CN109761799A - A method of catalysis glucose selective oxidation - Google Patents
A method of catalysis glucose selective oxidation Download PDFInfo
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- CN109761799A CN109761799A CN201711094451.6A CN201711094451A CN109761799A CN 109761799 A CN109761799 A CN 109761799A CN 201711094451 A CN201711094451 A CN 201711094451A CN 109761799 A CN109761799 A CN 109761799A
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Abstract
A method of catalysis glucose selective oxidation, air or oxygen is oxidant, and with TEMPO (2,2,6,6- tetramethyl piperidine -1- oxygen radical) and its derivative and metallic compound for composite catalyst system, water is solvent.The operation is simple, mild condition, and inversion rate of glucose is high, and the selectivity of product gluconic acid is good, has potential application prospect.
Description
Technical field
The present invention relates to a kind of methods for being catalyzed glucose selective oxidation, and in particular to one kind is catalyzed with composite catalyst system
The method of glucose selective oxidation, this method is using air or oxygen as oxidant, with TEMPO and its derivative and metallic compound
For catalyst, under temperate condition, water phase selective oxidation glucose prepares gluconic acid.
Background technique
Glucose is a kind of naturally occurring ring molecule containing 5 hydroxyls and ehter bond or containing 5 hydroxyls and one
The chain molecule of a aldehyde radical.It can be obtained from polysaccharide hydrolysis such as cellulose, starch, sucrose, it is from a wealth of sources, it is cheap and easy to get.And Portugal
Grape saccharic acid and its salt such as K-IAO, calcium gluconate etc., can be used for chemical industry recirculating cooling water system water treatment agent,
Steel surface processing agent.Food additives are alternatively arranged as food and medicine industry (Food
Technol.Biotechnol.2006,44,185-195.).It is a kind of important organic compound.
Usual glucose can prepare gluconic acid by selective oxidation.Existing method is in addition to biological oxidation process
(200710189929.3,201010545814.5,201210488451.5;J.Catal.2004,228,282-287) and electric
Chemical oxidization method (201310336025.4) is outside, in the majority with chemical oxidization method.Including metering oxidizing process and catalytic oxidation
(201310661638.5,201410011666.7).And it measures oxidizing process and needs to consume a large amount of oxidant stoichiometry, and some are needed
Want strong alkaline condition (chemistry world, 1991,10,472-474;Chemical industry and engineering, 2007,24,173-177;Green
Chem.2016,18,2308-2312.).The subsequent processing of product can generate waste liquid.
And using air or oxygen as oxidant, using catalysis oxidation means, realize that the selective oxidation of glucose prepares grape
Saccharic acid has many advantages, such as that efficient, technical process is simple, reaction condition is mild, there is very big research potential.In recent years, in grape
In terms of sugared Catalytic Oxidation, have much about using gold, platinum, palladium as the report of the noble metal catalyst system of main active component
(J.Catal.2006,244,122-125;Industrial Catalysis, 2007,15,5-11;Chemical industry and engineering, 2007,24,173-
177;Appl.Catal.A:Gen.2009,369,8-14;Appl.Catal.A:Gen.2011,401,73-82;
Appl.Catal.A:Gen.2014,479,103-111;J.Mol.Catal.A:Chem.2016,422,35-42.).Such is urged
Agent is expensive, and usually requires the preferable catalytic effect of competence exertion in alkaline environment.
Therefore, realize under cheap Non-precious Metal Catalysts system alkali free environment that glucose catalytic selective oxidation is one and great opens
Send out the research direction of potentiality.Xu Jie seminar is in oxynitrides (NOx) catalyst system done many research work
(Adv.Synth.Catal.2009,351,558-562;Tetrahedron Lett.2009,50,1677-1680;Green
Chem.2010,12,590-592;Catal.Commun.2010,11,732-735;Catal.Commun.2010,11,1189-
1192;Chin.J.Catal.2011,32,118-122;Adv.Synth.Catal.2011,353,226-230;
ChemSusChem 2011,4,51-54;Appl.Catal.A:Gen.2014,482,231-236.).NO free radical 2,2,6,
6- tetramethyl piperidine -1- oxygen radical (TEMPO) can aoxidize glucide with NaClO/NaBr co-catalysis
(Carbohydr.Res.1995,269,89-98;Cellulose 2006,13,679-687.);In addition, TEMPO is also extensive
Selective oxidation (Tetrahedron Lett.2001,42,6651-6653 applied to catalytic alcohol;J.Am.Chem.Soc.2004,
126,4112-4113;Chemical progress, 2007,11,1729-1735;Angew.Chem.Int.Ed.2014,53,8824-
8838.)。
The present invention is quasi- using air or oxygen as oxidant, using TEMPO and its derivative and metallic compound as catalyst system,
It realizes and is catalyzed glucose selective oxidation under temperate condition.
Summary of the invention
The purpose of the present invention is to provide a kind of new methods of efficient, low energy consumption glucose selective oxidation, and the present invention will
TEMPO and its derivative, metallic compound are used for the reaction of catalytic oxidation of glucose.
The technical solution of new method provided by the invention is as follows: a method of catalysis glucose selective oxidation, with air
Or oxygen is oxidant, using TEMPO and its derivative and metallic compound as catalyst system, in the closed pressurized reactor of solution-air
In, water phase obtains gluconic acid (the method provided by the present invention and primary product distribution by catalytic oxidation of glucose under temperate condition
As shown in Equation 1).
The new method of the glucose catalyticing oxidation provided by the invention of formula 1
Specific step is as follows:
Glucose solution is added in the closed pressurized reactor of solution-air;It is filled with oxygen-containing gas, guarantees certain oxygen point
Pressure;A certain amount of catalyst TEMPO and its derivative and metallic compound is added;Heating stirring carries out reaction certain time, instead
Should after obtain gluconic acid.Gained gluconic acid is quantified with HPLC.
Composite catalyst used includes TEMPO and its derivative and metallic compound, wherein TEMPO and its derivative are as follows:
TEMPO, 4- methyl TEMPO, 4- hydroxyl TEMPO, 4- methoxyl group TEMPO, 4- nitro TEMPO, 4- amino TEMPO, 4- acetyl ammonia
One of base TEMPO, 4- methylsulphur acidic group TEMPO, 4- cyano TEMPO, 4- carboxyl TEMPO or two kinds or more;TEMPO and its spread out
The dosage of biology be raw materials of glucose 0.05~20mol% (preferable amount is 0.5~15mol%, most preferred quantities for 2~
10mol%);Condition optimizing experiment shows TEMPO, 4- acetylamino TEMPO, 4- methylsulphur acidic group TEMPO, 4- carboxyl TEMPO, 4-
The good catalytic activity of nitro TEMPO.
Another component metals compound in composite catalyst used are as follows: cobalt acetate, acetylacetone cobalt (II), manganese acetate
(II), manganese dioxide, manganese sulfate, bismuth nitrate, sodium nitrite, ferric nitrate, manganese nitrate, copper nitrate, cobalt nitrate, copper chloride, bromination
One of copper, iron chloride or two kinds or more;The dosage of metallic compound be raw materials of glucose 0.05~20mol% (preferably
Dosage is 0.5~15mol%, and most preferred quantities are 2~10mol%).Condition optimizing experiment shows cobalt acetate, acetylacetone cobalt
(II), manganese acetate (II) good catalytic activity.
The molar ratio of TEMPO and its derivative and metallic compound is 20~0.1, is preferably in a proportion of 10~0.5, optimal
Selecting ratio is 5~1.
Reaction carries out in pressure reactor, can be oxygen source with oxygen, can also be directly oxygen source with air.Wherein oxygen
Gas partial pressure is 0.1~3.0MPa, and in a certain range as oxygen partial pressure increases, oxidizing reaction rate is improved, but oxygen pressure
Power is excessively high to will lead to side reaction, can also improve equipment cost.It is therefore preferable that oxygen partial pressure is 0.5~2.0MPa.
Reaction temperature is 40~160 DEG C, and the reaction time can be shortened by increasing reaction temperature, but also result in side reaction, because
This, preferable reaction temperature is 80~120 DEG C.
Reaction time be 2~for 24 hours, within the scope of certain time, with the reaction time increase conversion ratio improve, but react when
Between extend to after certain time, conversion ratio and selectivity of product are stablized, and preferred reaction time is 6~16h.
The invention has the characteristics that:
1. TEMPO and its derivative and metallic compound are multiple present invention firstly provides using air or oxygen as oxidant
Close catalyst system, the method for catalytic selectivity oxidizing glucose.
2. meeting environmentally protective theory using water as the solvent of glucose oxidation reaction in the present invention.
3. the present invention, for final oxygen source, is cleaned with air or oxygen, is cheap, environmental-friendly;Oxidation reaction condition mild (40
~160 DEG C), reaction process is easy to operate, highly-safe.
4. raw materials of glucose can be transformed by cellulose, starch, sucrose, cellobiose etc., from a wealth of sources, cheap easy
?.
Specific embodiment
Below by embodiment, the invention will be further described.
Embodiment 1:
By 2mmol glucose, 5mol% (relative to glucose) cobalt acetate, 5mol% (relative to glucose) TEMPO adds
Enter into 35mL reaction kettle, deionized water 6mL is added, closes kettle, being filled with oxygen pressure is 0.5MPa, 80 DEG C are warming up under stirring,
And keep 8h.It is then cooled to room temperature, is carefully depressurized to normal pressure.Whole products are transferred to 50mL volumetric flask, constant volume.It uses
The HPLC retention time of HPLC and standard substance is to primary product qualitative analysis.HPLC chromatogram outer marking quantitative method quantitatively divides product
Analysis.The conversion ratio of glucose and the yield of gluconic acid are calculated separately according to the following formula:
Conversion ratio [mol%]=(n0-n)/n0× 100%;
Yield [mol%]=nx/n0× 100%;
In formula, n0For the amount [mol] for reacting the preceding substance that glucose is added, n is the substance of remaining glucose after reaction
Amount [mol], nxFor the amount [mol] of the substance of generation product in reaction process.
The conversion ratio for calculating glucose is 93.5%, and the yield of gluconic acid is 77.4%.
Embodiment 2:
By 2mmol glucose, 10mol% (relative to glucose) acetylacetone cobalt (II), 10mol% is (relative to grape
Sugar) 4- hydroxyl TEMPO, it is added in 35mL reaction kettle, 6mL deionized water, closes kettle, being filled with oxygen pressure is 1.0MPa, stirring
Under be warming up to 100 DEG C, and keep 12h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According in embodiment 1
Method analyzes product, obtains the conversion ratio 82.7% of glucose, the yield 70.1% of gluconic acid.
Embodiment 3:
By 2mmol glucose, 5mol% (relative to glucose) manganese acetate (II), 10mol% (relative to glucose) 4-
Acetylamino TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.5MPa, under stirring
120 DEG C are warming up to, and keeps 16h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the side in embodiment 1
Method analyzes product, obtains the conversion ratio 94.0% of glucose, the yield 73.5% of gluconic acid.
Embodiment 4:
By 2mmol glucose, 20mol% (relative to glucose) manganese dioxide, 20mol% (relative to glucose) 4- ammonia
Base TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 0.1MPa, is warming up under stirring
140 DEG C, and keep 4h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.It analyzes and produces according to the method in embodiment 1
Object obtains the conversion ratio rate 81.6% of glucose, the yield 66.4% of gluconic acid.
Embodiment 5:
By 2mmol glucose, 2mol% (relative to glucose) manganese sulfate, 2mol% (relative to glucose) 4- acetyl ammonia
Base TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 3.0MPa, is warming up under stirring
160 DEG C, and keep 20h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the method analysis in embodiment 1
Product obtains the conversion ratio 91.3% of glucose, the yield 75.4% of gluconic acid.
Embodiment 6:
By 2mmol glucose, 5mol% (relative to glucose) bismuth nitrate, 8mol% (relative to glucose) 4- cyano
TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 2.0MPa, is warming up under stirring
120 DEG C, and keep 16h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the method analysis in embodiment 1
Product obtains the conversion ratio 92.1% of glucose, the yield 76.4% of gluconic acid.
Embodiment 7:
By 2mmol glucose, 0.5mol% (relative to glucose) sodium nitrite, 10mol% (relative to glucose)
TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.5MPa, is warming up to 80 under stirring
DEG C, and keep for 24 hours.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.It analyzes and produces according to the method in embodiment 1
Object obtains the conversion ratio 92.4% of glucose, the yield 60.7% of gluconic acid.
Embodiment 8:
By 2mmol glucose, 8mol% (relative to glucose) ferric nitrate, 8mol% (relative to glucose) 4- nitro
TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.5MPa, is warming up to 90 under stirring
DEG C, and keep 14h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.It analyzes and produces according to the method in embodiment 1
Object obtains the conversion ratio 89.3% of glucose, the yield 75.8% of gluconic acid.
Embodiment 9:
By 2mmol glucose, 15mol% (relative to glucose) manganese nitrate, 8mol% (relative to glucose) 4- methylsulphur
Acidic group TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.0MPa, stirs lower heating
To 80 DEG C, and keep 18h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the method analysis in embodiment 1
Product obtains the conversion ratio 90.3% of glucose, the yield 82.4% of gluconic acid.
Embodiment 10:
By 2mmol glucose, 5mol% (relative to glucose) copper nitrate, 10mol% (relative to glucose) 4- methylsulphur
Acidic group TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 0.5MPa, stirs lower heating
To 100 DEG C, and keep 2h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the method analysis in embodiment 1
Product obtains the conversion ratio 90.6% of glucose, the yield 67.3% of gluconic acid.
Embodiment 11:
By 2mmol glucose, 10mol% (relative to glucose) cobalt nitrate, 5mol% (relative to glucose) 4- nitro
TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.0MPa, is warming up to 40 under stirring
DEG C, and keep 4h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.Product is analyzed according to the method in embodiment 1,
Obtain the conversion ratio 73.6% of glucose, the yield 59.2% of gluconic acid.
Embodiment 12:
By 2mmol glucose, 0.05mol% (relative to glucose) copper chloride, 0.05mol% (relative to glucose) 4-
Methoxyl group TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 2.0MPa, is risen under stirring
Temperature keeps 16h to 160 DEG C.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the method in embodiment 1
Product is analyzed, the conversion ratio 81.1% of glucose, the yield 50.9% of gluconic acid are obtained.
Embodiment 13:
By 2mmol glucose, 6mol% (relative to glucose) copper bromide, 6mol% (relative to glucose) 4- carboxyl
TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.5MPa, is warming up to 60 under stirring
DEG C, and keep 3h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.Product is analyzed according to the method in embodiment 1,
Obtain the conversion ratio 82.0% of glucose, the yield 48.5% of gluconic acid.
Embodiment 14:
By 2mmol glucose, 8mol% (relative to glucose) iron chloride, 15mol% (relative to glucose) 4- methyl
TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.0MPa, is warming up under stirring
110 DEG C, and keep 10h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the method analysis in embodiment 1
Product obtains the conversion ratio 86.1% of glucose, the yield 77.2% of gluconic acid.
Embodiment 15:
By 2mmol glucose, 5mol% (relative to glucose) cobalt acetate, 10mol% (relative to glucose) TEMPO,
It is added in 35mL reaction kettle, 6mL deionized water, closes kettle, being filled with oxygen pressure is 1.0MPa, it is warming up to 100 DEG C under stirring, and
Keep 9h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.Product is analyzed according to the method in embodiment 1, is obtained
The conversion ratio 91.7% of glucose, the yield 79.1% of gluconic acid.
Embodiment 16:
By 2mmol glucose, 5mol% (relative to glucose) cobalt acetate, 15mol% (relative to glucose) 4- carboxyl
TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 0.5MPa, is warming up under stirring
120 DEG C, and keep 8h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.It analyzes and produces according to the method in embodiment 1
Object obtains the conversion ratio 87.5% of glucose, the yield 72.0% of gluconic acid.
Embodiment 17:
By 2mmol glucose, 10mol% (relative to glucose) acetylacetone cobalt (II), 10mol% is (relative to grape
Sugar) 4- acetylamino TEMPO, it is added in 35mL reaction kettle, 6mL deionized water, closes kettle, being filled with oxygen pressure is 1.5MPa,
It is warming up to 90 DEG C under stirring, and keeps 7h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According in embodiment 1
Method analyze product, obtain the conversion ratio 83.5% of glucose, the yield 72.2% of gluconic acid.
Embodiment 18:
By 2mmol glucose, 15mol% (relative to glucose) acetylacetone cobalt (II), 15mol% is (relative to grape
Sugar) 4- cyano TEMPO, it is added in 35mL reaction kettle, 6mL deionized water, closes kettle, being filled with oxygen pressure is 0.5MPa, stirring
Under be warming up to 60 DEG C, and keep 10h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the side in embodiment 1
Method analyzes product, obtains the conversion ratio 88.2% of glucose, the yield 71.5% of gluconic acid.
Embodiment 19:
By 2mmol glucose, 2mol% (relative to glucose) manganese acetate (II), 10mol% (relative to glucose) 4-
Nitro TEMPO is added in 35mL reaction kettle, 6mL deionized water, closes kettle, and being filled with oxygen pressure is 1.0MPa, stirs lower heating
To 50 DEG C, and keep 2h.After reaction, it is cooled to room temperature, is carefully depressurized to normal pressure.According to the method analysis in embodiment 1
Product obtains the conversion ratio 71.7% of glucose, the yield 54.3% of gluconic acid.
The operation is simple, mild condition, and inversion rate of glucose is high, and the selectivity of product gluconic acid is good, has latent
Application prospect.
The above, the specific embodiment of part only of the present invention, but protection scope of the present invention is not limited to that,
Also any restrictions caused by not because of the precedence of each embodiment to the present invention, it is any to be familiar with person skilled in the art of the present invention
In the technical scope that the present invention reports, it can easily think of the change or the replacement, should be covered by the protection scope of the present invention.
Therefore, protection scope of the present invention is not limited only to above embodiments, it should be subject to the protection scope in claims.
Claims (6)
1. it is a kind of be catalyzed glucose selective oxidation method, it is characterised in that: using air or oxygen as oxidant, TEMPO and its
Derivative and metallic compound are composite catalyst, water phase selective oxidation glucose.
2. according to claim 1 the method, it is characterised in that: the TEMPO derivative are as follows: 4- methyl TEMPO, 4- hydroxyl
TEMPO, 4- methoxyl group TEMPO, 4- nitro TEMPO, 4- amino TEMPO, 4- acetylamino TEMPO, 4- methylsulphur acidic group TEMPO,
One of 4- cyano TEMPO, 4- carboxyl TEMPO or two kinds or more.The dosage of TEMPO and its derivative is raw materials of glucose
0.05~20mol% (preferable amount is 0.5~15mol%, and most preferred quantities are 2~10mol%);
The structure and number of the representative TEMPO of formula 1 and its derivative.
3. according to claim 1 the method, it is characterised in that: another component metallic compound in the composite catalyst
Are as follows: cobalt acetate, acetylacetone cobalt (II), manganese acetate (II), manganese dioxide, manganese sulfate, bismuth nitrate, sodium nitrite, ferric nitrate, nitre
One of sour manganese, copper nitrate, cobalt nitrate, copper chloride, copper bromide, iron chloride or two kinds or more.The dosage of metallic compound is
0.05~20mol% of raw materials of glucose (preferable amount is 0.5~15mol%, and most preferred quantities are 2~10mol%).
4. according to the method for claim 1,2 or 3, it is characterised in that: mole of TEMPO and its derivative and metallic compound
Ratio is 20~0.1, is preferably in a proportion of 10~0.5, most preferred ratio is 5~1.
5. according to claim 1 the method, it is characterised in that: catalytic conversion process is with one of air or oxygen or two
Kind is oxygen source, and oxygen partial pressure is 0.1~3.0MPa;It is preferred that oxygen partial pressure is 0.5~2.0MPa.
6. according to claim 1 the method, it is characterised in that: reaction temperature be 40~160 DEG C, the reaction time be 2~for 24 hours;
Preferable reaction temperature is 80~120 DEG C, and preferred reaction time is 6~16h.
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WO2022253354A1 (en) * | 2021-05-29 | 2022-12-08 | 苏州大学 | Method for preparing carbonyl compound by oxidizing alcohol |
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CN105732363A (en) * | 2016-03-03 | 2016-07-06 | 华南农业大学 | Method for preparing gluconic acid by taking glucose as raw material under different working conditions |
CN106589143A (en) * | 2016-12-12 | 2017-04-26 | 万华化学集团股份有限公司 | Method for preparing C6-site selective carboxylation cellulose by using air as oxidizing agent |
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CN104119224A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Method for catalytic oxidation conversion of levulinic acid and levulinic acid ester |
CN105732363A (en) * | 2016-03-03 | 2016-07-06 | 华南农业大学 | Method for preparing gluconic acid by taking glucose as raw material under different working conditions |
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