CN109761799B - Method for catalyzing selective oxidation of glucose - Google Patents
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Abstract
A method for catalyzing selective oxidation of glucose, air or oxygen is used as oxidant, TEMPO (2,2,6, 6-tetramethyl piperidine-1-oxygen free radical) and its derivative and metallic compound are used as composite catalytic system, and water is used as solvent. The reaction has the advantages of simple operation, mild conditions, high glucose conversion rate, good selectivity of the product gluconic acid and potential application prospect.
Description
Technical Field
The invention relates to a method for catalyzing selective oxidation of glucose, in particular to a method for catalyzing selective oxidation of glucose by a composite catalytic system.
Background
Glucose is a naturally occurring cyclic molecule containing 5 hydroxyl groups and an ether linkage or a chain molecule containing 5 hydroxyl groups and an aldehyde group. Can be obtained by hydrolyzing polysaccharides such as cellulose, starch, sucrose and the like, and has wide sources, low price and easy obtainment. Gluconic acid and its salt such as potassium gluconate, calcium gluconate, etc. can be used as water treatment agent of circulating cooling water system in chemical industry and steel surface treatment agent. Can also be used as Food additive in Food and pharmaceutical industry (Food Technol. Biotechnol.2006,44, 185-. Is an important class of organic compounds.
Generally, glucose can be prepared by selective oxidation. The existing methods are mostly chemical oxidation methods except biological oxidation method (200710189929.3,201010545814.5,201210488451.5; J.Catal.2004,228,282-287) and electrochemical oxidation method (201310336025.4). Including metered oxidation and catalytic oxidation processes (201310661638.5,201410011666.7). Whereas the metered oxidation method requires the consumption of large amounts of metered oxidants and some require strongly alkaline conditions (chemical world, 1991,10, 472-. Subsequent treatment of the product will produce a waste stream.
The method for preparing the gluconic acid by selectively oxidizing the glucose by taking air or oxygen as an oxidant and adopting a catalytic oxidation means has the advantages of high efficiency, simple process, mild reaction conditions and the like, and has great research potential. In recent years, in the research of catalytic oxidation of glucose, there are many reports on noble metal catalyst systems with gold, platinum and palladium as main active components (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 catalysts are expensive and generally require an alkaline environment to exert a good catalytic effect.
Therefore, the realization of the glucose catalytic selective oxidation in the alkali-free environment of a cheap non-noble metal catalytic system is a research direction with great development potential. Xujie subject is in Nitrogen Oxide (NO)x) Much research work has been done on catalyst systems (adv. synth. catl.2009, 351, 558-562; tetrahedron Lett.2009,50, 1677-; green chem.2010,12, 590-592; total. Commun.2010,11, 732-735; Total.Commun.2010, 11, 1189-; chi.j.catal.2011, 32, 118-; adv.synth.catal.2011,353, 226-230; chemsus chem 2011,4, 51-54; appl.Catal.A: Gen.2014,482, 231-236.). Nitroxide free radical 2,2,6, 6-tetramethylpiperidine-1-oxyl (TEMPO) can be used together with NaClO/NaBr to catalyze the oxidation of carbohydrates (carbohydrate. Res.1995,269, 89-98; Cellulose 2006,13, 679-; TEMPO is also widely used in selective oxidation of catalytic alcohols (Tetrahedron Lett.2001,42, 6651-.
The invention aims to realize the selective oxidation of glucose under the mild condition by using air or oxygen as an oxidant and using TEMPO and derivatives thereof and metal compounds as a catalytic system.
Disclosure of Invention
The invention aims to provide a novel method for selective oxidation of glucose with high efficiency and low energy consumption.
The technical scheme of the new method provided by the invention is as follows: a method for catalyzing selective oxidation of glucose uses air or oxygen as oxidant, TEMPO and its derivative and metallic compound as catalytic system, and obtains gluconic acid by catalytic oxidation of glucose in water phase under mild condition in gas-liquid closed pressurized reactor (the method and main product distribution are shown in formula 1).
Formula 1 the present invention provides a novel method for the catalytic oxidation of glucose
The method comprises the following specific steps:
adding a glucose solution into a gas-liquid closed pressurized reactor; filling oxygen-containing gas to ensure a certain oxygen partial pressure; adding a certain amount of catalyst TEMPO and derivatives thereof and metal compounds; heating and stirring the mixture to react for a certain time, and obtaining the gluconic acid after the reaction. The gluconic acid obtained was quantified by HPLC.
The composite catalyst comprises TEMPO and derivatives thereof and metal compounds, wherein the TEMPO and the derivatives thereof are as follows: one or more of TEMPO, 4-methyl TEMPO, 4-hydroxy TEMPO, 4-methoxy TEMPO, 4-nitro TEMPO, 4-amino TEMPO, 4-acetamido TEMPO, 4-methanesulfonic acid TEMPO, 4-cyano TEMPO and 4-carboxyl TEMPO; the usage amount of TEMPO and derivatives thereof is 0.05-20 mol% (preferably 0.5-15 mol%, most preferably 2-10 mol%) of the raw material glucose; the condition optimization experiment shows that TEMPO, 4-acetamido TEMPO, 4-methanesulfonic acid TEMPO, 4-carboxyl TEMPO and 4-nitro TEMPO have good catalytic effect.
The other component of the metal compound in the composite catalyst is: one or more of cobalt acetate, cobalt (II) acetylacetonate, manganese (II) acetate, manganese dioxide, manganese sulfate, bismuth nitrate, sodium nitrite, ferric nitrate, manganese nitrate, cupric nitrate, cobalt nitrate, cupric chloride, cupric bromide and ferric chloride; the amount of the metal compound is 0.05 to 20 mol% (preferably 0.5 to 15 mol%, most preferably 2 to 10 mol%) of the raw material glucose. The condition optimization experiment shows that the catalytic effect of cobalt acetate, cobalt (II) acetylacetonate and manganese (II) acetate is better.
The molar ratio of TEMPO and derivatives thereof to the metal compound is 20-0.1, preferably 10-0.5, and most preferably 5-1.
The reaction is carried out in a pressure reactor, and oxygen can be used as an oxygen source or air can be directly used as the oxygen source. Wherein the oxygen partial pressure is 0.1-3.0 MPa, the oxidation reaction rate is improved along with the increase of the oxygen partial pressure in a certain range, but the oxygen pressure is too high, so that side reaction can be caused, and the equipment cost can also be improved. Therefore, the oxygen partial pressure is preferably 0.5 to 2.0 MPa.
The reaction temperature is 40-160 ℃, and the reaction time can be shortened by increasing the reaction temperature, but side reactions can also be caused, so the reaction temperature is preferably 80-120 ℃.
The reaction time is 2-24 h, the conversion rate is improved along with the increase of the reaction time within a certain time range, but after the reaction time is prolonged to a certain time, the conversion rate and the product selectivity are stable, and the preferable reaction time is 6-16 h.
The invention has the following characteristics:
1. the invention firstly provides a method for catalyzing and selectively oxidizing glucose by taking air or oxygen as an oxidizing agent and taking TEMPO and derivatives thereof and metal compounds as a composite catalytic system.
2. In the invention, water is used as a solvent for the oxidation reaction of glucose, thus meeting the concept of environmental protection.
3. The invention takes air or oxygen as the final oxygen source, is clean, cheap and environment-friendly; the oxidation reaction condition is mild (40-160 ℃), the reaction process is easy to operate, and the safety is high.
4. The raw material glucose can be converted from cellulose, starch, sucrose, cellobiose and the like, and has wide sources, low price and easy obtainment.
Detailed Description
The invention is further illustrated by the following examples.
Example 1:
adding 2mmol of glucose, 5 mol% (relative to glucose) of cobalt acetate and 5 mol% (relative to glucose) of TEMPO into a 35mL reaction kettle, adding 6mL of deionized water, closing the kettle, introducing oxygen under the pressure of 0.5MPa, heating to 80 ℃ under stirring, and keeping the temperature for 8 hours. Then cooled to room temperature and carefully depressurized to atmospheric pressure. The entire product was transferred to a 50mL volumetric flask and the volume was fixed. The main product was qualitatively analyzed using HPLC and HPLC retention time of the standard. The product was quantitatively analyzed by HPLC chromatography external standard quantitative method. The conversion rate of glucose and the yield of gluconic acid were calculated according to the following formulas:
conversion [ mol% ]]=(n0-n)/n0×100%;
The yield is [ mol%]=nx/n0×100%;
In the formula, n0The amount of glucose added [ mol ] before the reaction]N is the amount of glucose remaining after the reaction [ mol],nxThe amount of a substance which is a product formed during the reaction [ mol ]]。
The conversion of glucose was calculated to be 93.5% and the yield of gluconic acid was calculated to be 77.4%.
Example 2:
2mmol glucose, 10 mol% (relative to glucose) cobalt (II) acetylacetonate and 10 mol% (relative to glucose) 4-hydroxy TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged at 1.0MPa, and the temperature was raised to 100 ℃ with stirring and held for 12 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed by the method of example 1 to obtain a glucose conversion of 82.7% and a gluconic acid yield of 70.1%.
Example 3:
2mmol glucose, 5 mol% (relative to glucose) manganese (II) acetate, 10 mol% (relative to glucose) 4-acetamido TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged to 1.5MPa, the temperature was raised to 120 ℃ with stirring, and the reaction was maintained for 16 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 94.0% and a yield of gluconic acid of 73.5%.
Example 4:
2mmol glucose, 20 mol% (relative to glucose) manganese dioxide, 20 mol% (relative to glucose) 4-amino TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged at 0.1MPa, the temperature was raised to 140 ℃ with stirring and held for 4 h. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed by the method of example 1 to obtain a conversion of glucose of 81.6% and a yield of gluconic acid of 66.4%.
Example 5:
2mmol of glucose, 2 mol% (relative to glucose) of manganese sulfate and 2 mol% (relative to glucose) of 4-acetamido TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added into the reaction kettle, the kettle is closed, oxygen pressure is introduced into the reaction kettle to be 3.0MPa, the temperature is raised to 160 ℃ under stirring, and the reaction kettle is kept for 20 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 91.3% and a yield of gluconic acid of 75.4%.
Example 6:
2mmol of glucose, 5 mol% (relative to glucose) of bismuth nitrate and 8 mol% (relative to glucose) of 4-cyano TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added into the reaction kettle, the kettle is closed, oxygen pressure is introduced into the reaction kettle to be 2.0MPa, the temperature is raised to 120 ℃ under stirring, and the reaction kettle is kept for 16 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 92.1% and a yield of gluconic acid of 76.4%.
Example 7:
2mmol glucose, 0.5 mol% (relative to glucose) sodium nitrite and 10 mol% (relative to glucose) TEMPO are added into a 35mL reaction kettle, 6mL deionized water is added into the kettle, the kettle is closed, oxygen pressure is filled into the kettle to be 1.5MPa, the temperature is raised to 80 ℃ under stirring, and the temperature is kept for 24 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 92.4% and a yield of gluconic acid of 60.7%.
Example 8:
2mmol glucose, 8 mol% (relative to glucose) ferric nitrate, 8 mol% (relative to glucose) 4-nitro TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged at 1.5MPa, the temperature was raised to 90 ℃ with stirring and held for 14 h. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 89.3% and a yield of gluconic acid of 75.8%.
Example 9:
2mmol of glucose, 15 mol% (relative to glucose) of manganese nitrate and 8 mol% (relative to glucose) of 4-methanesulfonic acid group TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added, the kettle is closed, oxygen pressure is introduced to be 1.0MPa, the temperature is raised to 80 ℃ under stirring, and the temperature is maintained for 18 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 90.3% and a yield of gluconic acid of 82.4%.
Example 10:
2mmol of glucose, 5 mol% (relative to glucose) of copper nitrate and 10 mol% (relative to glucose) of 4-methanesulfonic acid group TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added, the kettle is closed, oxygen pressure is filled into the kettle to be 0.5MPa, the temperature is raised to 100 ℃ under stirring, and the temperature is kept for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 90.6% and a yield of gluconic acid of 67.3%.
Example 11:
2mmol of glucose, 10 mol% (relative to glucose) of cobalt nitrate and 5 mol% (relative to glucose) of 4-nitro TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added into the reaction kettle, the kettle is closed, oxygen pressure is introduced into the reaction kettle to be 1.0MPa, the temperature is raised to 40 ℃ under stirring, and the reaction kettle is kept for 4 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 73.6% and a yield of gluconic acid of 59.2%.
Example 12:
2mmol glucose, 0.05 mol% (relative to glucose) copper chloride, 0.05 mol% (relative to glucose) 4-methoxy TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged at 2.0MPa, the temperature was raised to 160 ℃ with stirring, and the reaction was maintained for 16 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed by the method of example 1 to obtain a conversion of glucose of 81.1% and a yield of gluconic acid of 50.9%.
Example 13:
2mmol of glucose, 6 mol% (relative to glucose) of copper bromide and 6 mol% (relative to glucose) of 4-carboxyl TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added into the reaction kettle, the kettle is closed, oxygen pressure is introduced into the reaction kettle to be 1.5MPa, the temperature is raised to 60 ℃ under stirring, and the reaction kettle is kept for 3 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed by the method of example 1 to obtain a glucose conversion of 82.0% and a gluconic acid yield of 48.5%.
Example 14:
2mmol glucose, 8 mol% (relative to glucose) ferric chloride and 15 mol% (relative to glucose) 4-methyl TEMPO are added into a 35mL reaction kettle, 6mL deionized water is added into the kettle, the kettle is closed, oxygen pressure is introduced into the kettle to be 1.0MPa, the temperature is raised to 110 ℃ under stirring, and the temperature is maintained for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed by the method of example 1 to obtain a conversion of glucose of 86.1% and a yield of gluconic acid of 77.2%.
Example 15:
2mmol of glucose, 5 mol% (relative to glucose) of cobalt acetate and 10 mol% (relative to glucose) of TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added into the reaction kettle, the kettle is closed, oxygen is filled into the reaction kettle, the pressure is 1.0MPa, the temperature is raised to 100 ℃ under stirring, and the reaction kettle is kept for 9 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed by the method of example 1 to obtain a conversion of glucose of 91.7% and a yield of gluconic acid of 79.1%.
Example 16:
2mmol of glucose, 5 mol% (relative to glucose) of cobalt acetate and 15 mol% (relative to glucose) of 4-carboxyl TEMPO are added into a 35mL reaction kettle, 6mL of deionized water is added into the reaction kettle, the kettle is closed, oxygen pressure is introduced into the reaction kettle to be 0.5MPa, the temperature is raised to 120 ℃ under stirring, and the reaction kettle is kept for 8 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 87.5% and a yield of gluconic acid of 72.0%.
Example 17:
2mmol glucose, 10 mol% (relative to glucose) cobalt (II) acetylacetonate and 10 mol% (relative to glucose) 4-acetamido TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged at 1.5MPa, and the temperature was raised to 90 ℃ with stirring and held for 7 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a glucose conversion of 83.5% and a gluconic acid yield of 72.2%.
Example 18:
2mmol glucose, 15 mol% (relative to glucose) cobalt (II) acetylacetonate and 15 mol% (relative to glucose) 4-cyano TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged at 0.5MPa, and the temperature was raised to 60 ℃ with stirring and held for 10 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed according to the method in example 1 to obtain a conversion of glucose of 88.2% and a yield of gluconic acid of 71.5%.
Example 19:
2mmol glucose, 2 mol% (relative to glucose) manganese (II) acetate, 10 mol% (relative to glucose) 4-nitro TEMPO were added to a 35mL reaction vessel, 6mL deionized water was added, the vessel was closed, oxygen pressure was charged to 1.0MPa, the temperature was raised to 50 ℃ with stirring, and the reaction was maintained for 2 hours. After the reaction was completed, the reaction mixture was cooled to room temperature and carefully reduced to normal pressure. The product was analyzed by the method of example 1 to obtain a conversion of glucose of 71.7% and a yield of gluconic acid of 54.3%.
The reaction has the advantages of simple operation, mild conditions, high glucose conversion rate, good selectivity of the product gluconic acid and potential application prospect.
Although the present invention has been described with reference to specific embodiments, the scope of the present invention is not limited thereto, and the present invention is not limited to the above embodiments, and any changes or substitutions that can be easily made by those skilled in the art within the technical scope of the present invention will be included in the technical scope of the present invention. Therefore, the protection scope of the present invention is not limited to the above embodiments, and the protection scope of the claims should be subject to.
Claims (7)
1. A method of catalyzing selective oxidation of glucose, comprising: using air or oxygen as an oxidant, using TEMPO or TEMPO derivatives and metal compounds as composite catalysts, and selectively oxidizing glucose in a water phase to prepare gluconic acid; the TEMPO derivative is: one or more than two of 4-methyl TEMPO, 4-nitro TEMPO, 4-methanesulfonic acid TEMPO and 4-cyano TEMPO; the usage amount of TEMPO or TEMPO derivatives is 0.05-20 mol% of the raw material glucose;
the metal compound is: one or more of cobalt acetate, cobalt (II) acetylacetonate, manganese (II) acetate, manganese dioxide, manganese sulfate, sodium nitrite, cupric chloride and cupric bromide; the dosage of the metal compound is 0.05-20 mol% of the raw material glucose.
2. The method of claim 1, wherein: the dosage of the metal compound is 0.5-15 mol% of the raw material glucose.
3. The method of claim 2, wherein: the dosage of the metal compound is 2-10 mol% of the raw material glucose.
4. A method as claimed in claim 1, 2 or 3, characterized by: the molar ratio of TEMPO or TEMPO derivatives to the metal compound is 20-0.1.
5. The method of claim 1, wherein: in the catalytic conversion process, one or two of air or oxygen is used as an oxygen source, and the oxygen partial pressure is 0.1-3.0 MPa.
6. The method of claim 1, wherein: the reaction temperature is 40-160 ℃, and the reaction time is 2-24 h.
7. The method of claim 6, wherein: the reaction temperature is 80-120 ℃, and the reaction time is 6-16 h.
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