Preparation method of catalyst for synthesizing piperazine through monoethanolamine catalytic amination one-step method

Abstract

The invention discloses a preparation method of a catalyst for synthesizing piperazine through a monoethanolamine catalytic amination one-step method. The catalyst is spherical particles prepared by taking a mixture containing gamma-Al2O3 and theta-Al2O3 as a matrix, wherein the specific surface area of the catalyst is 200-300 m<2> / g; the pore volume is 0.45-0.65 cm<3> / g; the particle size is 1.0-3.0 mm. The catalyst mainly comprises the following components: 0-15% of Ni, 0-10% of Co, 0-5% of Mo, 0-10% of Fe, and 0-5% of La. The preparation method of the catalyst comprises the following steps: dipping a carrier for 4.0-12.0 h, then performing dehydration, spraying and performing dehydration, drying, baking, and activating the substance to prepare the spherical particle-like catalyst. The preparation method has the advantages that the solid catalyst for synthesizing piperazine through the monoethanolamine catalytic amination one-step method is prepared; the preparation method of the catalyst adopts a dipping and spraying combined technology, so that the method is simple and convenient to operate; the catalytic medium is free from addition of noble metal, so that the preparation cost of the catalyst is obviously reduced. When the catalyst is used for synthesizing piperazine through the monoethanolamine catalytic amination one-step method, the preparation method has the characteristics of high reaction selectivity and high reaction yield.

Description

technical field

[0001] The invention relates to a preparation method of a catalyst for synthesizing piperazine by one-step method of catalytic amination of monoethanolamine. Background technique

[0002] Piperazine (also known as hexahydropyrazine, piperazine, piperazine, bis-dimethylamine, tetramethyldiamine, p-diazepine). It is a colorless transparent needle-like or leaf-like crystals. Molecular formula C 4 N 10 o 2 The molecular weight is 86.14. It is an important pharmaceutical intermediate and fine chemical raw material. In medicine, it is used as a pharmaceutical intermediate for the production of fluperazine, pyrazinoic acid, anthelmintic fosperidic acid, and fluphenazine, lactonidine, rifampicin and other drugs. In fine chemical industry: piperazine can be used as rubber vulcanizing agent, antioxidant, preservative, surfactant, synthetic resin, synthetic fiber, synthetic leather, etc.

[0003] U.S. Patent No. 3,112,318 discloses a method for generating piperaz...

Examples

Embodiment 1

[0016] The preparation method of the monoethanolamine-catalyzed amination one-step method for the synthesis of piperazine catalyst in this example includes the following steps: 1) Preparation of the carrier: use γ-Al 2 o 3 and θ-Al 2 o 3 The mixture is the carrier; it is made with a specific surface area of ​​250m 2 / g, the pore volume is 0.55cm 3 / g, a carrier of spherical particles with a particle size of 2.0 mm.

[0017] 2) Weigh Ni (NO 3 ) 2 .6H 2 O29.1g (0.1mol), Co (NO 3 ) 2 .6H 2 O17.50g (0.06mol), MO (NO 3 ) 3 .5H 2 O6.65g (0.015mol), Fe (NO 3 ) 3 .9H 2 O20.2g (0.05mol), the concentration of its element corresponding salt is: Ni is 0.22mol / L, Co is 0.13mol / L, Mo is 0.033mol / L, Fe is 0.11mol / L. Add deionized water and fully stir and dissolve in a water bath at 60±2°C to form a 450ml solution.

[0018] 3) Take 300ml of the prepared solution in step 2) and weigh 100g of γ-Al 2 o 3 and θ-Al 2 o 3 The carrier is placed therein and soaked for 6.0 hours. ...

Embodiment 2

[0021] The preparation method of the monoethanolamine-catalyzed amination one-step method for the synthesis of piperazine catalyst in this example includes the following steps: 1) Preparation of the carrier: use γ-Al 2 o 3 and θ-Al 2 o 3 The mixture is the carrier; it is made with a specific surface area of ​​200m 2 / g, the pore volume is 0.45cm 3 / g, a carrier of spherical particles with a particle size of 1.0 mm.

[0022] 2) Weigh Ni (NO 3 ) 2 .6H 2 O58.2g (0.2mol), Co (NO 3 ) 2 .6H 2 O29.0g (0.10mol), MO (NO 3 ) 3 .5H 2 O8.86g (0.02mol), Fe (NO 3 ) 3 .9H 2 O40.4g (0.10mol), La (NO 3 ) 3 .6H 2O8.66g (0.02mol), the concentration of its element corresponding salt is: Ni is 0.44mol / L, Co is 0.22mol / L, Mo is 0.044mol / L, Fe is 0.22mol / L, La is 0.44mol / L L. Add deionized water and fully stir and dissolve in a water bath at 60±2°C to form a 450ml solution.

[0023] 3) Take 300ml of prepared solution and weigh 100g of γ-Al 2 o 3 and θ-Al 2 o 3 The carrier wa...

Embodiment 3

[0026] The preparation method of the monoethanolamine-catalyzed amination one-step method for the synthesis of piperazine catalyst in this example includes the following steps: 1) Preparation of the carrier: use γ-Al 2 o 3 and θ-Al 2 o 3 The mixture is the carrier; it is made with a specific surface area of ​​300m 2 / g, the pore volume is 0.65cm 3 / g, a carrier of spherical particles with a particle size of 3.0 mm.

[0027] 2) Weigh Ni (NO 3 ) 2 .6H 2 O58.2g (0.2mol), Co (NO 3 ) 2 .6H 2 O29.0g (0.10mol), MO (NO 3 ) 3 .5H 2 O13.30g (0.03mol), La (NO 3 ) 3 .6H 2 O4.4g (0.01mol), the concentration of the corresponding salt of its element is: Ni is 0.44mol / L, Co is 0.22mol / L, Mo is 0.066mol / L, La is 0.022mol / L. Add deionized water and fully stir and dissolve in a water bath at 60±2°C to form a 450ml solution.

[0028] 3) Take 300ml of prepared solution and weigh 100g of γ-Al 2 o 3 and θ-Al 2 o 3 The carrier was placed therein and soaked for 12.0 hours.

[002...

technical field

[0001] The invention relates to a preparation method of a catalyst for synthesizing piperazine by one-step method of catalytic amination of monoethanolamine. Background technique

[0002] Piperazine (also known as hexahydropyrazine, piperazine, piperazine, bis-dimethylamine, tetramethyldiamine, p-diazepine). It is a colorless transparent needle-like or leaf-like crystals. Molecular formula C 4 N 10 o 2 The molecular weight is 86.14. It is an important pharmaceutical intermediate and fine chemical raw material. In medicine, it is used as a pharmaceutical intermediate for the production of fluperazine, pyrazinoic acid, anthelmintic fosperidic acid, and fluphenazine, lactonidine, rifampicin and other drugs. In fine chemical industry: piperazine can be used as rubber vulcanizing agent, antioxidant, preservative, surfactant, synthetic resin, synthetic fiber, synthetic leather, etc.

[0003] U.S. Patent No. 3,112,318 discloses a method for generating piperaz...

Examples

Embodiment 1

[0016] The preparation method of the monoethanolamine-catalyzed amination one-step method for the synthesis of piperazine catalyst in this example includes the following steps: 1) Preparation of the carrier: use γ-Al 2 o 3 and θ-Al 2 o 3 The mixture is the carrier; it is made with a specific surface area of ​​250m 2 / g, the pore volume is 0.55cm 3 / g, a carrier of spherical particles with a particle size of 2.0 mm.

[0017] 2) Weigh Ni (NO 3 ) 2 .6H 2 O29.1g (0.1mol), Co (NO 3 ) 2 .6H 2 O17.50g (0.06mol), MO (NO 3 ) 3 .5H 2 O6.65g (0.015mol), Fe (NO 3 ) 3 .9H 2 O20.2g (0.05mol), the concentration of its element corresponding salt is: Ni is 0.22mol / L, Co is 0.13mol / L, Mo is 0.033mol / L, Fe is 0.11mol / L. Add deionized water and fully stir and dissolve in a water bath at 60±2°C to form a 450ml solution.

[0018] 3) Take 300ml of the prepared solution in step 2) and weigh 100g of γ-Al 2 o 3 and θ-Al 2 o 3 The carrier is placed therein and soaked for 6.0 hours. ...

Embodiment 2

[0021] The preparation method of the monoethanolamine-catalyzed amination one-step method for the synthesis of piperazine catalyst in this example includes the following steps: 1) Preparation of the carrier: use γ-Al 2 o 3 and θ-Al 2 o 3 The mixture is the carrier; it is made with a specific surface area of ​​200m 2 / g, the pore volume is 0.45cm 3 / g, a carrier of spherical particles with a particle size of 1.0 mm.

[0022] 2) Weigh Ni (NO 3 ) 2 .6H 2 O58.2g (0.2mol), Co (NO 3 ) 2 .6H 2 O29.0g (0.10mol), MO (NO 3 ) 3 .5H 2 O8.86g (0.02mol), Fe (NO 3 ) 3 .9H 2 O40.4g (0.10mol), La (NO 3 ) 3 .6H 2O8.66g (0.02mol), the concentration of its element corresponding salt is: Ni is 0.44mol / L, Co is 0.22mol / L, Mo is 0.044mol / L, Fe is 0.22mol / L, La is 0.44mol / L L. Add deionized water and fully stir and dissolve in a water bath at 60±2°C to form a 450ml solution.

[0023] 3) Take 300ml of prepared solution and weigh 100g of γ-Al 2 o 3 and θ-Al 2 o 3 The carrier wa...

Embodiment 3

[0026] The preparation method of the monoethanolamine-catalyzed amination one-step method for the synthesis of piperazine catalyst in this example includes the following steps: 1) Preparation of the carrier: use γ-Al 2 o 3 and θ-Al 2 o 3 The mixture is the carrier; it is made with a specific surface area of ​​300m 2 / g, the pore volume is 0.65cm 3 / g, a carrier of spherical particles with a particle size of 3.0 mm.

[0027] 2) Weigh Ni (NO 3 ) 2 .6H 2 O58.2g (0.2mol), Co (NO 3 ) 2 .6H 2 O29.0g (0.10mol), MO (NO 3 ) 3 .5H 2 O13.30g (0.03mol), La (NO 3 ) 3 .6H 2 O4.4g (0.01mol), the concentration of the corresponding salt of its element is: Ni is 0.44mol / L, Co is 0.22mol / L, Mo is 0.066mol / L, La is 0.022mol / L. Add deionized water and fully stir and dissolve in a water bath at 60±2°C to form a 450ml solution.

[0028] 3) Take 300ml of prepared solution and weigh 100g of γ-Al 2 o 3 and θ-Al 2 o 3 The carrier was placed therein and soaked for 12.0 hours.

[002...

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