CN-118022772-B - Bi2S3/Bi2O4Application of composite material in synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid

Abstract

The invention relates to an application of a Bi 2 S 3 /Bi 2 O 4 composite material in synthesizing gamma-valerolactone by levulinic acid catalytic hydrogenation. The bismuth sulfide and bismuth tetroxide composite catalytic material Bi 2 S 3 /Bi 2 O 4 is prepared by using bismuth nitrate pentahydrate and sodium thiosulfate as raw materials and adopting a solvothermal method. The compound Bi 2 S 3 /Bi 2 O 4 material, the substrate levulinic acid and the alcohol solvent (hydrogen donor) are added into a quartz test tube, the photocatalysis reaction of the levulinic acid is completed under the argon atmosphere and the illumination condition, the yield of the product gamma-valerolactone can reach 81 percent after the reaction is carried out for 37 hours, and the higher product yield is realized under the mild reaction condition.

Inventors

• YU KAI
• AN WENJING
• LIU JINHAO
• Yang Chenghuo
• YANG QIYUAN

Assignees

• 南开大学

Dates

Publication Date

20260508

Application Date

20240207

Claims (6)

1. 1. An application of Bi 2 S 3 /Bi 2 O 4 composite material in synthesizing gamma-valerolactone by levulinic acid catalytic hydrogenation; the preparation method of the Bi 2 S 3 /Bi 2 O 4 composite material comprises the following steps: 1) Adding bismuth nitrate pentahydrate into an acetone solution at room temperature, stirring for 0.2-0.5h, adding sodium thiosulfate into the solution, and fully stirring, wherein the molar ratio of the bismuth nitrate pentahydrate to the sodium thiosulfate is 1:1.5-2.5; 2) Putting the obtained solution into a polytetrafluoroethylene reaction kettle, and putting the polytetrafluoroethylene reaction kettle into an oven for heating for 20-24 hours at 150-180 ℃; 3) And cooling the reaction kettle to room temperature, taking out the reaction product, washing with water and ethanol for three times respectively, then placing the reaction product in a vacuum oven at 45-50 ℃ for drying for 8-10h, and crushing to obtain the Bi 2 S 3 /Bi 2 O 4 composite material.
2. 2. The use according to claim 1, characterized in that said method for the catalytic hydrogenation of levulinic acid to gamma valerolactone comprises the steps of: 1) Adding freshly prepared Bi 2 S 3 /Bi 2 O 4 composite material, levulinic acid and hydrogen supply precursor into a sealed quartz test tube reactor respectively; 2) Respectively vacuumizing and introducing argon, and repeating for three times to make the reaction liquid in an argon atmosphere; 3) Placing the quartz test tube on a magnetic stirrer, and irradiating for 30-40h at room temperature by using a 30-100W low-pressure mercury lamp for reaction; 4) The reaction solution was filtered, and the levulinic acid conversion and gamma valerolactone yield were measured by gas chromatography.
3. 3. Use according to claim 2, characterized in that the power of the low-pressure mercury lamp is 30W and the irradiation time is 37h.
4. 4. Use according to claim 2, characterized in that the vacuum degree of the vacuum oven is 90kPa.
5. 5. The use according to claim 2, wherein the hydrogen donor precursor is isopropanol or ethanol.
6. 6. Use according to claim 2, characterized in that the Bi 2 S 3 /Bi 2 O 4 composite to levulinic acid mass ratio is 1:4.

Description

Application of Bi 2S3/Bi2O4 composite material in levulinic acid catalytic hydrogenation synthesis of gamma-valerolactone Technical Field The invention relates to an application of a Bi 2S3/Bi2O4 composite material in synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid, in particular to an application of the Bi 2S3/Bi2O4 composite material in synthesizing gamma-valerolactone by catalytic hydrogenation under the condition of illumination by taking levulinic acid as a raw material and taking a Bi 2S3/Bi2O4 composite material as a catalyst. Background Biomass is used as the only renewable green organic carbon source on the earth, has wide sources and low cost, can replace fossil resources to be converted into various conventional solid-liquid-gas fuel and other chemicals, and has good application prospect. Levulinic acid is an important biomass-based platform compound converted from cellulose or hemicellulose, and the product gamma-valerolactone of the hydrocyclization of the levulinic acid can be used as an organic intermediate of green solvents and fuel additives as well as various fine chemicals, and has wide application in industry. At present, most researches focus on the conversion of levulinic acid into gamma valerolactone by using a thermocatalytic method, but the thermocatalytic process is usually completed under the conditions of high temperature and high pressure by using hydrogen as a hydrogen source, and the reaction conditions are harsh and not environment-friendly enough. Chinese patent CN 104496945A discloses a method for preparing gamma-valerolactone by photocatalysis levulinic acid hydrogenation, which uses titanium dioxide catalyst loaded by metal platinum, and uses 300W high pressure mercury lamp to react for 12 hours, wherein gamma-valerolactone in the obtained liquid phase product accounts for 76%. With respect to the noble metal catalysts used in the above-mentioned publications, the conversion from levulinic acid to gamma valerolactone is accomplished using a thermocatalytic process in a concentrated manner, and none of them relates to the reduction of reaction costs using a non-noble metal photocatalyst, and the conversion from levulinic acid to gamma valerolactone is accomplished under mild green conditions. CN 103626228a discloses a sheet-shaped nano Bi 2S3 material prepared from bismuth nitrate and sodium thiosulfate, which is applied to the fields of photocell materials, photodiode materials, sensors and catalysis. CN103447052a discloses a method for preparing a hollow tree-shaped bismuth oxide-bismuth sulfide composite without a template agent, and the hollow tree-shaped bismuth oxide-bismuth sulfide composite can be used as a photocatalyst in reactions of visible light catalytic degradation of organic dye (rhodamine-B, methylene blue reaction), photocatalytic decomposition of organic matters, photocatalytic reduction of carbon dioxide to prepare organic matters such as methanol, photocatalytic water splitting to prepare hydrogen, and the like, wherein although the photocatalytic performance of the bismuth oxide-bismuth sulfide composite is mentioned, the conversion of levulinic acid to gamma valerolactone is not involved. Disclosure of Invention The invention aims to provide an application of a Bi 2S3/Bi2O4 composite material in synthesizing gamma-valerolactone through catalytic hydrogenation of levulinic acid. The method specifically uses a non-noble metal composite material Bi 2S3/Bi2O4 as a catalyst, uses an inexpensive alcohol solvent as a hydrogen donor, completes the synthesis of levulinic acid to gamma-valerolactone economically and efficiently under the illumination condition, and conveniently uses a gas chromatograph-mass spectrometer and a gas chromatograph to carry out qualitative and quantitative analysis on the reaction to obtain higher reactant conversion rate and product yield. The invention provides an application of Bi 2S3/Bi2O4 composite material in synthesizing gamma-valerolactone by levulinic acid catalytic hydrogenation. The method for synthesizing gamma-valerolactone by catalytic hydrogenation of levulinic acid in the application comprises the following steps: 1) Adding freshly prepared composite material Bi 2S3/Bi2O4 catalyst, levulinic acid and hydrogen supply precursor into a sealed quartz test tube reactor respectively; 2) Respectively vacuumizing and introducing argon, and repeating for three times to make the reaction liquid in an argon atmosphere; 3) The quartz tube is placed on a magnetic stirrer, and is irradiated with a 30-100W low-pressure mercury lamp for 30-40 hours at room temperature, preferably a 30W low-pressure mercury lamp for 37 hours. 4) The reaction solution was filtered, and the levulinic acid conversion and gamma valerolactone yield were measured by gas chromatography. The invention provides an application of Bi 2S3/Bi2O4 composite material in synthesizing gamma-valerolactone by levulinic acid catalytic hydro