Catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and preparing method thereof

Abstract

The invention relates to a catalyst for synthesizing cyclohexene by hydrogenation of benzene ring and a preparing method thereof. The catalyst consists of activated carbon carrier, metal ruthenium and promoter; the promoter is one or the mixture of more than two from platinum, palladium, rhodium, cobalt and nickel. The method comprises the following steps: pretreated activated carbon is added into water-soluble compound solution of metal ruthenium or mixed water-soluble precursor solution of the metal ruthenium and the promoter so as to be stirred and soaked, thus obtaining mixed slurry; the PH value of the mixed slurry is regulated by alkali compound aqueous solution, after stirring and filtering, the filter cake is washed to neutrality by water, and then after the filter cake is beaten by water, the PH value of the mixed slurry is regulated by the alkali compound aqueous solution, then a chemical reducer is added to reduce ruthenium carbon catalyst in liquid phase, and after washing, the filter cake is transferred into an oven so as to be dried, thus obtaining the product of the ruthenium carbon catalyst. The catalyst has good catalytic activity and high selectivity and is especially suitable for catalytic hydrogenation for synthesizing cyclohexene by the hydrogenation of benzene ring, and the preparing method has simple operation and short production period.

Description

technical field

[0001] The invention relates to a selective hydrogenation catalyst and a preparation method thereof, in particular to a benzene ring hydrogenation synthesis cyclohexene catalyst, a preparation method and application thereof. Background technique

[0002] There is a lively double bond in the cyclohexene ring. As an important organic chemical raw material, it is widely used in the production of pharmaceuticals, pesticides, feed additives, polyesters and other fine chemical products. It can be directly oxidized to adipic acid. Wacker method oxidation to generate cyclohexanone, or direct hydration to generate cyclohexanol. Adipic acid, cyclohexanone and cyclohexanol are very important chemical raw materials. Cyclohexene is not a natural product and must be obtained through chemical synthesis, and hydrogenation of benzene is the best way to obtain it. In particular, the partial hydrogenation of the benzene ring of nylon 66 is safer and more reliable than the tra...

Examples

Embodiment 1

[0024] Take by weighing 9.50 g of pretreated activated carbon, add 20 mL of precious metal ruthenium to 0.50 g of ruthenium trichloride aqueous solution and stir and impregnate for 5 hours, then adjust the pH of the mixed slurry to 9.0 with alkaline potassium hydroxide aqueous solution, and continue to stir for 3 hour, filter, the filter cake is washed with water to neutrality, after the filter cake is beaten with water, the pH of the mixed slurry is adjusted to 12.0 with alkaline potassium hydroxide aqueous solution, and the ruthenium carbon catalyst is reduced by adding potassium borohydride solution in liquid phase, and washed, The filter cake was transferred to an oven and dried at 100° C. for 5 hours to obtain a highly dispersed nano-ruthenium carbon-supported noble metal hydrogenation catalyst. Most of the ruthenium particle diameters of the nano-Ru / activated carbon catalyst are 40-80nm.

Embodiment 2

[0026] Take pretreated active carbon 9.50g, join 20ml noble metal ruthenium content and be 0.40g and auxiliary agent Co content be in the chloride aqueous solution of 0.10g and stir impregnation 5 hours, then adjust the mixed slurry with alkaline potassium hydroxide aqueous solution pH to 9.0, continue to stir for 3 hours, filter, wash the filter cake with water until neutral, beat the filter cake with water, adjust the pH of the mixed slurry to 12.0 with alkaline potassium hydroxide aqueous solution, and add potassium borohydride solution to the liquid phase The ruthenium carbon catalyst was reduced, washed, and the filter cake was transferred to an oven and dried at 100° C. for 5 hours to obtain a highly dispersed nano-ruthenium carbon-supported noble metal hydrogenation catalyst. Most of the metal particle diameters of the nanometer Ru-Co / activated carbon catalyst are 40-80nm.

Embodiment 3

[0028] Take pretreated active carbon 9.50g, join 20ml noble metal ruthenium content and be 0.45g and auxiliary agent Pd content be in the chloride aqueous solution of 0.05g and stir impregnation 5 hours, then adjust the mixed slurry with alkaline potassium hydroxide aqueous solution pH to 9.0, continue to stir for 3 hours, filter, wash the filter cake with water until neutral, beat the filter cake with water, adjust the pH of the mixed slurry to 12.0 with alkaline potassium hydroxide aqueous solution, and add potassium borohydride solution to the liquid phase The ruthenium carbon catalyst was reduced, washed, and the filter cake was transferred to an oven and dried at 100° C. for 5 hours to obtain a highly dispersed nano-ruthenium carbon-supported noble metal hydrogenation catalyst. Most of the metal particle diameters of the nanometer Ru-Pd / activated carbon catalyst are 40-80nm.

technical field

[0001] The invention relates to a selective hydrogenation catalyst and a preparation method thereof, in particular to a benzene ring hydrogenation synthesis cyclohexene catalyst, a preparation method and application thereof. Background technique

[0002] There is a lively double bond in the cyclohexene ring. As an important organic chemical raw material, it is widely used in the production of pharmaceuticals, pesticides, feed additives, polyesters and other fine chemical products. It can be directly oxidized to adipic acid. Wacker method oxidation to generate cyclohexanone, or direct hydration to generate cyclohexanol. Adipic acid, cyclohexanone and cyclohexanol are very important chemical raw materials. Cyclohexene is not a natural product and must be obtained through chemical synthesis, and hydrogenation of benzene is the best way to obtain it. In particular, the partial hydrogenation of the benzene ring of nylon 66 is safer and more reliable than the tra...

Examples

Embodiment 1

[0024] Take by weighing 9.50 g of pretreated activated carbon, add 20 mL of precious metal ruthenium to 0.50 g of ruthenium trichloride aqueous solution and stir and impregnate for 5 hours, then adjust the pH of the mixed slurry to 9.0 with alkaline potassium hydroxide aqueous solution, and continue to stir for 3 hour, filter, the filter cake is washed with water to neutrality, after the filter cake is beaten with water, the pH of the mixed slurry is adjusted to 12.0 with alkaline potassium hydroxide aqueous solution, and the ruthenium carbon catalyst is reduced by adding potassium borohydride solution in liquid phase, and washed, The filter cake was transferred to an oven and dried at 100° C. for 5 hours to obtain a highly dispersed nano-ruthenium carbon-supported noble metal hydrogenation catalyst. Most of the ruthenium particle diameters of the nano-Ru / activated carbon catalyst are 40-80nm.

Embodiment 2

[0026] Take pretreated active carbon 9.50g, join 20ml noble metal ruthenium content and be 0.40g and auxiliary agent Co content be in the chloride aqueous solution of 0.10g and stir impregnation 5 hours, then adjust the mixed slurry with alkaline potassium hydroxide aqueous solution pH to 9.0, continue to stir for 3 hours, filter, wash the filter cake with water until neutral, beat the filter cake with water, adjust the pH of the mixed slurry to 12.0 with alkaline potassium hydroxide aqueous solution, and add potassium borohydride solution to the liquid phase The ruthenium carbon catalyst was reduced, washed, and the filter cake was transferred to an oven and dried at 100° C. for 5 hours to obtain a highly dispersed nano-ruthenium carbon-supported noble metal hydrogenation catalyst. Most of the metal particle diameters of the nanometer Ru-Co / activated carbon catalyst are 40-80nm.

Embodiment 3

[0028] Take pretreated active carbon 9.50g, join 20ml noble metal ruthenium content and be 0.45g and auxiliary agent Pd content be in the chloride aqueous solution of 0.05g and stir impregnation 5 hours, then adjust the mixed slurry with alkaline potassium hydroxide aqueous solution pH to 9.0, continue to stir for 3 hours, filter, wash the filter cake with water until neutral, beat the filter cake with water, adjust the pH of the mixed slurry to 12.0 with alkaline potassium hydroxide aqueous solution, and add potassium borohydride solution to the liquid phase The ruthenium carbon catalyst was reduced, washed, and the filter cake was transferred to an oven and dried at 100° C. for 5 hours to obtain a highly dispersed nano-ruthenium carbon-supported noble metal hydrogenation catalyst. Most of the metal particle diameters of the nanometer Ru-Pd / activated carbon catalyst are 40-80nm.