Micro spherical hollow structure nickel-based hydrogenation catalyst as well as preparation method thereof

Abstract

The invention discloses a micro spherical hollow structure nickel-based hydrogenation catalyst as well as a preparation method thereof in the technical field of catalyst preparation. The method comprises the following steps: controlling the morphology of an aluminum raw material serving as a mold plate which is consumed gradually along with the reaction, inducing hydrotalcite assembly to obtain a micro spherical hollow hydrotalcite assembly body, and carrying out in-situ reduction to obtain the micro spherical hollow nickel-based catalyst. The catalyst material obtained by preparation has high specific surface area, and the internal empty cavity structure and the abundant open-framework structures have great actual application value. The catalyst has relatively high hydrogenation activity and selectivity when being used for catalyzing dimethyl terephthalate (DMT) benzene ring hydrogenation in the reaction for preparing dimethyl 1, 4-cyclohexanedicarboxylate.

Description

technical field

[0001] The invention belongs to the technical field of nickel-based hydrogenation catalyst preparation, in particular to a nickel-based hydrogenation catalyst with a microspherical hollow structure and a preparation method thereof. Background technique

[0002] Hydrotalcite is a multifunctional anionic layered material, also known as double hydroxyl composite metal hydroxide, and its general chemical formula can be expressed as [M 1-x 2+ m x 3+ (OH) 2 ] x+ (A n- ) x / n mH 2 O, where A n- Represents the anion that can be exchanged between layers, n is the number of charges, M 3+ ,M 2+ respectively represent trivalent and divalent metal cations, and x refers to the content of metal elements. Hydrotalcite has a layered structure, exchangeability of interlayer ions, and tunable denaturation of layer elements, and has a wide range of applications in catalysis, adsorption, biosensing, and optoelectronic materials. The performance of hydrotalcite flakes i...

Examples

Embodiment 1

[0015] Weigh 1.2716g of Al(H 2 PO 4 ) 3 Dissolve in 40mL of deionized water, then ultrasonically until completely dissolved into a transparent clear solution, reflux and stir in an oil bath at 90°C for 6 hours to obtain a white turbid colloidal solution, and then pour it into a polytetrafluoroethylene liner of a high-pressure hydrothermal reactor; Weigh 0.9608g of urea and 2.1028g of NiSO 4 ·6H 2 O was dissolved in 40mL deionized water, and then ultrasonicated until it was completely dissolved into a clear solution, poured into the polytetrafluoroethylene liner of the above-mentioned high-pressure hydrothermal reaction kettle, sealed evenly after stirring, and moved to a constant temperature oven at 100°C, and reacted for 12 hours. Take it out and cool it to room temperature; wash it with deionized water and absolute ethanol until neutral, and place the obtained product in a constant temperature drying oven at 70°C for 48 hours to obtain a micron-sized hollow spherical nick...

Embodiment 2

[0017] Weigh 0.9853g of aluminum sec-butoxide and dissolve it in 40mL of deionized water, sonicate until it completely dissolves into a transparent clear solution, reflux and stir in an oil bath at 100°C for 4 hours to obtain a white turbid colloidal solution, and then pour it into a high-pressure hydrothermal reactor for polymerization In tetrafluoroethylene liner; weigh 1.9216g urea and 3.1542gNiSO 4 ·6H 2 O was dissolved in 40mL of deionized water, and ultrasonic washer until it was completely dissolved to obtain a green transparent solution, which was transferred to the aforementioned liner, stirred until evenly mixed, sealed and sealed in the high-pressure hydrothermal kettle, and transferred to a 150°C In a constant temperature oven, after 12 hours of reaction, take it out and cool it to room temperature; wash it with deionized water and absolute ethanol until neutral, and place the product in a constant temperature drying oven at 70°C for 48 hours to obtain a micron-siz...

Embodiment 3

[0019] Weigh 2.6657g of Al 2 (SO 4 ) 3 18H 2 Dissolve O in 40mL deionized water, sonicate until completely dissolved into a transparent clear solution, reflux and stir in an oil bath at 70°C for 4 hours, cool to room temperature after the reaction, and transfer to a PTFE liner of a 100mL high-pressure hydrothermal reactor stand-by; then weigh 2.2430g of hexamethylenetetramine and 4.2056g of NiSO 4 ·6H 2 Dissolve O in 40mL deionized water, and ultrasonically sonicate until completely dissolved to obtain a green clear solution, which is then transferred to the previously described liner and stirred evenly; seal the high-pressure hydrothermal kettle and place it in a constant temperature oven at 140°C React for 24 hours; after the reaction, take out the reactor and cool to room temperature, wash with deionized water and absolute ethanol until the system pH is about 7, and then dry the obtained precipitate in a constant temperature drying oven at 60°C for 48 hours to obtain mi...

technical field

[0001] The invention belongs to the technical field of nickel-based hydrogenation catalyst preparation, in particular to a nickel-based hydrogenation catalyst with a microspherical hollow structure and a preparation method thereof. Background technique

[0002] Hydrotalcite is a multifunctional anionic layered material, also known as double hydroxyl composite metal hydroxide, and its general chemical formula can be expressed as [M 1-x 2+ m x 3+ (OH) 2 ] x+ (A n- ) x / n mH 2 O, where A n- Represents the anion that can be exchanged between layers, n is the number of charges, M 3+ ,M 2+ respectively represent trivalent and divalent metal cations, and x refers to the content of metal elements. Hydrotalcite has a layered structure, exchangeability of interlayer ions, and tunable denaturation of layer elements, and has a wide range of applications in catalysis, adsorption, biosensing, and optoelectronic materials. The performance of hydrotalcite flakes i...

Examples

Embodiment 1

[0015] Weigh 1.2716g of Al(H 2 PO 4 ) 3 Dissolve in 40mL of deionized water, then ultrasonically until completely dissolved into a transparent clear solution, reflux and stir in an oil bath at 90°C for 6 hours to obtain a white turbid colloidal solution, and then pour it into a polytetrafluoroethylene liner of a high-pressure hydrothermal reactor; Weigh 0.9608g of urea and 2.1028g of NiSO 4 ·6H 2 O was dissolved in 40mL deionized water, and then ultrasonicated until it was completely dissolved into a clear solution, poured into the polytetrafluoroethylene liner of the above-mentioned high-pressure hydrothermal reaction kettle, sealed evenly after stirring, and moved to a constant temperature oven at 100°C, and reacted for 12 hours. Take it out and cool it to room temperature; wash it with deionized water and absolute ethanol until neutral, and place the obtained product in a constant temperature drying oven at 70°C for 48 hours to obtain a micron-sized hollow spherical nick...

Embodiment 2

[0017] Weigh 0.9853g of aluminum sec-butoxide and dissolve it in 40mL of deionized water, sonicate until it completely dissolves into a transparent clear solution, reflux and stir in an oil bath at 100°C for 4 hours to obtain a white turbid colloidal solution, and then pour it into a high-pressure hydrothermal reactor for polymerization In tetrafluoroethylene liner; weigh 1.9216g urea and 3.1542gNiSO 4 ·6H 2 O was dissolved in 40mL of deionized water, and ultrasonic washer until it was completely dissolved to obtain a green transparent solution, which was transferred to the aforementioned liner, stirred until evenly mixed, sealed and sealed in the high-pressure hydrothermal kettle, and transferred to a 150°C In a constant temperature oven, after 12 hours of reaction, take it out and cool it to room temperature; wash it with deionized water and absolute ethanol until neutral, and place the product in a constant temperature drying oven at 70°C for 48 hours to obtain a micron-siz...

Embodiment 3

[0019] Weigh 2.6657g of Al 2 (SO 4 ) 3 18H 2 Dissolve O in 40mL deionized water, sonicate until completely dissolved into a transparent clear solution, reflux and stir in an oil bath at 70°C for 4 hours, cool to room temperature after the reaction, and transfer to a PTFE liner of a 100mL high-pressure hydrothermal reactor stand-by; then weigh 2.2430g of hexamethylenetetramine and 4.2056g of NiSO 4 ·6H 2 Dissolve O in 40mL deionized water, and ultrasonically sonicate until completely dissolved to obtain a green clear solution, which is then transferred to the previously described liner and stirred evenly; seal the high-pressure hydrothermal kettle and place it in a constant temperature oven at 140°C React for 24 hours; after the reaction, take out the reactor and cool to room temperature, wash with deionized water and absolute ethanol until the system pH is about 7, and then dry the obtained precipitate in a constant temperature drying oven at 60°C for 48 hours to obtain mi...

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