Load type transition metal catalyst and preparation method thereof and method for preparing picoline

Abstract

The invention provides a load type transition metal catalyst, which comprises a porous support and a transition metal complex which is loaded on the porous support, the general formula of the transition metal complex is R1(Z)yMR2, wherein R1 and R2 are the same or different, and are respectively substituted or unsubstituted cyclopentadienyl, substituted or unsubstituted indenyl and substituted or unsubstituted fluorenyl, wherein y is 0 or 1, Z is a linked group for connecting R1 and R2, and M is transition metal element. The invention further provides a method for preparing load type transition metal catalyst, which comprises leading the porous support and the transition metal complex to contact under the existence of dissolvent, and removing dissolvent. The invention further provides a method for preparing picoline through adopting load type transition metal catalyst. The load type transition metal catalyst can effectively prompt methyl cyanide and acetylene to react for preparing 2-picoline.

Description

technical field

[0001] The invention relates to a supported transition metal catalyst, a preparation method of the supported transition metal catalyst and a method for preparing picoline by using the supported transition metal catalyst. Background technique

[0002] As an important chemical intermediate, picoline is also an important raw material for fine chemicals, and can be used in many fields, for example, as a raw material for medicine and agrochemicals. In the picoline series, 2-picoline can be used to produce long-acting sulfonamide, antiallergic drug chlorpheniramine, pesticide intermediates, feed and feed intermediates, and can also be used to prepare herbicide drugs. At present, the method for producing 2-picoline mainly contains two kinds, one is to refine 2-picoline with coal tar, the main defect of this method is low yield, poor quality, and coal tar resources are also quite poor; the other The first is to produce 2-picoline by the ammonia aldehyde method. The ...

Examples

Embodiment 1

[0025] This example is used to illustrate the supported transition metal catalyst provided by the present invention and its preparation method.

[0026] (1) make 1 kg of SiO with an average particle diameter of 30 nanometers, a specific surface area of ​​507 square meters per gram, and a porosity of 0.74%. 2 The support was heated at 300 °C for 6 hours under a vacuum of 4 Pa, and then cooled to room temperature under a nitrogen atmosphere to obtain 0.994 kg of dehydrated and dehydroxylated SiO 2 carrier;

[0027] (2) Under a nitrogen atmosphere, the SiO obtained in (1) 2 Add the carrier to 9500 ml of tetrahydrofuran, stir well to make a suspension;

[0028] (3) At room temperature, under a nitrogen atmosphere, 2 moles of cyclopentadienyl sodium and 1.2 moles of anhydrous CoCl 2 Add to 300 ml of tetrahydrofuran and carry out contact reaction for 3.2 hours, vacuum filter the mixture obtained after the reaction (absolute pressure, that is, vacuum degree is 0.01MPa), then obtai...

Embodiment 2

[0035]This example is used to illustrate the supported transition metal catalyst provided by the present invention and its preparation method.

[0036] (1) Make 1 kilogram of SiO with an average particle diameter of 300 nanometers, a specific surface area of ​​200 square meters per gram, and a porosity of 0.51%. 2 The support was heated at 500 °C for 2 hours under a vacuum of 4 Pa, and then cooled to room temperature under a nitrogen atmosphere to obtain 0.997 kg of dehydrated and dehydroxylated SiO 2 carrier;

[0037] (2) Under a nitrogen atmosphere, the SiO obtained in (1) 2 Add the carrier to 9500 ml of toluene and stir well to make a suspension;

[0038] (3) At room temperature, under a nitrogen atmosphere, 2 moles of tetramethylcyclopentadienyl sodium and 1.3 moles of anhydrous CoCl 2 Add to 250 ml of tetrahydrofuran and carry out contact reaction for 2 hours, vacuum filter the mixture obtained after the reaction (absolute pressure, that is, vacuum degree is 0.01MPa), ...

Embodiment 3

[0045] This example is used to illustrate the supported transition metal catalyst provided by the present invention and its preparation method.

[0046] (1) make 1 kilogram of particle diameter be 10 nanometers, specific surface area be 700 square meters per gram, porosity 0.79% TiO 2 and SiO 2 Composite support (TiO 2 with SiO 2 The molar ratio of 1:70) was heated at 200 ° C for 10 hours under a vacuum of 4 Pa, and then cooled to room temperature under a nitrogen atmosphere to obtain 0.992 kg of dehydrated and dehydroxylated TiO 2 -SiO 2 Composite carrier;

[0047] (2) Under a nitrogen atmosphere, the TiO obtained in (1) 2 -SiO 2 The composite carrier is added to 9500 ml of pentane and stirred well to make a suspension;

[0048] (3) At room temperature, under a nitrogen atmosphere, mix 2 moles of indenyl sodium and 1.1 moles of anhydrous CoCl 2 Add to 200 ml of tetrahydrofuran and carry out contact reaction for 2.5 hours, vacuum filter the mixture obtained after the r...

technical field

[0001] The invention relates to a supported transition metal catalyst, a preparation method of the supported transition metal catalyst and a method for preparing picoline by using the supported transition metal catalyst. Background technique

[0002] As an important chemical intermediate, picoline is also an important raw material for fine chemicals, and can be used in many fields, for example, as a raw material for medicine and agrochemicals. In the picoline series, 2-picoline can be used to produce long-acting sulfonamide, antiallergic drug chlorpheniramine, pesticide intermediates, feed and feed intermediates, and can also be used to prepare herbicide drugs. At present, the method for producing 2-picoline mainly contains two kinds, one is to refine 2-picoline with coal tar, the main defect of this method is low yield, poor quality, and coal tar resources are also quite poor; the other The first is to produce 2-picoline by the ammonia aldehyde method. The ...

Examples

Embodiment 1

[0025] This example is used to illustrate the supported transition metal catalyst provided by the present invention and its preparation method.

[0026] (1) make 1 kg of SiO with an average particle diameter of 30 nanometers, a specific surface area of ​​507 square meters per gram, and a porosity of 0.74%. 2 The support was heated at 300 °C for 6 hours under a vacuum of 4 Pa, and then cooled to room temperature under a nitrogen atmosphere to obtain 0.994 kg of dehydrated and dehydroxylated SiO 2 carrier;

[0027] (2) Under a nitrogen atmosphere, the SiO obtained in (1) 2 Add the carrier to 9500 ml of tetrahydrofuran, stir well to make a suspension;

[0028] (3) At room temperature, under a nitrogen atmosphere, 2 moles of cyclopentadienyl sodium and 1.2 moles of anhydrous CoCl 2 Add to 300 ml of tetrahydrofuran and carry out contact reaction for 3.2 hours, vacuum filter the mixture obtained after the reaction (absolute pressure, that is, vacuum degree is 0.01MPa), then obtai...

Embodiment 2

[0035]This example is used to illustrate the supported transition metal catalyst provided by the present invention and its preparation method.

[0036] (1) Make 1 kilogram of SiO with an average particle diameter of 300 nanometers, a specific surface area of ​​200 square meters per gram, and a porosity of 0.51%. 2 The support was heated at 500 °C for 2 hours under a vacuum of 4 Pa, and then cooled to room temperature under a nitrogen atmosphere to obtain 0.997 kg of dehydrated and dehydroxylated SiO 2 carrier;

[0037] (2) Under a nitrogen atmosphere, the SiO obtained in (1) 2 Add the carrier to 9500 ml of toluene and stir well to make a suspension;

[0038] (3) At room temperature, under a nitrogen atmosphere, 2 moles of tetramethylcyclopentadienyl sodium and 1.3 moles of anhydrous CoCl 2 Add to 250 ml of tetrahydrofuran and carry out contact reaction for 2 hours, vacuum filter the mixture obtained after the reaction (absolute pressure, that is, vacuum degree is 0.01MPa), ...

Embodiment 3

[0045] This example is used to illustrate the supported transition metal catalyst provided by the present invention and its preparation method.

[0046] (1) make 1 kilogram of particle diameter be 10 nanometers, specific surface area be 700 square meters per gram, porosity 0.79% TiO 2 and SiO 2 Composite support (TiO 2 with SiO 2 The molar ratio of 1:70) was heated at 200 ° C for 10 hours under a vacuum of 4 Pa, and then cooled to room temperature under a nitrogen atmosphere to obtain 0.992 kg of dehydrated and dehydroxylated TiO 2 -SiO 2 Composite carrier;

[0047] (2) Under a nitrogen atmosphere, the TiO obtained in (1) 2 -SiO 2 The composite carrier is added to 9500 ml of pentane and stirred well to make a suspension;

[0048] (3) At room temperature, under a nitrogen atmosphere, mix 2 moles of indenyl sodium and 1.1 moles of anhydrous CoCl 2 Add to 200 ml of tetrahydrofuran and carry out contact reaction for 2.5 hours, vacuum filter the mixture obtained after the r...

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