CN108911961B - Method for preparing tartronic acid by catalytic oxidation of glycerin - Google Patents
Method for preparing tartronic acid by catalytic oxidation of glycerin Download PDFInfo
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- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
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Abstract
The invention discloses a method for preparing tartronic acid by catalytic oxidation of glycerol, which takes potassium-modified nitrogen-doped mesoporous carbon material loaded Pt as a catalyst, and catalytically oxidizes the glycerol under mild and non-alkaline conditions to prepare the tartronic acid in one step, wherein the mild conditions are as follows: the reaction temperature is lower than 60 ℃ and the reaction is carried out under normal pressure. Modifying the nitrogen-doped mesoporous carbon material by using potassium species, so that the alkalinity of the carrier is improved; secondly, the potassium-modified nitrogen-doped mesoporous carbon material is used as a carrier to prepare a supported Pt-based catalyst, so that the catalytic oxidation activity of the Pt-based catalyst is improved; thirdly, glycerin is catalyzed and oxidized under mild and non-alkaline conditions to prepare tartronic acid in one step, so that the use of alkali and the occurrence of related side reactions are avoided.
Description
Technical Field
The invention relates to a method for preparing tartronic acid, in particular to a method for preparing tartronic acid by catalytic oxidation of glycerin. The method can realize the one-step preparation of the tartronic acid by efficiently catalyzing and oxidizing the glycerol under mild temperature and non-alkaline conditions. Belongs to the field of chemical engineering.
Background
Tartronic acid is a platform chemical with higher added value, is widely applied in the field of medicine, can inhibit the conversion of saccharides in a human body into fat, prevents the accumulation of fat in the human body, and has the effects of losing weight and preventing coronary heart disease (Green Chemistry,2011,13, 1960-. Industrial tartronic acid is mainly prepared from maleic acid as a raw material by a potassium permanganate oxidation method, and has the defects of high production cost, serious pollution and the like (RSC Advance,2016,6, 41007-. Therefore, the method for preparing the tartronic acid by the green and atom-economic chemoselective catalytic oxidation glycerin has obvious application potential.
The supported metal (Au, Pd and Pt) catalyst has good catalytic effect under alkaline condition, and can realize complete conversion of glycerol under mild condition (Catalysis Today,2005,102, 203-212.). However, in most work, glyceric acid is the major product and tartronic acid is a by-product (Accounts of Chemical Research,2015,48, 1403-1412). Therefore, in order to increase the yield of tartronic acid, it is possible to increase the catalytic oxidation activity of the supported noble metal catalyst and to suppress the formation of excessive oxidation products.
Few studies have been reported on the direct preparation of tartronic acid by catalytic oxidation of glycerol. Kimura et al made the first attempt, they prepared palladium (Ce-Bi-Pd/C) and palladium/platinum (Ce-Bi-Pd-Pt/C) catalysts with activated carbon as a carrier by using cerium and bismuth as catalyst promoters, achieved complete conversion of glycerol, and reached 58% yield of tartronic acid, and the study of the catalytic reaction mechanism also confirmed that glycerol was first oxidized to glyceric acid and then continued to be oxidized to tartronic acid (Patent JP199395253,1994). Xujie et al reported 2014 that tartronic acid was prepared under mild conditions using an Au/HY catalyst with 98% conversion of glycerol and 80% yield of tartronic acid. The small size of Au nanoparticles was shown to significantly promote the formation of tartronic acid (Chinese Journal of Catalysis,2014,35, 1653-. Chaudhari et al, 2017 reported that glycerol was oxidized to tartronic acid under mild conditions with a phase-shifting PtFe nanocomposite catalyst in 59% yield, the catalytic activity was improved because the Pt-Fe bimetallic structure shifts from disordered face-centered cubic (fcc) to ordered and lattice distorted face-centered tetragonal (fct) (Industrial & Engineering Chemistry Research,2017,56, 13157-13164).
However, the above reactions are all carried out under alkaline conditions, and the presence of strong base makes some products in the reaction system interconvertible, thereby masking the product selectivity nature of the catalyst and increasing the difficulty of product analysis, separation and catalyst mechanism study (Chinese Journal of Catalysis,2017,38, 537-). 544). Therefore, there is a need to develop non-basic catalytic systems for the catalytic oxidation of glycerol to tartronic acid.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for preparing tartronic acid by catalytic oxidation of glycerol at mild temperature under non-alkaline conditions in one step. Modifying the nitrogen-doped mesoporous carbon material by using potassium element to improve the alkalinity of the carrier; secondly, the potassium-modified nitrogen-doped mesoporous carbon material is used as a carrier to prepare a supported Pt-based catalyst, so that the catalytic oxidation activity of the Pt-based catalyst is improved; thirdly, glycerin is catalyzed and oxidized under mild and non-alkaline conditions to prepare tartronic acid in one step, so that the use of alkali and the occurrence of related side reactions are avoided.
In order to achieve the purpose, the invention adopts the following technical scheme:
a method for preparing tartronic acid by catalytic oxidation of glycerol uses Pt loaded by a potassium-modified nitrogen-doped mesoporous carbon material as a catalyst, and prepares the tartronic acid by one-step catalytic oxidation of a glycerol aqueous solution under mild and non-alkaline conditions.
Preferably, O is introduced during the reaction in the preparation method2。
Preferably, the molar ratio of glycerol to metallic Pt particles (0-valent Pt element) is: 100-1000.
Preferably, the concentration of the glycerol aqueous solution is 50 to 1000mmol/L, and more preferably 300 to 1000 mmol/L.
Preferably, the mild conditions are: the reaction temperature is lower than 60 ℃ and the reaction is carried out under normal pressure.
More preferably, the flow rate of the oxygen gas is 5 to 200mL/min, and still more preferably 10 to 100 mL/min.
Further preferably, the catalytic reaction time is 1 to 10 hours. In general, when the reaction temperature is high, the reaction time is short and when the reaction temperature is low, the reaction time is prolonged as appropriate for obtaining a malonic acid in a high yield. The reaction time is properly selected within 1-10 hours after the experiment.
Preferably, the loading amount of Pt in the potassium-modified nitrogen-doped mesoporous carbon material-loaded Pt catalyst is as follows: 1% -5%; the content of potassium is: 2.13% -6.56%; the content of nitrogen is: 5.47-13.73%, wherein the loading amount and the content are mass contents.
Further preferably, the loading amount of Pt in the Pt catalyst loaded with the potassium-modified nitrogen-doped mesoporous carbon material is as follows: 1 to 2 percent.
Preferably, the preparation method of the potassium-modified nitrogen-doped mesoporous carbon material-supported Pt catalyst comprises the following steps: adding H to aqueous polyvinyl alcohol solution2PtCl6Configuration H2PtCl6A solution; to H2PtCl6Adding a certain amount of NaBH into the solution4And (3) forming a dark brown sol, adding a potassium modified nitrogen-doped mesoporous carbon material (K-NMC) after 30 minutes, stirring for 2 hours, filtering, washing and drying to obtain a black powdery potassium modified nitrogen-doped mesoporous carbon material-loaded Pt catalyst (Pt/K-NMC).
In the above preparation method, polyvinyl alcohol (PVA) is used as a stabilizer.
Further preferred, NaBH4The concentration of (A) is 10-1000 mmol/L; NaBH4The molar ratio of the metal Pt to the metal Pt is 1-10: 1.
Further preferred, NaBH4The concentration of (A) is 100 to 200 mmol/L.
Further preferably, the polyvinyl alcohol (PVA) has an average molecular weight of 9000 to 10000g/mol and H2PtCl6The concentration is 0.1-1.5 mmol/L, and the mass ratio of PVA to Pt is 1-10: 1.
Further preferably, H2PtCl6The concentration is 0.2-0.4 mmol/L; the mass ratio of PVA to Pt is 1.2-5: 1.
Further preferably, the preparation method of the potassium-modified nitrogen-doped mesoporous carbon material (K-NMC) comprises the following steps:
(1) preparing a nitrogen-doped mesoporous carbon material by using silicon spheres as a hard template, phenolic resin as a carbon source and melamine as a nitrogen source, wherein the nitrogen content is 9.56-13.73%; or block polyether (Pluronic F127) is used as a soft template, phenolic resin is used as a carbon source, dicyandiamide is used as a nitrogen source, and the nitrogen-doped mesoporous carbon material is prepared by an evaporation induction self-assembly method, wherein the nitrogen content is 5.47-10.56%;
(2) uniformly mixing KOH and the nitrogen-doped mesoporous carbon (NMC), and heating in a nitrogen atmosphere for activation treatment to obtain a solid I;
(3) adding ethanol into the NMC subjected to KOH activation treatment, heating and refluxing for 5 hours, filtering, washing to be neutral, and drying to obtain a solid II;
(4) and heating the solid II in a nitrogen atmosphere to roast at high temperature to obtain the potassium-modified nitrogen-doped mesoporous carbon material (K-NMC).
Further preferably, in the step (1), the KOH and the NMC are mixed in a ball milling or grinding mode, the activation treatment temperature is 500-800 ℃, and the activation treatment time is 0.1-2.0 hours.
More preferably, the temperature of the activation treatment is 600 to 700 ℃, and the time of the activation treatment is 0.5 to 1.0 hour.
Further preferably, the high-temperature roasting temperature in the step (3) is 1000-1400 ℃, and the roasting treatment time is 0.5-2.0 hours.
Further preferably, the high-temperature roasting temperature is 1000-1200 ℃, and the roasting treatment time is 0.5-1.0 hour.
The invention has the beneficial effects that:
(1) the nitrogen-doped mesoporous carbon material adopted by the invention has the advantages of various preparation methods, wide raw material source, low cost and the like.
(2) The potassium-modified nitrogen-doped mesoporous carbon material has the advantages of simple preparation method, strong alkalinity, good stability and the like, and is beneficial to loading of Pt metal.
(3) The Pt-based catalyst prepared by the invention has the characteristics of high catalytic oxidation activity, mild reaction conditions, high stability, easiness in recycling and the like.
Drawings
FIG. 1 shows the stability evaluation of the catalyst used in example 1.
Detailed Description
The present invention will be further described with reference to the accompanying drawings and examples, which are provided for the purpose of illustration only and are not intended to limit the scope of the invention.
Example 1:
firstly, preparing a catalyst:
(1) the molar ratio of the nitrogen-doped mesoporous carbon material prepared by using the silicon spheres as a hard template, the phenolic resin as a carbon source and the melamine as a nitrogen source is 2:1), and the content of the obtained nitrogen is 13.73%.
The method comprises the following specific steps: 3.67g of phenol were put into a 250ml Erlenmeyer flask, 50ml of 200mmol/LNaOH solution was added thereto and stirred for 10min, and after 6.33g of 37% formaldehyde was added dropwise thereto, it was heated under stirring in a water bath at 70 ℃ for 40 min. Then adding 4.92g of melamine and 9.50g of formaldehyde (the molar ratio of the melamine to the phenol is 1: 1; or adding 9.84g of melamine and 12.67g of formaldehyde, the molar ratio of the melamine to the phenol is 2:1), continuing to heat and stir for 30min, adding 50g of 30% silica sol (Ludox SM-30), stirring uniformly, transferring the mixed solution to a sealed bottle, placing the sealed bottle into an oven, keeping the temperature of the oven at 80 ℃ for 3 days, opening the bottle cap, drying for one day, taking out the solid, grinding the solid into powder, placing the powder into a crucible, placing the crucible into a tube furnace, and performing vacuum evaporation on the mixed solution in a vacuum furnace under the condition of N2And raising the temperature to 800 ℃ at the temperature rise rate of 5 ℃/min under the protection of gas, keeping the temperature for 3 hours, finally soaking the carbonized sample in 5% HF for 24 hours to remove silicon spheres, washing the sample with distilled water, and drying the washed sample to obtain the nitrogen-doped mesoporous carbon material. Wherein the nitrogen content is 9.56% when the molar ratio of melamine to phenol is 1:1 and 13.74% when the molar ratio of melamine to phenol is 2: 1.
(2) Uniformly mixing 0.2g of the nitrogen-doped mesoporous carbon material with 0.4g of KOH in a ball mill, and then adding the mixture into N2Heating at a rate of 3 deg.C/min under atmosphere and maintaining at 600 deg.C for 1 hr;
(3) the activated sample was boiled under reflux in 80 ℃ ethanol (250mL) for 5 hours, filtered and washed with boiled distilled water until pH was neutral;
(4) the samples obtained were dried in a vacuum oven at 110 ℃ and then N2Heating at the speed of 10 ℃/min in the atmosphere and keeping at 1000 ℃ for 1 hour to obtain the potassium modified mesoporous carbon material; the mass content of potassium in the obtained potassium modified mesoporous carbon material is 6.56%;
(5) preparation of 0.4 mmol/L50 mLH2PtCl6A solution to which polyvinyl alcohol (PVA) (having an average molecular weight of 9000 to 10000g/mol, a mass ratio of PVA to Pt of 1.2:1) was added
(6) The newly prepared 100mmol/LNaBH4(NaBH4Molar ratio Pt metal 5) solution was added quickly to the above solution to form a dark brown sol, and after 30 minutes the support material was added with vigorous stirring. The amount of support material required was calculated to give a final metal loading of 2%. (ICP-OES found 2.02%)
(7) After stirring for 2 hours, the product was collected by filtration and washed several times with deionized water. The resulting black powder was dried overnight in an oven at 110 ℃ for catalytic testing.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a predetermined amount of Pt-based catalyst (glycerol/Pt molar ratio: 250) were charged into a reactor, stirred, and O was introduced at room temperature (25 ℃ C.)2(10mL/min) was subjected to an oxidation reaction for 5 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 85.5% and the yield of tartronic acid was 64.5%.
The catalyst was centrifuged off, washed several times with deionized water and dried in an oven at 110 ℃ overnight. The above catalytic experiment was repeated 4 times in succession to evaluate the stability of the catalyst, and the results are shown in FIG. 1. As can be seen from FIG. 1, the catalyst has no obvious change in the conversion rate of glycerol and the yield of tartronic acid in 5 consecutive catalytic reactions, and shows good catalytic stability.
Example 2
Preparation of catalyst
The catalyst preparation method is the same as in example 1.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio: 100) were charged into a reactor, stirred, and O was introduced at room temperature (25 ℃ C.)2(10mL/min) was subjected to an oxidation reaction for 5 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 94.2% and the yield of tartronic acid was 72.4%.
Example 3
Preparation of catalyst
The catalyst preparation method is the same as in example 1.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio of 250) were charged into a reactor, stirred, and O was introduced under mild conditions (40 ℃ C.)2(10mL/min) was subjected to oxidation for 3 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 91.3% and the yield of tartronic acid was 63.3%.
Example 4
Preparation of catalyst
The catalyst preparation method is the same as in example 1.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio of 250) were charged into a reactor, stirred, and O was introduced under mild conditions (50 ℃ C.)2(10mL/min) was subjected to oxidation for 2 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 90.5% and the yield of tartronic acid was 62.1%.
Example 5
Preparation of catalyst
The catalyst preparation method is the same as in example 1.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 1000mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio of 250) were charged into a reactor, stirred, and O was introduced under mild conditions (60 ℃ C.)2(100mL/min) was subjected to an oxidation reaction for 1 hour. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 78.3% and the yield of tartronic acid was 56.1%.
Example 6
Firstly, preparing a catalyst:
(1) by the method in example 1, the nitrogen-doped mesoporous carbon material is obtained by adjusting the amount of melamine (the molar ratio of melamine to phenol is 1:1), and the content of nitrogen is 9.56%;
(2) uniformly mixing 0.2g of the nitrogen-doped mesoporous carbon material with 0.4g of KOH in a ball mill, and then adding the mixture into N2Heating at a rate of 3 deg.C/min under atmosphere and maintaining at 600 deg.C for 1 hr;
(3) the activated sample was boiled under reflux in 80 ℃ ethanol (250mL) for 5 hours, filtered and washed with boiled distilled water until pH was neutral;
(4) the samples obtained were dried in a vacuum oven at 110 ℃ and then N2Heating at the speed of 10 ℃/min in the atmosphere and keeping at 1000 ℃ for 1 hour to obtain the potassium modified mesoporous carbon material; the mass content of potassium in the obtained potassium modified mesoporous carbon material is 3.28%;
(5) preparation of 0.4 mmol/L50 mL H2PtCl6A solution, and adding polyvinyl alcohol (PVA) (average molecular weight 9000 to 10000g/mol, mass ratio of PVA to Pt is 1.2: 1;
(6) the newly prepared 100mmol/LNaBH4(NaBH4Molar ratio Pt metal 5) solution was added quickly to the above solution to form a dark brown sol, and after 30 minutes the support material was added with vigorous stirring. The amount of support material required was calculated to give a final metal loading of 2% (ICP-OES found 2.06%).
(7) After stirring for 2 hours, the product was collected by filtration and washed several times with deionized water. The resulting black powder was dried overnight in an oven at 110 ℃ for catalytic testing.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio: 250) were charged into a reactor, stirred, and O was introduced at room temperature (25 ℃ C.)2(10mL/min) was subjected to an oxidation reaction for 5 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 76.2% and the yield of tartronic acid was 55.8%.
Example 7
Firstly, preparing a catalyst:
(1) the potassium-modified mesoporous carbon material prepared in example 6 was used as a catalyst carrier;
(2) preparation of 0.4 mmol/L50 mL H2PtCl6A solution, and adding polyvinyl alcohol (PVA) (average molecular weight 9000 to 10000g/mol, mass ratio of PVA to Pt is 1.2: 1;
(3) the newly prepared 100mmol/LNaBH4(NaBH4Molar ratio Pt metal 5) solution was added quickly to the above solution to form a dark brown sol, and after 30 minutes the support material was added with vigorous stirring. The amount of support material required was calculated to give a final metal loading of 1% (ICP-OES found 1.03%).
(4) After stirring for 2 hours, the product was collected by filtration and washed several times with deionized water. The resulting black powder was dried overnight in an oven at 110 ℃ for catalytic testing.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio: 250) were charged into a reactor, stirred, and O was introduced at room temperature (25 ℃ C.)2(10mL/min) was subjected to an oxidation reaction for 5 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 68.3% and the yield of tartronic acid was 44.7%.
Example 8
Preparation of catalyst
(1) The nitrogen-doped mesoporous carbon material is prepared by an evaporation-induced self-assembly method by taking block polyether (Pluronic F127) as a soft template, phenolic resin as a carbon source and dicyandiamide as a nitrogen source, wherein the nitrogen content is 10.56%.
The preparation method comprises the following steps: 1g F127 g and 2g dicyandiamide were completely dissolved in 16g ethanol and 8g water in a water bath at a temperature below 50 ℃, then 20% resol ethanol solution was added and stirred in a water bath at 50 ℃ for 30 minutes. The finally obtained light orange transparent clear solution was poured into a petri dish, placed in an oven at 50 ℃ to evaporate the solvent for 6 hours to obtain a transparent composite film, and then heated to 100 ℃ for 24 hours to perform heat curing. The resulting composite film is scraped off and crushed into small pieces for pyrolysis and carbonization. The mixture was heated to 350 ℃ at a heating rate of 1 ℃/min for 3 hours in a tube furnace under a nitrogen atmosphere to carry out pyrolysis, and then heated to 800 ℃ at a heating rate of 2.5 ℃/min for 3 hours to carry out carbonization.
(2) 0.1g of nitrogen-doped mesoporous carbon material was uniformly mixed with 0.5g of KOH in a ball mill. Then the mixture is added to N2Heat at a rate of 5 ℃/min under atmosphere and hold at 700 ℃ for 0.5 hour.
(3) The activated sample was heated to reflux in ethanol (250mL) for 5 hours, filtered and washed with boiling distilled water until pH was neutral.
(4) The samples obtained were dried in a vacuum oven at 110 ℃ and then N2Heating at the speed of 10 ℃/min in the atmosphere and keeping the temperature at 1200 ℃ for 0.5 hour to obtain the potassium modified mesoporous carbon material, wherein the mass content of potassium in the obtained potassium modified mesoporous carbon material is 5.14%.
(5) Preparation of 0.2mmol/L H2PtCl650mL of the solution, and to this solution was added polyvinyl alcohol (PVA) (average molecular weight 9000 to 10000g/mol, mass ratio of PVA to Pt 5: 1.
(6) The newly prepared 200mmol/LNaBH4(NaBH4Molar ratio Pt metal 5) solution was added quickly to the above solution to form a dark brown sol, and after 10 minutes the support material was added with vigorous stirring. The amount of support material required was calculated to give a final metal loading of 2.3% (ICP-OES found to be 2.32%).
(7) After stirring for 2 hours, the product was collected by filtration and washed several times with deionized water. The resulting black powder was dried overnight in an oven at 110 ℃ for catalytic testing.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio of 250) were charged into a reactor, stirred, and O was introduced under mild conditions (50 ℃ C.)2(10mL/min) was subjected to oxidation for 2 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 87.8% and the yield of tartronic acid was 60.7%.
Example 9
Preparation of catalyst
The catalyst preparation method is the same as in example 8.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
200mL of 500mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio of 250) were charged into a reactor, stirred, and O was introduced under mild conditions (60 ℃ C.)2(50mL/min) was subjected to an oxidation reaction for 1 hour. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 80.5% and the yield of tartronic acid was 58.7%.
Example 10
Preparation of catalyst
The catalyst preparation method is the same as in example 8.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
10mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (molar ratio of glycerol/Pt: 1000) were charged into a reactor, stirred, and O was introduced under mild conditions (25 ℃ C.)2(50mL/min) was subjected to an oxidation reaction for 10 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 63.6% and the yield of tartronic acid was 40.2%.
Example 11
Preparation of catalyst
The catalyst preparation method is the same as in example 8.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
200mL of 1000mmol/L glycerol aqueous solution and a Pt-based catalyst (glycerol/Pt molar ratio of 100) were charged into a reactor, stirred, and O was introduced under mild conditions (60 ℃ C.)2(100mL/min) was subjected to an oxidation reaction for 5 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 100% and the yield of tartronic acid was 39.1%.
Example 12
Firstly, preparing a catalyst:
(1) adjusting the using amount of dicyandiamide to be 1g by using the method in the embodiment 8 to obtain the nitrogen-doped mesoporous carbon material, wherein the nitrogen content is 5.47%;
(2) 0.1g of nitrogen-doped mesoporous carbon material was uniformly mixed with 0.5g of KOH in a ball mill. Then the mixture is added to N2Heat at a rate of 5 ℃/min under atmosphere and hold at 700 ℃ for 0.5 hour.
(3) The activated sample was heated to reflux in ethanol (250mL) for 5 hours, filtered and washed with boiling distilled water until pH was neutral.
(4) The samples obtained were dried in a vacuum oven at 110 ℃ and then N2Heating at the speed of 10 ℃/min in the atmosphere and keeping the temperature at 1200 ℃ for 0.5 hour to obtain the potassium modified mesoporous carbon material, wherein the mass content of potassium in the obtained potassium modified mesoporous carbon material is 2.13 percent;
(5) preparation of 50mL of 0.2mmol/L H2PtCl6A solution, and to this solution polyvinyl alcohol (PVA) (average molecular weight 9000 to 10000g/mol, PVA to Pt mass ratio 5: 1) was added.
(6) The newly prepared 200mmol/LNaBH4(NaBH4Molar ratio Pt metal 5) solution was added quickly to the above solution to form a dark brown sol, and after 10 minutes the support material was added with vigorous stirring. The amount of support material required was calculated to give a final metal loading of 2.3% (ICP-OES found 2.26%).
(7) After stirring for 2 hours, the product was collected by filtration and washed several times with deionized water. The resulting black powder was dried overnight in an oven at 110 ℃ for catalytic testing.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio of 250) were charged into a reactor, stirred, and O was introduced under mild conditions (25 ℃ C.)2(10mL/min) was subjected to an oxidation reaction for 5 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 72.4% and the yield of tartronic acid was 46.7%.
Example 13
Firstly, preparing a catalyst:
(1) the potassium-modified mesoporous carbon material prepared in example 12 was used as a catalyst carrier;
(2) preparation of 50mL of 0.2mmol/L H2PtCl6A solution, and to this solution polyvinyl alcohol (PVA) (average molecular weight 9000 to 10000g/mol, PVA to Pt mass ratio 5: 1) was added.
(3) The newly prepared 200mmol/LNaBH4(NaBH4Molar ratio Pt metal 5) solution was added quickly to the above solution to form a dark brown sol, and after 10 minutes the support material was added with vigorous stirring. The amount of support material required was calculated to give a final metal loading of 1% (ICP-OES found 0.97%).
(4) After stirring for 2 hours, the product was collected by filtration and washed several times with deionized water. The resulting black powder was dried overnight in an oven at 110 ℃ for catalytic testing.
Secondly, catalyzing oxidation of glycerin to prepare tartronic acid
50mL of 300mmol/L aqueous glycerol solution and a Pt-based catalyst (glycerol/Pt molar ratio of 250) were charged into a reactor, stirred, and O was introduced under mild conditions (25 ℃ C.)2(10mL/min) was subjected to an oxidation reaction for 5 hours. After the catalyst was separated by centrifugation, quantitative analysis was performed on the supernatant, and the conversion of glycerin was 58.7% and the yield of tartronic acid was 40.1%.
Although the embodiments of the present invention have been described with reference to the accompanying drawings, the scope of the present invention is not limited thereto, and various modifications and variations which do not require inventive efforts and which are made by those skilled in the art are within the scope of the present invention.
Claims (8)
1. The method for preparing tartronic acid by catalytic oxidation of glycerol is characterized in that potassium modified nitrogen-doped mesoporous carbon material loaded Pt is used as a catalyst, glycerol is catalytically oxidized under mild and non-alkaline conditions to prepare tartronic acid in one step, and the mild conditions are as follows: the reaction temperature is lower than 60 ℃ and the reaction is carried out under normal pressure; the loading amount of Pt in the potassium-modified nitrogen-doped mesoporous carbon material-loaded Pt catalyst is as follows: 1% -5%; the content of potassium is: 2.13% -6.56%; the content of nitrogen is: 5.47% -13.73%, and the preparation method of the potassium-modified nitrogen-doped mesoporous carbon material supported Pt catalyst comprises the following steps: adding H to aqueous polyvinyl alcohol solution2PtCl6Configuration H2PtCl6A solution; to H2PtCl6Adding a certain amount of NaBH into the solution4And (3) forming a dark brown sol from the solution, adding the potassium modified nitrogen-doped mesoporous carbon material after 30 minutes, stirring for 2 hours, filtering, washing and drying to obtain a black powdery potassium modified nitrogen-doped mesoporous carbon material-loaded Pt catalyst.
2. The method for preparing tartronic acid by catalytic oxidation of glycerin as claimed in claim 1, characterized by that in the course of reaction of the above-mentioned preparation method O is introduced2。
3. The method for preparing tartronic acid by catalytic oxidation of glycerol according to claim 1, characterized in that the molar ratio of glycerol to metallic Pt particles is: 100-1000.
4. The method for preparing tartronic acid by catalytic oxidation of glycerin according to claim 2, wherein the flow rate of oxygen is 5 to 200 mL/min.
5. The method for preparing tartronic acid by catalytic oxidation of glycerin according to claim 1, characterized in that the catalytic reaction time is 1-10 hours.
6. Root of herbaceous plantThe method of claim 5, wherein NaBH is used to catalyze the oxidation of glycerol to tartronic acid4The concentration of (A) is 10-1000 mmol/L; NaBH4The molar ratio of the metal Pt to the metal Pt is 1-10: 1; the average molecular weight of the polyvinyl alcohol is 9000-10000 g/mol; h2PtCl6The concentration is 0.1-1.5 mmol/L, and the mass ratio of PVA to Pt is 0.1-10: 1.
7. The method for preparing tartronic acid by catalytic oxidation of glycerol according to claim 5, wherein the method for preparing the potassium-modified nitrogen-doped mesoporous carbon material comprises the following steps:
(1) taking silicon spheres or block polyether as a hard template, phenolic resin as a carbon source, and melamine or dicyandiamide as a nitrogen source; preparing a nitrogen-doped mesoporous carbon material by an evaporation-induced self-assembly method;
(2) after KOH and the nitrogen-doped mesoporous carbon are uniformly mixed, heating the mixture in a nitrogen atmosphere to carry out activation treatment, thus obtaining a solid I;
(3) adding the nitrogen-doped mesoporous carbon subjected to KOH activation treatment into ethanol, heating and refluxing for 5 hours, filtering, washing to neutrality, and drying to obtain a solid II;
(4) and heating the solid II in a nitrogen atmosphere to roast at high temperature to obtain the potassium-modified nitrogen-doped mesoporous carbon material (K-NMC).
8. The method for preparing tartronic acid by catalytic oxidation of glycerin according to claim 7, characterized in that, in the step (1), KOH and NMC are mixed by ball milling or grinding; the temperature of the activation treatment is 500-800 ℃; the activation treatment time is 0.1-2.0 hours; and (3) roasting at the high-temperature roasting temperature of 1000-1400 ℃ for 0.5-2.0 hours.
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| JP2013035805A (en) * | 2011-08-10 | 2013-02-21 | National Institute Of Advanced Industrial Science & Technology | Catalyst for liquid phase oxidation reaction of glycerol and oxidation reaction method of glycerol using the catalyst |
| CN103145545A (en) * | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Method of preparing propanoldiacid through catalytic oxidation of glycerol |
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| JP2013035805A (en) * | 2011-08-10 | 2013-02-21 | National Institute Of Advanced Industrial Science & Technology | Catalyst for liquid phase oxidation reaction of glycerol and oxidation reaction method of glycerol using the catalyst |
| CN103145545A (en) * | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Method of preparing propanoldiacid through catalytic oxidation of glycerol |
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| Platinum nanoparticles supported on N-doped carbon nanotubes for the selective oxidation of glycerol to glyceric acid in a base-free aqueous solution;Shasha Chen等;《RSC Advances》;20150327;第5卷;第1699-1707页 * |
| Selective Oxidation of Glycerol to Glyceric Acid in Base-Free Aqueous Solution at Room Temperature Catalyzed byPlatinum Supported on Carbon Activated with Potassium Hydroxide;Hua Tan等;《CHEMCATCHEM》;20160418;第8卷;第31566-31574页 * |
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