CN108452793A - A kind of monosaccharide epimerization reaction catalyst - Google Patents

A kind of monosaccharide epimerization reaction catalyst Download PDF

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CN108452793A
CN108452793A CN201710087176.9A CN201710087176A CN108452793A CN 108452793 A CN108452793 A CN 108452793A CN 201710087176 A CN201710087176 A CN 201710087176A CN 108452793 A CN108452793 A CN 108452793A
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catalyst
monosaccharide
quantum dot
reaction
metal
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CN108452793B (en
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张建
张业新
张亚杰
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Ningbo Institute of Material Technology and Engineering of CAS
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Ningbo Institute of Material Technology and Engineering of CAS
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/14—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of germanium, tin or lead
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/30—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
    • B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H1/00—Processes for the preparation of sugar derivatives
    • 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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  • Biotechnology (AREA)
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Abstract

The present invention provides a kind of monosaccharide epimerization reaction catalyst and its preparation and recovery methods, and the catalyst is the metal oxide quantum dot hydrosol, wherein the metal is selected from the group：Molybdenum, tungsten, tin, or combinations thereof.The catalyst utilization is high, selectivity is good, recycling is convenient.

Description

A kind of monosaccharide epimerization reaction catalyst
Technical field
The invention belongs to chemical fields, and in particular, to arrive a kind of monosaccharide epimerization reaction catalyst and its preparation And recovery method.
Background technology
Rare sugar, such as mannose, lyxose, ribose etc. have important application in fields such as food, pharmacy and clinical medicine, But it is very rare compared with nature largely existing glucose and fructose.Monosaccharide epimerization reaction is to obtain rare sugar Important means, common catalyst be epimerase.Epimerase use condition is harsh (alkaline condition), quick to impurity Sense, reaction temperature window narrows (62 DEG C or so) are limited to thermodynamical equilibrium, and yield is not high, and the separation and recovery operation of enzyme is non- It is often cumbersome.In comparison, the use condition of inorganic salts catalyst is relatively wide in range, can higher temperature (80-150 DEG C) into Row, obtains higher yield.Such catalyst can be divided into two classes, homogeneous catalyst and heterogeneous catalyst.Homogeneous catalyst has Solubility can be contacted fully with monosaccharide molecule, such as sodium molybdate, ammonium molybdate.CN102807593A discloses a kind of D-MANNOSE Preparation method, with ammonium molybdate be catalyzed glucose epimerism mannose is obtained by the reaction.But such catalyst is difficult to detach Recycling, and addition inorganic acid is needed to ensure that reaction is in acidic environment, further increase the difficulty of product separation.It is another kind of Catalyst, i.e. heterogeneous catalyst, it is not soluble in water, it is easily detached from reaction system, such as molybdenum base heteropoly acid.CN104004030A is disclosed A kind of glucose epimerism produces the catalyst of mannose, i.e. Tungstenic compound, including tungsten oxide, tungsten carbide, tungsten nitride, Tungsten phosphide and tungsten sulfide etc..But heterogeneous catalyst could be contacted fully with monosaccharide molecule by stirring, catalyst usage amount Greatly, efficiency is low.
In conclusion this field still lacks, a kind of utilization rate is high, selectivity is good, the convenient monosaccharide epimerization of recycling is anti- Answer catalyst.
Invention content
The present invention provides a kind of monosaccharide epimerization reaction catalyst and preparation method thereof and its use, recycling side Method, the catalyst have the advantages that utilization rate is high, selectivity is good, recycling is convenient.
In the first aspect of the present invention, a kind of monosaccharide epimerization reaction catalyst is provided, the catalyst includes The metal oxide quantum dot hydrosol of catalytically effective amount, wherein the metal is selected from the group：Molybdenum, tungsten, tin, or combinations thereof.
In another preferred example, the catalyst is selected from the group：The molybdenum oxide quantum dot hydrosol, tungsten oxide quantum dot are water-soluble Glue, the tin oxide quantum dot hydrosol, or combinations thereof.
In another preferred example, in the catalyst, a concentration of 0.1-1g/L of the metal oxide quantum dot.
In another preferred example, the size of the quantum dot is 1-50 nanometers.
In another preferred example, the size of the quantum dot is 2-40 nanometers.
In another preferred example, the size of the quantum dot is 3-30 nanometers.
In another preferred example, the method includes the steps：
(i) it is reacted with metal simple-substance with peroxide water, to obtain the metal oxide quantum dot hydrosol；Its In, the metal is selected from the group：Molybdenum, tungsten, tin, or combinations thereof；And the mass ratio that feeds intake of the metal simple-substance and peroxide water It is 1 × 10-4~1 × 10-3：1；
The monosaccharide epimerism is prepared with the metal oxide quantum dot hydrosol with optional step (ii) Change catalysts.
In another preferred example, the mass ratio that feeds intake of the metal simple-substance and peroxide water is 1 × 10-3~1 × 10-2：1 (in terms of the peroxide water content in aqueous solution).
In another preferred example, the metal is metal simple-substance powder.
In another preferred example, the peroxide water is the peroxide water that mass fraction is 5-50%.
In another preferred example, the peroxide water is the peroxide water that mass fraction is 10-35%.
In another preferred example, it is described be heated to be heat at a reflux temperature.
In another preferred example, the heating temperature is 50-150 DEG C.
In another preferred example, the heating temperature is 80-130 DEG C.
In another preferred example, the heating time is 1-36h.
In another preferred example, the heating time is 12-24h.
The second aspect of the present invention provides a kind of method of catalysis monosaccharide epimerization reaction, the method includes Step：Catalyst described in first aspect present invention is mixed with monosaccharide, it is molten to form epimerization catalyst-monosaccharide mixing Liquid, heating are reacted；Preferably, the heating uses microwave radiation mode and/or ultraviolet radiation mode.
In another preferred example, in the mixed solution further include solvent selected from the group below：Water, DMSO, DMF, methanol, second Alcohol, isopropanol, acetic acid, or combinations thereof.
In another preferred example, the monosaccharide is hexose and/or pentose.
In another preferred example, the monosaccharide is selected from the group：Glucose, mannose, arabinose, ribose, xylose, lysol Sugar, or combinations thereof.
In another preferred example, the reaction carries out in closed reactor.
In another preferred example, in the epimerization catalyst-monosaccharide mixed solution, monosaccharide concentration 20-500 Grams per liter.
In another preferred example, the mass ratio that feeds intake of catalyst (in terms of the metal oxide quantum point mass) and monosaccharide It is 0.5 × 10–4-1×10–2：1.
In another preferred example, the mass ratio that feeds intake of the catalyst and monosaccharide is 1 × 10–4-1×10–3：1.
In another preferred example, the mass ratio that feeds intake of the catalyst and monosaccharide is 5 × 10–4-2.5×10–3：1.
In another preferred example, the reaction temperature is 50-180 DEG C.
In another preferred example, the temperature of the reaction is 70-140 DEG C.
In another preferred example, the time of the reaction is 0.5-10 hours.
In another preferred example, the heating uses microwave radiation mode.
In another preferred example, the heating is aided with ultraviolet radiation.
In another preferred example, reaction solution is stirred in reaction process.
In another preferred example, 0-300 revs/min of the rotating speed being stirred.
In third aspect present invention, a kind of catalyst recovery method is provided, which is characterized in that the method includes steps Suddenly：With the catalyst after completion of the reaction, DC electric field is applied to the solution containing catalyst, is urged described in driving Agent penetrates filter membrane, the catalyst being recycled.
In another preferred example, catalyst monosaccharide epimerization reaction as described above.
In another preferred example, the catalyst is entered through after filter membrane in new monosaccharide solutions.
In another preferred example, the voltage of the DC electric field is 10-100 volts.
In another preferred example, current density is 0.01-5 amperes/square decimeter.
In another preferred example, the filter membrane is selected from the group：Miillpore filter, ultrafiltration membrane, NF membrane, or combinations thereof.
In another preferred example, the aperture of the filter membrane is 2nm-450nm.
It should be understood that within the scope of the present invention, above-mentioned each technical characteristic of the invention and in below (eg embodiment) specifically It can be combined with each other between each technical characteristic of description, to form a new or preferred technical solution.As space is limited, herein No longer tire out one by one and states.
Description of the drawings
Fig. 1 is the yield of glucose epimerization product mannose and the selective change with reaction temperature in embodiment 1 Change curve graph；
Fig. 2 is a kind of preferred catalyst electrophoresis retracting device schematic diagram of the present invention；
Wherein, 1 is filter membrane, and 2 be the monosaccharide solutions of catalysis reaction, and 3 be new monosaccharide solutions, and 4 be container, and 5 is positive, 6 It is power supply for cathode, 7.
Specific implementation mode
The present inventor's in-depth study by long-term finds to use metal oxide quantum dot hydrosol catalyst, simultaneous Have the polymolecularity of homogeneous catalyst and the separability of heterogeneous catalyst.Quantum dot being capable of stable dispersion shape in aqueous solution At colloidal sol, it can fully be acted on monosaccharide molecule, improve its utilization rate.By applying DC electric field, electrophoretic may be used The recycling for realizing metal oxide quantum site catalyst, realizes recycling for catalyst.On this basis, it completes The present invention.
A kind of monosaccharide epimerization reaction catalyst
The present invention provides a kind of monosaccharide epimerization reaction catalyst, the catalyst is metal oxide quantum dot The hydrosol, wherein the metal is selected from the group：Molybdenum, tungsten, tin, or combinations thereof.
Preferably, the catalyst is selected from the group：The molybdenum oxide quantum dot hydrosol, the tungsten oxide quantum dot hydrosol, oxidation The tin quantum dot hydrosol, or combinations thereof.
Preferably, the size of the quantum dot is 1-50 nanometers.It is highly preferred that the size of the quantum dot is received for 3-30 Rice.
A kind of preparation method of monosaccharide epimerization reaction catalyst
The present invention provides a kind of preparation method of monosaccharide epimerization reaction catalyst, the method includes the steps：
(i) metal simple-substance is added in peroxide water, wherein the metal is selected from the group：Molybdenum, tungsten, tin or its group It closes；
(ii) it heats, it is cooling.
Wherein, metal simple-substance can be in any form added in peroxide water, it is therefore preferable to metal simple-substance powder.Preferred Embodiment in, the peroxide water is the peroxide water that mass fraction is 5-50%, the peroxide water of more preferably 10-35%.Gold The mass ratio that feeds intake for belonging to simple substance and peroxide water is not particularly limited, it is therefore preferable to 1 × 10-4~1 × 10-3：1；
The heating temperature of the reaction is 50-150 DEG C, it is therefore preferable to 80-130 DEG C, more preferably be added at a reflux temperature Heat is reacted.Reaction time is not particularly limited, it is preferable that the heating time is that 1-36h is more preferably 12-24h.
A method of catalysis monosaccharide epimerization reaction
The present invention provides it is a kind of catalysis monosaccharide epimerization reaction method, the method includes the steps：This is sent out The bright catalyst is mixed in monosaccharide in solvent, and heating is reacted.The preferably described solvent is water.Preferably, described Heating uses microwave radiation mode and/or ultraviolet radiation mode.
In a preferred embodiment, the monosaccharide is hexose and/or pentose.The more preferably described monosaccharide is selected from down Group：Glucose, mannose, arabinose, ribose, xylose, lyxose, or combinations thereof.
The reaction can react in any common heating device, it is preferable that the reaction is in closed reactor Middle progress.
In another preferred example, the mixed monosaccharide concentration of the catalyst is 20-500 grams per liters.
Preferably, the mass ratio that feeds intake of the catalyst and monosaccharide is 1 × 10–4-1×10–3.It is highly preferred that the catalysis Agent (in terms of metal oxide quantum point mass) and the mass ratio that feeds intake of monosaccharide are 5 × 10–4-2.5×10–3。
In a preferred embodiment, the reaction temperature of the reaction is 50-180 DEG C.It is highly preferred that the temperature of the reaction It is 70-140 DEG C.The reaction time is not particularly limited, and the preferred reaction time is 0.5-10 hours, more preferably 0.5- 10 hours.
In another preferred example, it also needs to be stirred reaction solution in reaction process, promotes the generation of reaction.Stirring Speed be not particularly limited, it is preferable that 0-300 revs/min of the rotating speed being stirred.
After reaction, the catalyst can be recycled by ultrafiltration or Electro Sorb/parsing.
A kind of recovery method of monosaccharide epimerization reaction catalyst
The present invention provides a kind of recovery method of catalyst, the method includes the steps：It is urged with of the present invention Agent is catalyzed after completion of the reaction, applies DC electric field to the solution, the catalyst is driven to penetrate filter membrane.
In preferred embodiments, it is molten to enter new monosaccharide through after filter membrane under electric field action for the catalyst In liquid, and then it is catalyzed the new monosaccharide solutions.
Wherein, voltage, the electric current of the DC electric field applied are not particularly limited.Preferably, the DC electric field Voltage be 10-100 volts.Preferably, current density is 0.01-5 amperes/square decimeter.
The filter membrane is also not particularly limited.The filter membrane can be not through monosaccharide through the catalyst.It is excellent Selection of land, the filter membrane are selected from the group：Miillpore filter, ultrafiltration membrane, NF membrane, or combinations thereof.Preferred aperture is 2nm-450nm.
Advantages of the present invention：
(1) monosaccharide epimerization reaction catalyst of the present invention be can stable suspersion in aqueous solution metal The quantum dot of oxide has had both the polymolecularity of homogeneous catalyst and the separability of heterogeneous catalyst.Quantum dot can be steady Fixed dispersion forms colloidal sol in aqueous solution, can fully be acted on monosaccharide molecule, improve its utilization rate.Particularly, quantum confinement Effect imparts the high surface energy of catalyst, shows higher catalytic activity.The reaction carries out in neutral aqueous solution, nothing Any additive of palpus, has wider temperature operating window and very high selectivity.
(2) compared with general inorganic salts catalyst, catalyst usage amount of the invention reduces an order of magnitude, this hair Bright catalyst/monosaccharide rate of charge is generally 0.0001~0.01.
(3) since quantum dot carries charge, generally negative electrical charge in aqueous solution, by applying can driving for DC electric field Momentum point is across the filter membrane for playing buffer action, into new monosaccharide solutions, that is, uses electrophoretic to realize metal oxide The recycling of quantum site catalyst realizes recycling for catalyst.
Below in conjunction with specific embodiment, further illustrate the present invention.It should be understood that description below is only the optimal of the present invention Embodiment is selected, and is not construed as the limitation for the scope of the present invention.On the basis of fully understanding the present invention, In the following examples, the experimental methods for specific conditions are not specified, usually according to normal condition, or according to proposed by manufacturer Condition, those skilled in the art can make technical scheme of the present invention nonessential change, such change should by regarding To be included among protection scope of the present invention.
Embodiment 1
15 grams of metal molybdenum powders are distributed in 30kg15wt% peroxide water to (mass ratio of molybdenum powder and peroxide water is 5 × 10–4), 100 DEG C are heated at reflux 24 hours, are cooled to room temperature, and obtain the molybdenum oxide quantum dot hydrosol, and wherein molybdenum oxide quantum dot is a concentration of 959 mg/litres, 3 nanometers of average grain diameter.
1.78 liters of molybdenum oxide quantum dot hydrosols and 2kg glucose are taken, while being distributed in 18.22 liters of water, glucose is dense Spend 100 grams per liters, the mass ratio that feeds intake of molybdenum oxide quantum dot and glucose is 8.5 × 10–4.By mixed liquor in closed reactor, Respectively at being reacted at the temperature such as 80,90,100,110,120,130 DEG C 4 hours, during which stirred with 50 revs/min.Reaction terminates Afterwards, the yield of gained epimer mannose and selectivity as shown in Figure 1,110 DEG C of later sweet dew sugar yields 30% More than, close to thermodynamical equilibrium yield, 90-120 DEG C of interval selection>97%.
Molybdenum oxide quantum site catalyst is recycled using electrophoretic separation method, as shown in Figure 2.Use 45 microns of miillpore filter (1) solution (2) after reacting 1 liter 110 DEG C is with 1 liter of new glucose solution (100 grams per liter of concentration) (3) in same container (4) Middle isolation.Respectively positive (5) and cathode graphite rod are inserted into glucose solution (2) after new glucose solution (3) and reaction (6), power supply (7) is opened, 0.05 ampere/square decimeter of current density is powered 3 hours, molybdenum oxide quantum dot is fully transferred to In new glucose solution, the yield of then repeatedly 110 DEG C of reaction, mannose is 30%, selectivity 95%.
Embodiment 2
The molybdenum oxide quantum dot hydrosol and 200 grams of mannoses that 450 milliliters of embodiments 1 synthesize are taken, while being distributed to 3.8 liters In water, the mass ratio that feeds intake of 44 grams per liter of mannose concentration, molybdenum oxide quantum dot and mannose is 8.8 × 10–4.Mixed liquor is existed It in closed reactor, is heated using microwave radiation, is reacted 6 hours in 110 DEG C.The yield of epimer glucose is 65%, Selectivity 97%.After being recycled using nanofiltration, step as above is repeated, the yield of glucose is 62%, selectivity 90%.
Embodiment 3
0.1 gram of metal tungsten powder is taken, is distributed in 200 grams of 25wt% hydrogen peroxide that (tungsten powder and peroxide water quality are than 5 × 10–4), 100 DEG C are heated at reflux 15 hours, are cooled to room temperature, and obtain the tungsten oxide quantum dot hydrosol, and wherein tungsten oxide quantum dot is a concentration of 640 mg/litres, 5 nanometers of average grain diameter.
500 milliliters of tungsten oxide quantum dot hydrosols and 500 grams of arabinoses are taken, while being distributed in 0.93 liter of water, I The mass ratio that feeds intake of uncle's 520 grams per liter of sugared concentration, tungsten oxide quantum dot and arabinose is 6.4 × 10–.By mixed liquor closed It is reacted 8 hours for 110 DEG C in reaction kettle.It is reacted 10 hours in 120 DEG C in closed reactor, the yield of epimer ribose is 35%, selectivity 80%.
Tungsten oxide quantum site catalyst is recycled using electrophoretic separation method, as shown in Figure 2.Use 45 microns of miillpore filter 1 Solution 2 after 1 liter of 110 DEG C of reaction is isolated with 1 liter of new arabinose solution (520 grams per liter of concentration) 3 in same container 4. It is inserted into anode 5 and cathode graphite rod 6 in arabinose solution 2 after new glucose solution 3 and reaction respectively, opens power supply 7, 3 ampere/square decimeter of current density is powered 1 hour, quantum dot is fully transferred in new glucose solution, is then repeated The yield of 110 DEG C of reaction, ribose is 30%, selectivity 95%.
Embodiment 4
0.05 gram of metallic tin powder is taken, is distributed in 200 grams of 35wt% peroxide water that (Sn powder and peroxide water quality are than 2.5 × 10–4), 100 DEG C are heated at reflux 36 hours, are cooled to room temperature, and obtain the tin oxide quantum dot hydrosol, wherein tin oxide quantum dot concentration For 320 mg/litres, 25 nanometers of average grain diameter.
800 milliliters of tin oxide quantum dot hydrosols and 100 grams of ribose are taken, while being distributed in 0.93 liter of water, ribose concentration The mass ratio that feeds intake of 105 grams per liters, tin oxide quantum dot and ribose is 1.28 × 10–3.By mixed liquor 110 in closed reactor DEG C reaction 10 hours, be aided with 50 watts of ultraviolet radiations (400-315 nanometers of wavelength).The yield of epimer arabinose is 70%, selectivity 91%.
Embodiment 5
2 liters of the molybdenum oxide quantum dot hydrosol and 2kg xyloses that Example 1 synthesizes, while being distributed in 18 liters of water, xylose The mass ratio that feeds intake of 100 grams per liter of concentration, molybdenum oxide quantum dot and xylose is 9.6 × 10–4.By mixed liquor in closed reactor It is reacted 0.5 hour in 90 DEG C, the yield of epimer lyxose is 35%, selectivity 85%.
Embodiment 6
5 liters of the molybdenum oxide quantum dot hydrosol and 2kg lyxoses that Example 1 synthesizes, while being distributed in 15 liters of DMSO, The mass ratio that feeds intake of 100 grams per liter of xylose concentration, molybdenum oxide quantum dot and lyxose is 2.4 × 10–3.By mixed liquor closed anti- It answers in kettle and is reacted 1 hour in 100 DEG C, the yield that epimer carrys out xylose is 58%, selectivity 89%.
All references mentioned in the present invention is incorporated herein by reference, independent just as each document It is incorporated as with reference to such.In addition, it should also be understood that, after reading the above teachings of the present invention, those skilled in the art can To be made various changes or modifications to the present invention, such equivalent forms equally fall within model defined by the application the appended claims It encloses.

Claims (10)

1. a kind of monosaccharide epimerization reaction catalyst, which is characterized in that the catalyst includes the metal of catalytically effective amount The oxide quantum dots hydrosol, wherein the metal is selected from the group：Molybdenum, tungsten, tin, or combinations thereof.
2. catalyst as described in claim 1, which is characterized in that the size of the quantum dot is 1-50 nanometers.
3. a kind of preparation method of catalyst as claimed in claim 1 or 2, which is characterized in that the method includes the steps：
(i) it is reacted with metal simple-substance with peroxide water, to obtain the metal oxide quantum dot hydrosol；Wherein, The metal is selected from the group：Molybdenum, tungsten, tin, or combinations thereof；And the mass ratio that feeds intake of the metal simple-substance and peroxide water is 1 ×10-4~1 × 10-3：1；
It is anti-that the monosaccharide epimerization is prepared with optional step (ii) the metal oxide quantum dot hydrosol Answer catalyst.
4. a kind of method of catalysis monosaccharide epimerization reaction, which is characterized in that the method includes the steps：By claim 1 or 2 any catalyst are mixed with monosaccharide, form epimerization catalyst-monosaccharide mixed solution, and heating carries out anti- It answers；Preferably, the heating uses microwave radiation mode and/or ultraviolet radiation mode.
5. method as claimed in claim 4, which is characterized in that further include solvent selected from the group below in the mixed solution：Water, DMSO, DMF, methanol, ethyl alcohol, isopropanol, acetic acid, or combinations thereof.
6. method as claimed in claim 4, which is characterized in that single in the epimerization catalyst-monosaccharide mixed solution A concentration of 20-500 grams per liters of sugar.
7. method as claimed in claim 4, which is characterized in that the catalyst (in terms of metal oxide quantum point mass) with The mass ratio that feeds intake of monosaccharide is 0.5 × 10–4-1×10–2：1.
8. method as claimed in claim 4, which is characterized in that the reaction temperature is 50-180 DEG C.
9. a kind of catalyst recovery method, which is characterized in that the method includes the steps：It has been reacted with the catalyst Bi Hou applies DC electric field to the solution containing catalyst, the catalyst is driven to penetrate filter membrane, the catalysis being recycled Agent.
10. method as claimed in claim 9, which is characterized in that the filter membrane is selected from the group：Miillpore filter, ultrafiltration membrane, nanofiltration Film, or combinations thereof.
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CN109053375A (en) * 2018-07-30 2018-12-21 南京林业大学 A kind of method that oil tea husk as raw material full constituent utilizes
WO2020062156A1 (en) * 2018-09-29 2020-04-02 中国科学院宁波材料技术与工程研究所 Continuous flow catalytic reactor, assembling method therefor and application therefor
CN110961041A (en) * 2018-09-29 2020-04-07 中国科学院宁波材料技术与工程研究所 Continuous flow catalytic reactor, method of assembling same and use thereof

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