CN113024370B - Method for preparing formic acid from biomass polyol - Google Patents

Method for preparing formic acid from biomass polyol Download PDF

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CN113024370B
CN113024370B CN201911250187.XA CN201911250187A CN113024370B CN 113024370 B CN113024370 B CN 113024370B CN 201911250187 A CN201911250187 A CN 201911250187A CN 113024370 B CN113024370 B CN 113024370B
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formic acid
glycerol
cerium dioxide
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CN113024370A (en
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王峰
任濮宁
罗能超
高著衍
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Dalian Institute of Chemical Physics of CAS
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Abstract

The invention relates to a method for preparing formic acid by photo-thermally catalyzing biomass polyalcohol C-C bond oxidation and fracture with a cerium dioxide-based catalyst. The method uses glycerol, xylose, glucose, fructose, sucrose, cellobiose or starch as a reaction substrate, oxygen as an oxidant, cerium dioxide or supported cerium dioxide as a catalyst, and realizes the selective oxidation of the reaction substrate to formic acid under the irradiation of visible light of 400-650 nm at a certain temperature. The reaction process is as follows: dissolving a substrate in a solvent, adding a catalyst, sealing a reactor, replacing with oxygen for three times, keeping a certain pressure, and irradiating with 400-650 nm visible light at 40-150 ℃ for reaction to generate formic acid. The synthesis method can play an important role in preparing the formic acid by the high-selectivity oxidation of the biomass polyol.

Description

Method for preparing formic acid from biomass polyol
Technical Field
The invention relates to a method for preparing formic acid, in particular to a method for photo-thermally catalyzing biomass polyol glycerol, xylose, glucose, fructose, sucrose, cellobiose or starch to be oxidized into formic acid by using cerium dioxide or supported cerium dioxide.
Background
The development of renewable resources is imminent due to the increasing exhaustion of fossil energy and environmental pollution and greenhouse effect caused by the use of fossil energy, and the development of biomass, which is a carbon resource rich in natural content and unique in renewable energy, plays an important role in solving the energy crisis (chem.rev.2018,118(2), 505-. The biomass includes lignocellulose, sugar, biological oil and fat, etc., and is a polymer with rich oxygen content and composed of C skeleton. The selective oxidative cleavage of the biomass C-C bond not only can convert the biomass C-C bond into a high value-added small molecular compound, but also can introduce a new functional group such as a carboxylic acid group.
Formic acid is one of basic organic chemical raw materials, and can be widely used for tanning pesticides, dyes, leather and the likeBesides, formic acid can be converted into high-purity H by a photo-electric or thermal method2Are excellent hydrogen storage materials (Energy Fuels 2017,31(11),12603-&Environmental Science 2019) and formic acid direct fuel cell is also a way of direct supply of formic acid (chem.rev.2014,114(10), 5117-. The C-C bond of biomass polyol such as glycerol, xylose, glucose, fructose, sucrose, cellobiose or starch is selectively oxidized and broken to formic acid, so that the efficient utilization of biomass can be realized, a hydrogen donor raw material with a high additional value can be provided, and the method has important significance for the high-value utilization of biomass and the application to the current energy problem.
At present, the method for breaking the C-C bond of the biomass polyol is mostly a reaction catalyzed by solid acid under hydrothermal conditions, and the method usually needs to load noble metal, have higher reaction temperature and high concentration of H2O2Meanwhile, the problem of low selectivity also often exists; photocatalysis and electrocatalysis due to mild reaction conditions, selective oxidative cleavage of the C-C bond of catalytic biomass to formic acid has been increasingly emphasized in recent years (ACS Catal.2018,8 (3); 2129-. By TiO2The photocatalytic oxidation of glucose in 0.03M NaOH solution can result in 35% formic acid yield (ACS Sustainable Chemistry)&Engineering 2017,5(8),6377-2After the Au nano particles are loaded, the catalyst can efficiently convert glycerol into formic acid under visible light due to the LSPR effect of the Au particles under illumination. In the photocatalytic conversion of biomass polyols, H is often used in an alkaline solution to increase the selectivity of the reaction2O2As an oxidizing agent, there are other problems such as low reactivity and low conversion rate.
Reactions which can not be realized by pure photocatalysis or thermal catalysis can be realized by utilizing the photo-thermal synergistic effect, and high reaction activity and selectivity can be obtained in the process. Recent studies show that the ceria-based catalyst has higher activity in the aspect of photothermal catalytic organic matter conversion (ACS Catal.2015,5,3278-3286, J.Phys.chem.C 2013,117,24242-24249, J.Phys.chem.C 2011,115, 14050-14057). The cerium dioxide-based catalyst is of great significance for biomass conversion under photothermal conditions.
Disclosure of Invention
The invention relates to a method for preparing formic acid by using a cerium dioxide-based catalyst to photo-thermally catalyze the oxidative cleavage of a C-C bond of biomass polyol. The method uses glycerol, xylose, glucose, fructose, sucrose, cellobiose or starch as a reaction substrate, oxygen as an oxidant, cerium dioxide or supported cerium dioxide as a catalyst, and realizes selective oxidation to formic acid by irradiation of 400-650 nm visible light at 40-150 ℃. The invention realizes the high-selectivity conversion of renewable biomass polyol to formic acid under the photo-thermal condition, and the synthesis method has important effect on the high-selectivity oxidation of the biomass polyol to the formic acid.
The technical scheme adopted by the invention is as follows:
dissolving a substrate in a solvent, adding a catalyst, sealing a reactor, replacing with oxygen for three times, keeping a certain pressure, irradiating with 400-650 nm visible light at 40-150 ℃ for reaction for not less than 0.5h, and generating formic acid.
The catalyst is loaded with metal in an amount of 0.5mol% -2.0 mol% except pure cerium dioxide.
The catalyst used in the reaction is cerium dioxide or supported metal cerium dioxide, wherein: loaded with cerium dioxide M/CeO2Can be as follows: ag2O/CeO2，NiO/CeO2，ZnO/CeO2，Fe2O3/CeO2，CuO/CeO2，V2O5/CeO2，Co3O4/CeO2，MnO2/CeO2，Mg/CeO2One or more than two of them.
The biomass polyol is glycerol, xylose, glucose, fructose, sucrose, cellobiose or starch.
The concentration of a reaction substrate is 0.05-0.5 mmol/mL, the dosage of a catalyst is 50-100 mg, and the volume of a solvent is 25 mL.
The solvent is acetonitrile or water.
The reaction system is carried out in an oxygen atmosphere of 0.1 to 0.6 MPa.
The reaction temperature is 40-150 ℃.
The wavelength of a visible light source used for the reaction is 400-650 nm, the light source has a single wavelength, a mixed wavelength or a continuous wavelength, and the light intensity can be 50-240 mW/cm2。
The reaction time is more than 0.5 h.
Compared with the traditional method for preparing formic acid, the method has the following advantages:
1. the raw materials are easy to obtain and can be regenerated;
2. the reaction condition is mild, and the energy consumption is low;
3. the catalyst has high activity, the highest conversion rate can reach 100 percent, and the highest selectivity is more than 90 percent
Detailed Description
In order to further explain the present invention in detail, several specific embodiments are given below, but the present invention is not limited to these embodiments.
Example 1
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 98%.
Example 2
Mixing 1.25mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 99%.
Example 3
12.5mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2Irradiating visible light with a wavelength of 455nm for 10h to reactAfter the end of the reaction, the conversion of glycerol was 198% and the yield of formic acid was 95% by HPLC.
Example 4
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C with 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 98%.
Example 5
10mmol of glycerol, 100mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 99%.
Example 6
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL acetonitrile, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation of visible light having a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 90% and the yield of formic acid was 85%.
Example 7
10mmol of glycerol and 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.1Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 82% and the yield of formic acid was 80%.
Example 8
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.6Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 99%.
Example 9
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 98%.
Example 10
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 40 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 50% and the yield of formic acid was 48%.
Example 11
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 150 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, the conversion of glycerol was 100% and the yield of formic acid was 89% by HPLC.
Example 12
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation with a wavelength of 400nm, and after completion of the reaction, the conversion of glycerol was 100% and the yield of formic acid was 90% by HPLC.
Example 13
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 650nm, and after completion of the reaction, the conversion of glycerol was 80% and the yield of formic acid was 78% by HPLC.
Example 14
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, and maintaining pressureThe force is 0.5Mpa, and the light intensity is 50mW/cm at 120 DEG C2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 60% and the yield of formic acid was 55%.
Example 15
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and irradiating at 120 deg.C with light intensity of 240mW/cm2The reaction was carried out for 10 hours under irradiation of visible light having a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 97%.
Example 16
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 0.5h under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 30% and the yield of formic acid was 27%.
Example 17
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 9 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 95% and the yield of formic acid was 90%.
Example 18
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 98%.
Example 19
Mixing 10mmol of glycerol and 50mg of CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2Irradiating with visible light with wavelength of 455nm for 10 hr, and quantifying by HPLC to obtain glycerol conversion rateThe yield of formic acid was 56% and 60%.
Example 20
10mmol of glycerol, 50mg of 0.5mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 80% and the yield of formic acid was 76%.
Example 21
10mmol of glycerol and 50mg2 mol% of CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 99%.
Example 22
Mixing 10mmol of glycerol and 50mg of 1 mol% Ag2O/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation of visible light having a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 78% and the yield of formic acid was 70%.
Example 23
10mmol of glycerol and 50mg of 1mol percent NiO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 58% and the yield of formic acid was 55%.
Example 24
10mmol of glycerol, 50mg of 1 mol% ZnO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, the conversion of glycerol was 70% and the yield of formic acid was 66% by HPLC.
Example 25
Adding 10mmol ofGlycerol, 50mg 1 mol% Fe2O3/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 88% and the yield of formic acid was 78%.
Example 26
10mmol of glycerol, 50mg of 1 mol% V2O5/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, the conversion of glycerol was 77% and the yield of formic acid was 58% by HPLC.
Example 27
Mixing 10mmol of glycerol and 50mg of 1 mol% Co3O4/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, the conversion of glycerol was 80% and the yield of formic acid was 68% by HPLC.
Example 28
Mixing 10mmol of glycerol and 50mg of 1 mol% MnO2/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, the conversion of glycerol was 40% and the yield of formic acid was 33% by HPLC.
Example 29
10mmol of glycerol, 50mg of 1 mol% MgO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 98%.
Example 30
Mixing 8mmol xylose, 50mg 1 mol% CuO/CeO2Dispersed in 25mL of waterAdding magnetons, replacing with oxygen for three times, maintaining the pressure at 0.5Mpa, and maintaining the light intensity at 120 deg.C under 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion was 98% and the yield of formic acid was 96%.
Example 31
Mixing 8mmol glucose, 50mg 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion was 97% and the yield of formic acid was 96%.
Example 32
Mixing 8mmol of fructose, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion was 96% and the yield of formic acid was 94%.
Example 33
Mixing 8mmol xylose, 50mg 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion was 98% and the yield of formic acid was 96%.
Example 34
6mmol of sucrose, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion was 99% and the yield of formic acid was 96%.
Example 35
5mmol of cellobiose, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2Irradiating visible light with wavelength of 455nm for reaction for 10 hr, and reactingThe conversion, determined by HPLC, was 90% and the formic acid yield was 85%.
Example 36
4mmol of starch, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation of visible light having a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion was 89% and the yield of formic acid was 85%.
Example 37
Dispersing 10mmol glycerol and 50mg CuO in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C with 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, the conversion of glycerol was 5% and the yield of formic acid was 0% by HPLC.
Example 38
Mixing 10mmol of glycerol and 50mg of TiO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, the conversion of glycerol was 20% and the yield of formic acid was 10% by HPLC.
Example 39
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, replacing with oxygen for three times, maintaining pressure at 0.5Mpa, and maintaining light intensity at 120 deg.C of 200mW/cm2The reaction was carried out for 10 hours under visible light irradiation at a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 100% and the yield of formic acid was 98%.
Example 40
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magnetons, replacing with oxygen for three times, maintaining the pressure at 0.5Mpa, reacting at 120 deg.C for 10h, and quantifying by HPLC after the reaction is finished, wherein the conversion rate of glycerol is 5% and the yield of formic acid is 0%.
EXAMPLE 41
10mmol of glycerol, 50mg of 1 mol% CuO/CeO2Dispersing in 25mL water, adding magneton, and replacing with oxygenMaintaining the pressure at 0.5Mpa after three times, and applying light intensity at 200mW/cm at 25 deg.C2The reaction was carried out for 10 hours under irradiation with visible light having a wavelength of 455nm, and after completion of the reaction, quantitative determination was carried out by HPLC, whereby the conversion of glycerol was 10% and the yield of formic acid was 8%.

Claims (8)

1. A method for preparing formic acid, which is characterized in that: the method comprises the steps of taking cerium dioxide and/or supported cerium dioxide as a catalyst, taking one or more than two of glycerol, xylose, glucose, fructose, sucrose, cellobiose and starch as a reaction substrate, forming a photo-thermal catalysis system by the catalyst and the reaction substrate, adding acetonitrile and/or water as a solvent, taking oxygen as an oxidant, irradiating the mixture at the oxygen pressure of 0.1-0.8 MPa and 400-650 nm visible light at the temperature of 40-150 ℃ to convert the biomass polyol into formic acid.
2. The method of claim 1, wherein:
the method comprises the following specific steps: dissolving one or more of glycerol, xylose, glucose, fructose, sucrose, cellobiose or starch in a solvent, adding cerium dioxide and/or supported cerium dioxide, sealing the reactor, replacing the gas in the reactor with oxygen for more than 1 time, keeping the pressure of 0.1-0.8 MPa, and irradiating with 400-650 nm visible light at the temperature of 40-150 ℃ for reaction to generate an oxidation product formic acid.
3. A method according to claim 1 or 2, characterized in that: the catalyst used in the reaction is cerium dioxide or supported cerium dioxide, wherein:
(1) the cerium dioxide is CeO2(ii) a (2) Loaded with cerium dioxide M/CeO2Can be as follows: ag2O/CeO2，NiO/CeO2，ZnO/CeO2，Fe2O3/CeO2，CuO/CeO2，V2O5/CeO2，Co3O4/CeO2，MnO2/CeO2，MgO/CeO2One or more than two of the above; a in A/B is supported metal oxide, whereinThe supported metal mole fraction is 0.5mol% -2.0 mol%.
4. A method according to claim 3, characterized by:
the supported metal catalyst is prepared by an impregnation method: dispersing the loaded metal oxide in the loaded metal precursor solution, stirring for 12-20 h, evaporating water at 80-120 ℃, and treating in air at 400 ℃ for 2-4 h.
5. The method of claim 1, wherein: the concentration of the biomass polyol reaction substrate is 0.05-0.5 mmol/mL, the dosage of the catalyst is 50-100 mg, and the volume of the solvent is 25 mL.
6. The method of claim 1, wherein: the temperature of the reaction system is 40-150 ℃.
7. The method of claim 1, wherein: the wavelength of a visible light source used for the reaction is 400-650 nm, the light source has a single wavelength, a mixed wavelength or a continuous wavelength, and the light intensity can be 50-240 mW/cm2。
8. The method of claim 1, wherein: the reaction time is more than or equal to 0.5 h.
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CN102741211A (en) * 2010-01-29 2012-10-17 瓦克化学股份公司 Method for producing carboxylic acids having 1-3 carbon atoms from renewable resources
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