Application of Bi2S3 / Bi2O4 composite materials in the catalytic hydrogenation of levulinic acid to γ-valerol

Abstract

The application relates to application of a Bi2S3 / Bi2O4 composite material in catalytic hydrogenation synthesis of gamma-valerolactone from acetylenic acid. A composite catalytic material Bi2S3 / Bi2O4 of bismuth sulfide and bismuth tetroxide is prepared by using bismuth nitrate pentahydrate and sodium thiosulfate as raw materials and by adopting a solvothermal method. The composite Bi2S3 / Bi2O4 material, a substrate acetylenic acid and an alcohol solvent (a hydrogen donor) are added into a quartz test tube, and the photocatalytic reaction of the acetylenic acid is completed under an argon atmosphere and illumination, so that the yield of the product gamma-valerolactone can reach 81% after 37 hours of reaction, and a high product yield is realized under mild reaction conditions.

Description

Technical Field

[0001] This invention relates to the application of a Bi2S3 / Bi2O4 composite material in the catalytic hydrogenation of levulinic acid to synthesize γ-valerol, specifically using levulinic acid as a raw material and the Bi2S3 / Bi2O4 composite material as a catalyst to complete the hydrogenation to γ-valerol under light irradiation. Background Technology

[0002] Biomass, as the only renewable green organic carbon source on Earth, is widely available and inexpensive. It can replace fossil resources and be converted into various conventional solid, liquid, and gaseous fuels and other chemicals, showing great promise for applications.

[0003] Alecithinic acid, an important biomass-based platform compound, is derived from cellulose or hemicellulose. Its hydrogenated cyclization product, γ-valerolactone, has wide industrial applications as a green solvent, fuel additive, and organic intermediate for various fine chemicals.

[0004] Currently, most research focuses on using thermocatalysis to convert levulinic acid to γ-valerol. However, thermocatalysis typically uses hydrogen as a hydrogen source under high temperature and high pressure conditions, which are harsh and not environmentally friendly.

[0005] Chinese patent CN 104496945A discloses a method for photocatalytic hydrogenation of levulinic acid to prepare γ-valerol, using a platinum-supported titanium dioxide catalyst. After reacting with a 300W high-pressure mercury lamp for 12 hours, the liquid product obtained contains 76% γ-valerol.

[0006] Compared to the precious metal catalysts used in the aforementioned patents, which focus on using thermocatalysis to complete the conversion of levulinic acid to γ-valerol, none of them involve using non-precious metal photocatalysts to reduce reaction costs or to complete the conversion of levulinic acid to γ-valerol under mild and green conditions.

[0007] CN 103626228A discloses a method for preparing sheet-like nano-Bi2S3 materials using bismuth nitrate and sodium thiosulfate as raw materials, which can be applied to photovoltaic cell materials, photodiode materials, sensors and catalysis.

[0008] CN103447052A discloses a template-free method for preparing hollow dendritic bismuth oxide-bismuth sulfide composites. These hollow dendritic bismuth oxide-bismuth sulfide composites can be used as photocatalysts in visible light catalytic degradation of organic dyes (Rhodamine-B, methylene blue reaction), photocatalytic decomposition of organic matter, photocatalytic reduction of carbon dioxide to produce methanol and other organic matter, and photocatalytic water splitting to produce hydrogen. Although the photocatalytic performance of the bismuth oxide-bismuth sulfide composites is mentioned, its application to the conversion of levulinic acid to γ-valerol is not discussed. Summary of the Invention

[0009] The purpose of this invention is to provide an application of Bi2S3 / Bi2O4 composite material in the catalytic hydrogenation synthesis of γ-valerolactone from levulinic acid. Specifically, the non-precious metal composite material Bi2S3 / Bi2O4 is used as a catalyst, and inexpensive alcohol solvents are used as hydrogen donors. Under light irradiation, the synthesis of γ-valerolactone from levulinic acid is completed economically, efficiently, greenly, and mildly. The reaction can be easily qualitatively and quantitatively analyzed using gas chromatography-mass spectrometry and gas chromatography, resulting in high reactant conversion rates and product yields.

[0010] The application of the Bi₂S₃ / Bi₂O₄ composite material provided by this invention in the catalytic hydrogenation of levulinic acid to synthesize γ-valerolactone. The method for the catalytic hydrogenation of levulinic acid to synthesize γ-valerolactone in this application includes the following steps:

[0011] 1) Freshly prepared composite material Bi2S3 / Bi2O4 catalyst, levulinic acid and hydrogen-donating precursor were added to a sealed quartz test tube reactor respectively;

[0012] 2) Evacuate the air and introduce argon gas three times to ensure the reaction solution is in an argon atmosphere;

[0013] 3) Place the quartz test tube on a magnetic stirrer and irradiate it with a 30-100W low-pressure mercury lamp for 30-40 hours at room temperature; preferably a 30W low-pressure mercury lamp, irradiation time 37 hours.

[0014] 4) Filter the reaction solution and use gas chromatography to determine the conversion rate of levulinic acid and the yield of γ-valerol.

[0015] The application of the Bi2S3 / Bi2O4 composite material provided by this invention in the catalytic hydrogenation synthesis of γ-valerate from levulinic acid, and the preparation method of the Bi2S3 / Bi2O4 composite material includes the following steps:

[0016] 1) At room temperature, add bismuth nitrate pentahydrate to acetone solution and stir for 0.2-0.5 h, then add sodium thiosulfate and stir thoroughly.

[0017] 2) The obtained solution is placed in a polytetrafluoroethylene reaction vessel and heated in an oven at 150-180℃ for 20-24 hours;

[0018] 3) Cool the reactor to room temperature, remove the reaction product, wash it three times with water and three times with ethanol, and then dry it in a vacuum oven at 45-50℃ (vacuum degree 90kPa) for 8-10 hours. Pulverize it to obtain composite Bi2S3 / Bi2O4 catalyst powder.

[0019] In the preparation method of the composite Bi₂S₃ / Bi₂O₄ catalyst material, the molar ratio of bismuth nitrate pentahydrate and sodium thiosulfate in step 1) is 1:1.5-3. The mass ratio of the composite catalyst material Bi₂S₃ / Bi₂O₄ to levulinic acid is 1:4.

[0020] The application of the Bi2S3 / Bi2O4 composite material provided by this invention in the catalytic hydrogenation synthesis of γ-valerol from levulinic acid, wherein the hydrogen donor precursor is isopropanol or ethanol.

[0021] This invention provides an application of a Bi₂S₃ / Bi₂O₄ composite material in the catalytic hydrogenation synthesis of γ-valerol from levulinic acid. Using bismuth nitrate pentahydrate and sodium thiosulfate as raw materials, a composite catalytic material (Bi₂S₃ / Bi₂O₄) of bismuth sulfide and bismuth tetroxide is prepared by a solvothermal method. Specifically, using the non-precious metal composite material Bi₂S₃ / Bi₂O₄ as the catalyst and inexpensive alcohol solvents as hydrogen donors, the synthesis of levulinic acid to γ-valerol is achieved economically, efficiently, greenly, and mildly under light irradiation. The reaction can be conveniently qualitatively and quantitatively analyzed using gas chromatography-mass spectrometry and gas chromatography, yielding high reactant conversion rates and product yields.

[0022] The key advantages of this invention are: 1) The synthesized composite Bi₂S₃ / Bi₂O₄ catalyst material can synthesize the composite material of bismuth sulfide and bismuth tetroxide in a one-pot reaction under solvothermal conditions, resulting in a simple and low-cost synthesis process; 2) This invention is carried out under light and room temperature conditions, making the reaction mild, green, and efficient. For example, the yield of the product γ-valerolactone can reach 81% after 37 hours of reaction. Attached Figure Description

[0023] Figure 1 The image shows the XRD pattern of Bi2S3 / Bi2O4-1 obtained in this invention.

[0024] Figure 2 The image shows the SEM spectrum of Bi2S3 / Bi2O4-1 obtained in this invention.

[0025] Figure 3 This is the mass spectrum of γ-valerolactone, the product of this invention. Detailed Implementation

[0026] The following is a further description of the invention, but not a limitation thereof.

[0027] The specific preparation method of the Bi2S3 / Bi2O4 photocatalyst in the preparation method of the composite Bi2S3 / Bi2O4 material (photocatalyst) of this invention can be found in the following reference: R.-t. Guo, et al. Photocatalytic reduction of CO2 into CO over nanostructure Bi2S3 quantum dots / g-C3N4composites with Z-scheme mechanism. Applied Surface Science, 2020, 500: 144059.

[0028] Example 1

[0029] First, 0.668 mmol of bismuth nitrate pentahydrate was added to 35 mL of acetone and stirred for 0.5 h. Then, 1 mmol of sodium thiosulfate was added and stirred for 0.5 h. The solution was then transferred to a 100 mL polytetrafluoroethylene reactor and heated in an oven at 180 °C for 24 h. After the reactor cooled, the catalyst material in the reaction solution was washed three times each with water and ethanol. Then, it was placed in a vacuum oven at 50 °C (vacuum degree 90 kPa) and dried for 8 h. The dried catalyst was ground into powder and labeled as Bi2S3 / Bi2O4-1. Add 50 mg of the above catalyst, 200 mg of levulinic acid (catalyst to levulinic acid mass ratio of 1:4), and 10 mL of isopropanol sequentially to a 50 mL quartz tube. Seal the tube, evacuate and then introduce argon gas three times, until the final reaction solution is in an argon atmosphere. Place the quartz tube on a magnetic stirrer and use a low-pressure mercury lamp (220V 30W, Guangzhou Xingchuang Electronics Co., Ltd., XC230803) for 37 h of reaction. After filtering the reaction solution using a 0.22 μm organic filter membrane, gas chromatography is used to determine the conversion rate of levulinic acid and the yield of γ-valerolactone.

[0030] Assay method: 0.1 mL of 1000 ppm dodecane (internal standard) in isopropanol solution was added to 0.7 mL of filtered reaction solution to prepare the test solution. The content of substrate and product in the test solution was determined by gas chromatography using the internal standard method. The gas chromatography analysis conditions were: FID detector, injection port temperature 250℃, column temperature 140℃, detector temperature 260℃, injection volume 1 μL, and detection time 21 min. Finally, the conversion rate of levulinic acid and the yield of γ-valerolactone in the reaction were calculated by calculating the area ratio of substrate and product to the internal standard dodecane and comparing with the standard curve. The results are listed in Table 1.

[0031] Example 2

[0032] First, 0.668 mmol of bismuth nitrate pentahydrate was added to 35 mL of acetone and stirred for 0.5 h. Then, 1.33 mmol of sodium thiosulfate was added and stirred for 0.5 h. The solution was then transferred to a 100 mL polytetrafluoroethylene reactor and heated in an oven at 180 °C for 24 h. After the reactor cooled, the catalyst material in the reaction solution was washed three times each with water and ethanol. Then, it was dried in a vacuum oven at 50 °C (vacuum degree 90 kPa) for 8 h. The dried catalyst was ground into powder and labeled as Bi2S3 / Bi2O4-2. 50 mg of the above catalyst, 200 mg of levulinic acid (catalyst to levulinic acid mass ratio of 1:4) and 10 mL of isopropanol were added sequentially to a 50 mL quartz tube. The tube was sealed, and the reaction was evacuated and purged with argon gas three times. Finally, the reaction solution was in an argon atmosphere. The quartz tube was placed on a magnetic stirrer and reacted for 37 h using a low-pressure mercury lamp (220V 30W, Guangzhou Xingchuang Electronics Co., Ltd., XC230803). After filtering the reaction solution, the conversion rate of levulinic acid and the yield of γ-valerolactone were determined by gas chromatography. The determination method was the same as in Example 1, and the results are listed in Table 1.

[0033] Example 3

[0034] First, 0.668 mmol of bismuth nitrate pentahydrate was added to 35 mL of acetone and stirred for 0.5 h. Then, 1.67 mmol of sodium thiosulfate was added and stirred for 0.5 h. The solution was then transferred to a 100 mL polytetrafluoroethylene reactor and heated in an oven at 180 °C for 24 h. After the reactor cooled, the catalyst material in the reaction solution was washed three times each with water and ethanol. Then, it was dried in a vacuum oven at 50 °C (vacuum degree 90 kPa) for 8 h. The dried catalyst was ground into powder and labeled as Bi2S3 / Bi2O4-3. 50 mg of the above catalyst, 200 mg of levulinic acid (catalyst to levulinic acid mass ratio of 1:4) and 10 mL of isopropanol were added sequentially to a 50 mL quartz tube. The tube was sealed, and the reaction was evacuated and purged with argon gas three times. Finally, the reaction solution was in an argon atmosphere. The quartz tube was placed on a magnetic stirrer and reacted for 37 h using a low-pressure mercury lamp (220V 30W, Guangzhou Xingchuang Electronics Co., Ltd., XC230803). After filtering the reaction solution, the conversion rate of levulinic acid and the yield of γ-valerolactone were determined by gas chromatography. The determination method was the same as in Example 1, and the results are listed in Table 1.

[0035] Example 4

[0036] First, 0.668 mmol of bismuth nitrate pentahydrate was added to 35 mL of acetone and stirred for 0.5 h. Then, 2 mmol of sodium thiosulfate was added and stirred for 0.5 h. The solution was then transferred to a 100 mL polytetrafluoroethylene reactor and heated in an oven at 180 °C for 24 h. After the reactor cooled, the catalyst material in the reaction solution was washed three times each with water and ethanol. Then, it was placed in a 50 °C vacuum oven (90 kPa vacuum) to dry for 8 h. The dried catalyst was ground into powder and labeled as Bi2S3 / Bi2O4-4. 50 mg of the above catalyst, 200 mg of levulinic acid (catalyst to levulinic acid mass ratio of 1:4) and 10 mL of isopropanol were added sequentially to a 50 mL quartz tube. The tube was sealed, and the reaction was evacuated and purged with argon gas three times. Finally, the reaction solution was in an argon atmosphere. The quartz tube was placed on a magnetic stirrer and reacted for 37 h using a low-pressure mercury lamp (220V 30W, Guangzhou Xingchuang Electronics Co., Ltd., XC230803). After filtering the reaction solution, the conversion rate of levulinic acid and the yield of γ-valerolactone were determined by gas chromatography. The determination method was the same as in Example 1, and the results are listed in Table 1.

[0037] Example 5

[0038] The catalyst preparation process was the same as in Example 1. Then, 50 mg of Bi2S3 / Bi2O4-4 catalyst, 200 mg of levulinic acid (catalyst to levulinic acid mass ratio of 1:4) and 10 mL of ethanol were added sequentially to a 50 mL quartz tube. The test tube was sealed, and vacuum and argon gas were introduced three times. Finally, the reaction solution was in an argon atmosphere. The quartz test tube was placed on a magnetic stirrer and reacted for 37 h using a low-pressure mercury lamp (220V 30W, Guangzhou Xingchuang Electronics Co., Ltd., XC230803). After filtering the reaction solution, the conversion rate of levulinic acid and the yield of γ-valerolactone were determined by gas chromatography. The determination method was the same as in Example 1, and the results are listed in Table 1.

[0039] .

Claims

1. The application of a Bi₂S₃ / Bi₂O₄ composite material in the catalytic hydrogenation synthesis of γ-valerate from levulinic acid; the preparation method of the Bi₂S₃ / Bi₂O₄ composite material comprises the following steps: 1) At room temperature, add bismuth nitrate pentahydrate to an acetone solution and stir for 0.2-0.5 h, then add sodium thiosulfate and stir thoroughly; the molar ratio of bismuth nitrate pentahydrate to sodium thiosulfate is 1:1.5-2.

5. 2) The obtained solution is placed in a polytetrafluoroethylene reaction vessel and heated in an oven at 150-180℃ for 20-24 hours; 3) Cool the reactor to room temperature, remove the reaction product, wash it three times with water and three times with ethanol, and then dry it in a vacuum oven at 45-50℃ for 8-10 hours. After pulverizing, the Bi2S3 / Bi2O4 composite material is obtained.

2. The application according to claim 1, characterized in that... The method for the catalytic hydrogenation of levulinic acid to synthesize γ-valerol includes the following steps: 1) Freshly prepared Bi2S3 / Bi2O4 composite material, levulinic acid and hydrogen-donating precursor were added to a sealed quartz test tube reactor respectively; 2) Evacuate the air and introduce argon gas three times to ensure the reaction solution is in an argon atmosphere; 3) Place the quartz test tube on a magnetic stirrer and irradiate it with a 30-100W low-pressure mercury lamp at room temperature for 30-40 hours to carry out the reaction; 4) Filter the reaction solution and use gas chromatography to determine the conversion rate of levulinic acid and the yield of γ-valerol.

3. The application according to claim 2, characterized in that... The low-pressure mercury lamp has a power of 30W and an irradiation time of 37 hours.

4. The application according to claim 2, characterized in that... The vacuum oven has a vacuum level of 90 kPa.

5. The application according to claim 2, characterized in that... The hydrogen-donating precursor is isopropanol or ethanol.

6. The application according to claim 2, characterized in that Bi The mass ratio of 2S3 / Bi2O4 composite material to levulinic acid is 1:4.

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