CN110015953A - Method for preparing acetophenone by nano-gold catalyst catalyzing ethylbenzene oxidation reaction - Google Patents

Abstract

The invention discloses a method for preparing acetophenone by catalyzing the oxidation of ethylbenzene by nano-gold catalyst. 20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water are added to a reactor, and the reaction is carried out at 80 DEG C and normal pressure. The target product acetophenone is prepared in 2 hours, and the invention also specifically discloses the preparation process of the nano-gold catalyst. The preparation process of the nano-gold catalyst in the present invention is simple, the prepared nano-gold catalyst has high catalytic activity and high stability, shows high catalytic activity in the ethylbenzene oxidation reaction, and can obtain high yield of acetophenone.

Description

Method for preparing acetophenone by nano-gold catalyst catalyzing ethylbenzene oxidation reaction

technical field

The invention belongs to the technical field of preparation of nano-gold catalysts and the preparation of acetophenone by catalyzing ethylbenzene oxidation reaction, and particularly relates to a method for preparing acetophenone by catalyzing ethylbenzene oxidation reaction of nano-gold catalysts.

Background technique

Heterogeneous catalysts have broad application prospects in production and are widely used in fine chemical and petroleum refining processes, of which supported metal catalysts are considered to be one of the most important catalysts. Gold nanoparticles have received extensive attention since they were discovered to possess unique catalytic activity in aerobic oxidation reactions. However, due to the sensitivity of gold nanoparticles, the stability of supported nano-gold catalysts limits its industrial application. Therefore, the preparation of highly active and stable supported nano-gold catalysts has become a challenging task. In the present invention, a mesoporous carbon material is used as a catalyst carrier, and the confinement effect of its mesoporous pores is used to improve the stability of nano-gold particles. The inventive nano-gold catalyst was prepared by ethylbenzene oxidation reaction to prepare acetophenone to evaluate its catalytic activity.

SUMMARY OF THE INVENTION

The technical problem solved by the present invention is to provide a method for preparing acetophenone by catalyzing the oxidation of ethylbenzene by a nano-gold catalyst, wherein the preparation process of the nano-gold catalyst is simple, and the prepared nano-gold catalyst has higher catalytic activity and higher It exhibits high catalytic activity in the ethylbenzene oxidation reaction, and can obtain acetophenone in high yield.

The present invention adopts the following technical scheme in order to solve the above-mentioned technical problems, the method for preparing acetophenone by nano-gold catalyst catalyzing ethylbenzene oxidation reaction is characterized in that the specific process is:

Step S1: Preparation of nano-gold catalyst, 3 g of resorcinol was weighed and dissolved in 10 mL of water, 1.2 g of F127 was added and stirred until it was completely dissolved, and 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% hexamethylenediamine were added respectively. Formaldehyde solution, react at 90 ℃, centrifuge and dry the obtained product, calcinate at 800 ℃ in an inert atmosphere to obtain carbon material, weigh 1 g of carbon material, add 1-1.5 mL of chloroauric acid solution, in which chloroauric acid The concentration of the solution is 0.04-0.06 mol/L, fully stirred and then allowed to stand at room temperature for 30-60 min, then sealed and dried at 50°C, and then heat-treated in an inert atmosphere at 300°C to obtain nano-gold catalyst;

Step S2: ethylbenzene oxidation reaction, 20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water were added to the reactor, and the target product acetophenone was obtained by reacting at 80 °C and normal pressure for 2 hours.

The method for preparing acetophenone by catalyzing the oxidative reaction of ethylbenzene by a nano-gold catalyst of the present invention is characterized in that the specific steps are:

Step S1: Preparation of nano-gold catalyst, 3 g of resorcinol was weighed and dissolved in 10 mL of water, 1.2 g of F127 was added and stirred until it was completely dissolved, and 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% hexamethylenediamine were added respectively. The formaldehyde solution was reacted at 90 °C, the obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material, 1 g of the carbon material was weighed, and 1.03 mL of chloroauric acid solution was added. The concentration was 0.05 mol/L, fully stirred, and then allowed to stand at room temperature for 30 min, then sealed and dried at 50 °C, and then heat-treated in an inert atmosphere at 300 °C to obtain nano-gold catalyst;

Step S2: ethylbenzene oxidation reaction, add 20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water into the reactor, and react at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product is subjected to gas chromatography. Analytical test, the conversion rate of ethylbenzene is 100%, and the yield of acetophenone is 95%.

The method for preparing acetophenone by catalyzing the oxidative reaction of ethylbenzene by a nano-gold catalyst of the present invention is characterized in that the specific steps are:

Step S1: Preparation of nano-gold catalyst, 3 g of resorcinol was weighed and dissolved in 10 mL of water, 1.2 g of F127 was added and stirred until it was completely dissolved, and 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% hexamethylenediamine were added respectively. The formaldehyde solution was reacted at 90 °C, the obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material, 1 g of the carbon material was weighed, and 1.5 mL of chloroauric acid solution was added. The concentration was 0.05 mol/L, fully stirred, and then allowed to stand at room temperature for 30 min, then sealed and dried at 50 °C, and then heat-treated in an inert atmosphere at 300 °C to obtain nano-gold catalyst;

Step S2: ethylbenzene oxidation reaction, add 20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water into the reactor, and react at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product is subjected to gas chromatography. Analytical test, the conversion rate of ethylbenzene is 100%, and the yield of acetophenone is 97%.

Compared with the prior art, the present invention has the following beneficial effects: the preparation process of the nano-gold catalyst in the present invention is simple, and the prepared nano-gold catalyst has a uniform size distribution of about 3 nm; under mild reaction conditions, the nano-gold catalyst has The high catalytic activity and selectivity solve the problems of harsh reaction conditions in industry, and the high selectivity also saves the cost for the separation process of the target product. Compared with the existing technology, the invention has simple operation, low preparation cost, and conforms to the industrial application value.

Description of drawings

Fig. 1 is the transmission electron microscope picture of the gold nano-catalyst that the embodiment of the present invention 1 makes;

Fig. 2 is the XRD pattern of the nano-gold catalyst prepared in Example 1 of the present invention.

Detailed ways

The above-mentioned content of the present invention is described in further detail below through the examples, but it should not be understood that the scope of the above-mentioned subject matter of the present invention is limited to the following examples, and all technologies realized based on the above-mentioned content of the present invention belong to the scope of the present invention.

Example 1

Weigh 3 g of resorcinol and dissolve it in 10 mL of water, add 1.2 g of F127 and stir until it is completely dissolved, then add 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% formaldehyde solution respectively, react at 90 °C, and mix The obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material. 1 g of the carbon material was weighed, and 1.03 mL of chloroauric acid solution was added, wherein the concentration of the chloroauric acid solution was 0.05 mol/L, and the mixture was fully stirred. After standing at room temperature for 30 min, then sealed and dried at 50 °C, and then heat-treated in an inert atmosphere at 300 °C to obtain nano-gold catalyst;

20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water were added to the reactor, and the reaction was carried out at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product was analyzed and tested by gas chromatography. The conversion rate of ethylbenzene was measured. is 100%, and the yield of acetophenone is 95%.

Example 2

Weigh 3 g of resorcinol and dissolve it in 10 mL of water, add 1.2 g of F127 and stir until it is completely dissolved, then add 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% formaldehyde solution respectively, react at 90 °C, and mix The obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material. 1 g of the carbon material was weighed, and 1.03 mL of chloroauric acid solution was added, wherein the concentration of the chloroauric acid solution was 0.06 mol/L, and the solution was fully stirred. After standing at room temperature for 30 min, then sealed and dried at 50 °C, and then heat-treated in an inert atmosphere at 300 °C to obtain nano-gold catalyst;

20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water were added to the reactor, and the reaction was carried out at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product was analyzed and tested by gas chromatography. The conversion rate of ethylbenzene was measured. was 91%, and the yield of acetophenone was 95%.

Example 3

Weigh 3 g of resorcinol and dissolve it in 10 mL of water, add 1.2 g of F127 and stir until it is completely dissolved, then add 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% formaldehyde solution respectively, react at 90 °C, and mix The obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material. 1 g of the carbon material was weighed, and 1.5 mL of chloroauric acid solution was added, wherein the concentration of the chloroauric acid solution was 0.05 mol/L, and the solution was fully stirred. After standing at room temperature for 30 min, then sealed and dried at 50 °C, and then heat-treated in an inert atmosphere at 300 °C to obtain nano-gold catalyst;

20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water were added to the reactor, and the reaction was carried out at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product was analyzed and tested by gas chromatography. The conversion rate of ethylbenzene was measured. is 100%, and the yield of acetophenone is 97%.

Example 4

Weigh 3 g of resorcinol and dissolve it in 10 mL of water, add 1.2 g of F127 and stir until it is completely dissolved, then add 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% formaldehyde solution respectively, react at 90 °C, and mix The obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material. 1 g of the carbon material was weighed, and 1 mL of chloroauric acid solution was added, wherein the concentration of the chloroauric acid solution was 0.04 mol/L, and the solution was fully stirred. After standing at room temperature for 60 min, then sealing and drying at 50 °C, and then heat treatment in an inert atmosphere and 300 °C to obtain nano-gold catalyst;

20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water were added to the reactor, and the reaction was carried out at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product was analyzed and tested by gas chromatography. The conversion rate of ethylbenzene was measured. was 95%, and the yield of acetophenone was 96%.

The above embodiments describe the basic principles, main features and advantages of the present invention. Those skilled in the art should understand that the present invention is not limited by the above embodiments. The above embodiments and descriptions only describe the principles of the present invention. Without departing from the scope of the principles of the present invention, the present invention may have various changes and improvements, and these changes and improvements all fall within the protection scope of the present invention.

Claims (3)

1. the method for preparing acetophenone by nano-gold catalyst catalysis ethylbenzene oxidation reaction, it is characterized in that concrete process is: Step S1: Preparation of nano-gold catalyst, 3 g of resorcinol was weighed and dissolved in 10 mL of water, 1.2 g of F127 was added and stirred until it was completely dissolved, and 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% hexamethylenediamine were added respectively. Formaldehyde solution, react at 90 ℃, centrifuge and dry the obtained product, calcinate at 800 ℃ in an inert atmosphere to obtain carbon material, weigh 1 g of carbon material, add 1-1.5 mL of chloroauric acid solution, in which chloroauric acid The concentration of the solution is 0.04-0.06 mol/L, fully stirred and then allowed to stand at room temperature for 30-60 min, then sealed and dried at 50°C, and then heat-treated in an inert atmosphere at 300°C to obtain nano-gold catalyst; Step S2: ethylbenzene oxidation reaction, 20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water were added to the reactor, and the target product acetophenone was obtained by reacting at 80 °C and normal pressure for 2 hours. 2. nano-gold catalyst catalysis ethylbenzene oxidation reaction according to claim 1 prepares the method for acetophenone, it is characterized in that concrete steps are: Step S1: Preparation of nano-gold catalyst, 3 g of resorcinol was weighed and dissolved in 10 mL of water, 1.2 g of F127 was added and stirred until it was completely dissolved, and 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% hexamethylenediamine were added respectively. The formaldehyde solution was reacted at 90 °C, the obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material, 1 g of the carbon material was weighed, and 1.03 mL of chloroauric acid solution was added. The concentration was 0.05 mol/L, fully stirred, and then allowed to stand at room temperature for 30 min, then sealed and dried at 50 °C, and then heat-treated in an inert atmosphere at 300 °C to obtain nano-gold catalyst; Step S2: ethylbenzene oxidation reaction, add 20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water into the reactor, and react at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product is subjected to gas chromatography. Analytical test, the conversion rate of ethylbenzene is 100%, and the yield of acetophenone is 95%. 3. nano-gold catalyst catalysis ethylbenzene oxidation reaction according to claim 1 prepares the method for acetophenone, it is characterized in that concrete steps are: Step S1: Preparation of nano-gold catalyst, 3 g of resorcinol was weighed and dissolved in 10 mL of water, 1.2 g of F127 was added and stirred until it was completely dissolved, and 0.15 g of 1,6-hexanediamine and 4.4 g of 37wt% hexamethylenediamine were added respectively. The formaldehyde solution was reacted at 90 °C, the obtained product was centrifuged and dried, and calcined at 800 °C in an inert atmosphere to obtain a carbon material, 1 g of the carbon material was weighed, and 1.5 mL of chloroauric acid solution was added. The concentration was 0.05 mol/L, fully stirred, and then allowed to stand at room temperature for 30 min, then sealed and dried at 50 °C, and then heat-treated in an inert atmosphere at 300 °C to obtain nano-gold catalyst; Step S2: ethylbenzene oxidation reaction, add 20 mg of nano-gold catalyst, 4 mmol of ethylbenzene and 6 mL of water into the reactor, and react at 80 °C and normal pressure for 2 hours. After the reaction, the reaction product is subjected to gas chromatography. Analytical test, the conversion rate of ethylbenzene is 100%, and the yield of acetophenone is 97%.