Application of fullerene as catalyst in catalytic hydrogenation reaction of nitro aromatic compound

Abstract

The invention discloses application of fullerene as a catalyst in a catalytic hydrogenation reaction of a nitro aromatic compound. The nitro aromatic compound comprises nitrobenzene, chloronitrobenzene and nitro aromatic aldehyde, ketone and nitrile. The fullerene catalyst is any one of univalent C60 negative ions, bivalent C60 negative ions, a mixture of the univalent C60 negative ions and the bivalent C60 negative ions, and univalent C70 negative ions. The fullerene negative ion catalyst is obtained by reducing with a Ni-Al alloy in a sodium hydroxide water solution. By using a nonmetal system, hydrogen molecules are activated, and the nitro hydrogenation reaction is selectively catalyzed. The catalyst has the remarkable advantages of high activity and high selectivity, and reduces the ecological risk and environmental hazard generated by catalytic reaction.

Description

technical field

[0001] The invention relates to the application of a catalyst, in particular to the application of fullerene as a catalyst in the selective hydrogenation of nitro aromatic compounds to prepare amino aromatic compounds and azoxy aromatic compounds. Background technique

[0002] Efficient and selective catalytic hydrogenation of aromatic nitro compounds is of great significance in the industrial field. Aminoaromatic compounds are very important chemical intermediates, which can be used to synthesize various fine chemicals such as pesticides, drugs, and photoelectric functional molecules. At present, the preparation methods of aminoaromatic compounds include: metal powder-acid chemical reduction method, electrochemical reduction method, and catalytic hydrogenation method.

[0003] 1. The metal powder-acid chemical reduction method produces a large amount of inorganic salt waste and by-products, which not only pollutes the environment, but also wastes resources ...

Examples

preparation example Construction

[0020] The preparation method of each substance is as follows:

[0021] Monovalent C 60 Preparation of negative ions: In 25mL tetrahydrofuran, add C 60 0.036g, 0.130g of Ni-Al alloy powder, and 0.400g of sodium hydroxide. Under stirring, blow nitrogen into the solution to remove dissolved air. After 30 minutes, add 5.0mL of freshly distilled distilled water to initiate the reaction. After 60 minutes, stop stirring , standing still for 30 minutes, the system is divided into two layers, the monovalent C 60 Negative ions are dissolved in tetrahydrofuran, and the upper layer of tetrahydrofuran C is taken out 60 Negative ion solution, spare.

[0022] Monovalent C 70 Preparation of negative ions: In 25mL tetrahydrofuran, add C 70 0.036g, 0.130g of Ni-Al alloy powder, and 0.400g of sodium hydroxide. Under stirring, blow nitrogen into the solution to remove dissolved air. After 30 minutes, add 5.0mL of freshly distilled distilled water to initiate the reaction. After 60 minutes, ...

specific Embodiment 1

[0024] 1.0g nitrobenzene, 40ml tetrahydrofuran and 0.036g C 60 Molecular catalyst (0.05mmol) joins in the stainless steel reactor of 100ml, seals autoclave, fills H 2 Inflate to a pressure of 2.0MPa, then vent. Repeat the operation three times to remove the air in the kettle. Finally H 2 Charge to 5.0MPa, heat to 140°C, and react for 4.0 hours. During the reaction process, mechanical stirring was carried out at a speed of 500 revolutions per minute (500 r.p.m.). After the reaction was over, the reactor was naturally cooled to room temperature, and N 2 The gas is purged twice to remove the H in the kettle 2 . The catalyst is recovered from the reaction solution by centrifugation at a speed of 12000 r.p.m. The organic clear liquid was diluted with methanol and analyzed and identified by GCMS-QP2010 (SHIMADZU) mass spectrometer. The results showed that the conversion rate of nitrobenzene was 3.84%, and the selectivity of aniline was 88%.

specific Embodiment 2

[0025] Pass hydrogen gas to get rid of the air in the reactor, and under hydrogen atmosphere, 1.0g nitrobenzene, 40ml tetrahydrofuran and 0.036g monovalent C 60 Negative ion catalyst (0.05mmol) joins in the stainless steel reactor of 100ml, seals autoclave, fills with H 2 Inflate to a pressure of 2.0MPa, then vent. Repeat the operation three times to remove the air in the kettle. Finally H 2 Charge to 2.0MPa, heat to 100°C, and react for 4.0 hours. During the reaction process, mechanical stirring was carried out at a speed of 500 revolutions per minute (500 r.p.m.). After the reaction was over, the reactor was naturally cooled to room temperature, and N 2 The gas is purged twice to remove the H in the kettle 2 . The catalyst is recovered from the reaction solution by centrifugation at a speed of 12000 r.p.m. The organic clear liquid was diluted with methanol and analyzed and identified by GCMS-QP2010 (SHI MADZU) mass spectrometer. The results showed that the conversion ...

technical field

[0001] The invention relates to the application of a catalyst, in particular to the application of fullerene as a catalyst in the selective hydrogenation of nitro aromatic compounds to prepare amino aromatic compounds and azoxy aromatic compounds. Background technique

[0002] Efficient and selective catalytic hydrogenation of aromatic nitro compounds is of great significance in the industrial field. Aminoaromatic compounds are very important chemical intermediates, which can be used to synthesize various fine chemicals such as pesticides, drugs, and photoelectric functional molecules. At present, the preparation methods of aminoaromatic compounds include: metal powder-acid chemical reduction method, electrochemical reduction method, and catalytic hydrogenation method.

[0003] 1. The metal powder-acid chemical reduction method produces a large amount of inorganic salt waste and by-products, which not only pollutes the environment, but also wastes resources ...

Examples

preparation example Construction

[0020] The preparation method of each substance is as follows:

[0021] Monovalent C 60 Preparation of negative ions: In 25mL tetrahydrofuran, add C 60 0.036g, 0.130g of Ni-Al alloy powder, and 0.400g of sodium hydroxide. Under stirring, blow nitrogen into the solution to remove dissolved air. After 30 minutes, add 5.0mL of freshly distilled distilled water to initiate the reaction. After 60 minutes, stop stirring , standing still for 30 minutes, the system is divided into two layers, the monovalent C 60 Negative ions are dissolved in tetrahydrofuran, and the upper layer of tetrahydrofuran C is taken out 60 Negative ion solution, spare.

[0022] Monovalent C 70 Preparation of negative ions: In 25mL tetrahydrofuran, add C 70 0.036g, 0.130g of Ni-Al alloy powder, and 0.400g of sodium hydroxide. Under stirring, blow nitrogen into the solution to remove dissolved air. After 30 minutes, add 5.0mL of freshly distilled distilled water to initiate the reaction. After 60 minutes, ...

specific Embodiment 1

[0024] 1.0g nitrobenzene, 40ml tetrahydrofuran and 0.036g C 60 Molecular catalyst (0.05mmol) joins in the stainless steel reactor of 100ml, seals autoclave, fills H 2 Inflate to a pressure of 2.0MPa, then vent. Repeat the operation three times to remove the air in the kettle. Finally H 2 Charge to 5.0MPa, heat to 140°C, and react for 4.0 hours. During the reaction process, mechanical stirring was carried out at a speed of 500 revolutions per minute (500 r.p.m.). After the reaction was over, the reactor was naturally cooled to room temperature, and N 2 The gas is purged twice to remove the H in the kettle 2 . The catalyst is recovered from the reaction solution by centrifugation at a speed of 12000 r.p.m. The organic clear liquid was diluted with methanol and analyzed and identified by GCMS-QP2010 (SHIMADZU) mass spectrometer. The results showed that the conversion rate of nitrobenzene was 3.84%, and the selectivity of aniline was 88%.

specific Embodiment 2

[0025] Pass hydrogen gas to get rid of the air in the reactor, and under hydrogen atmosphere, 1.0g nitrobenzene, 40ml tetrahydrofuran and 0.036g monovalent C 60 Negative ion catalyst (0.05mmol) joins in the stainless steel reactor of 100ml, seals autoclave, fills with H 2 Inflate to a pressure of 2.0MPa, then vent. Repeat the operation three times to remove the air in the kettle. Finally H 2 Charge to 2.0MPa, heat to 100°C, and react for 4.0 hours. During the reaction process, mechanical stirring was carried out at a speed of 500 revolutions per minute (500 r.p.m.). After the reaction was over, the reactor was naturally cooled to room temperature, and N 2 The gas is purged twice to remove the H in the kettle 2 . The catalyst is recovered from the reaction solution by centrifugation at a speed of 12000 r.p.m. The organic clear liquid was diluted with methanol and analyzed and identified by GCMS-QP2010 (SHI MADZU) mass spectrometer. The results showed that the conversion ...