a result as shown in table 1, as can be seen from Table 1, catalyst has good
Good repeat performance, after three circulations, fructose yield is still up to 31%.Method of testing and test condition and enforcement
Example 1 is identical.
The tetrabutyl proline ionic liquid reusability of table 1
Embodiments of the present invention are simultaneously not restricted to the described embodiments, and other any spirit without departing from the present invention are real
Matter and the change, modification, replacement made under principle, combine, simplify, should be equivalent substitute mode, being included in the present invention
Protection domain within.
Claims (6)
1. a kind of method that alkali ionic liquid catalysis glucose isomerase prepares fructose, it is characterised in that with alkali ionic liquid
It is raw material with glucose, addition water is solvent；Glucose concentration in system is 0.1-1mol/L；Ionic-liquid catalyst is to Portugal
Grape sugar concentration is 10-30mol%；Reaction temperature is 70-120 DEG C；Reaction time is 10-60min；
The ionic-liquid catalyst is the basic functionalized ionic liquid being made up of cation and anion；The cation is
Alkyl substituted imidazole, quaternary ammonium or alkyl replace morpholine；Anion is carboxylate radical, hydroxyl, carbonate or proline root.
2. a kind of method that according to claim 1 alkali ionic liquid catalysis glucose isomerase prepares fructose, its feature exists
In the ionic-liquid catalyst is with the one kind in following structural formula：
3. according to claim 1 a kind of alkali ionic liquid is catalyzed the method that glucose isomerase prepares fructose, its feature
It is that the glucose initial reaction concentration is 0.1-1mol/L.
4. according to claim 1 a kind of alkali ionic liquid is catalyzed the method that glucose isomerase prepares fructose, its feature
It is that the ionic liquid is 10-20mol% relative to the concentration of glucose.
5. according to claim 1 a kind of alkali ionic liquid is catalyzed the method that glucose isomerase prepares fructose, its feature
It is that the reaction temperature is 80-100 DEG C.
6. according to claim 1 a kind of alkali ionic liquid is catalyzed the method that glucose isomerase prepares fructose, its feature
It is that the reaction time is 20-50min.
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Cited By (4)
| 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 |
| CN111454304A (en) * | 2020-04-30 | 2020-07-28 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through guanidino ionic liquid |
| CN112546674A (en) * | 2020-12-23 | 2021-03-26 | 浙江华康药业股份有限公司 | System and method for inhibiting glucose from isomerizing into fructose in anion exchange column |
| CN113788865A (en) * | 2021-06-29 | 2021-12-14 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material |
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Cited By (7)
| 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 |
| CN111454304A (en) * | 2020-04-30 | 2020-07-28 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through guanidino ionic liquid |
| CN111454304B (en) * | 2020-04-30 | 2021-07-20 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through guanidino ionic liquid |
| CN112546674A (en) * | 2020-12-23 | 2021-03-26 | 浙江华康药业股份有限公司 | System and method for inhibiting glucose from isomerizing into fructose in anion exchange column |
| CN113788865A (en) * | 2021-06-29 | 2021-12-14 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material |
| CN113788865B (en) * | 2021-06-29 | 2024-03-19 | 华南理工大学 | Method for preparing fructose by catalyzing glucose isomerization through ionic liquid loaded by organic metal framework material |
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