Composite solid super acidic catalyst and preparation method thereof

Abstract

The invention discloses a rear-earth-containing compound solid super acidic catalyst and a preparation method thereof. The catalyst consists of a ZrO2 carrier containing a sulfate ion, a TiO2 carrier, a nickel oxide and a halide of aluminum, wherein, the content of the sulfate ion is 10 to 20 wt percent, the content of the carrier of ZrO2 is 30 to 50 wt percent, the content of the carrier of TiO2 is 30 to 50 wt percent, the content of the halide of aluminum is 1 to 5 wt percent, the water content in the catalyst is less than 0.1 wt percent, the content of the nickel oxide is 1 to 5 wt percent and the specific surface of the catalyst is 100 to 300 square meters per gram. The halide of aluminum is aluminum fluoride or aluminum chloride or mixture of aluminum fluoride and aluminum chloride. The catalyst made by the invention has low water content, high specific surface, high content of SO4<2->, high acid strength and high catalytic efficiency.

Description

technical field

[0001] The present invention relates to a kind of composite solid superacid catalyst and preparation method thereof, more specifically relate to a kind of modified ZrO containing sulfate ion 2 Supported solid superacid catalyst and its preparation method. Background technique

[0002] A solid superacid is a solid acid with a stronger acidity than 100% sulfuric acid, expressed by the Hammett acidity function, the H of 100% sulfuric acid 0 =-11.93, while the H of the solid superacid 0 <-11.93. Compared with traditional catalysts, solid superacids have the following characteristics: (1) high catalytic efficiency, less dosage, less side reactions, and less by-products; (2) can be used at high temperatures, reusable, and the separation of catalysts and products is simple ; (3) non-corrosive, not polluting the environment; (4) the preparation method is simple and can be prepared by general metal salts. Due to the above advantages, the research and applicatio...

Examples

preparation example Construction

[0017] The preparation method of above-mentioned composite solid superacid catalyst comprises the following steps:

[0018] a. Under ice-water bath conditions, the titanium tetrachloride aqueous solution with a concentration of 1 to 5wt% and the zirconium oxychloride aqueous solution with a concentration of 1 to 5wt% are mixed, the weight ratio of the titanium tetrachloride aqueous solution to the zirconium oxychloride aqueous solution 1:0.5~2, add ethanol as a dispersant, then add ammonia water and stir to make the pH value of the mixed solution in the range of 9~10, generate zirconium hydroxide and titanium hydroxide precipitation, add 0.1~0.5mol / L nitric acid solution to generate the sol of zirconium hydroxide and titanium hydroxide;

[0019] b. Filter and wash the sol until the pH of the filtrate is 6.9-7.1 without Cl - ions, followed by drying to obtain ZrO 2 and TiO 2 mixed precursor oxides;

[0020] c. Mix the above-mentioned mixed precursor oxide with aluminum hali...

Embodiment 1

[0028] Under the condition of ice-water bath, the concentration of 1wt% TiCl 4 The aqueous solution and the zirconium oxychloride aqueous solution with a concentration of 1 wt% are mixed according to the ratio of 1:0.5, and ethanol is added as a dispersant, and the volume ratio of the mixed liquid to ethanol is 1:5. Use ammonia water to adjust the pH value of the solution to the range of 9-10, and stir when adding the ammonia water to form zirconium hydroxide and titanium hydroxide precipitates. Then add 0.1mol / L nitric acid solution to the precipitate to generate zirconium hydroxide and titanium hydroxide sol, and the relative ratio of the precipitate to the nitric acid solution is 1:0.1. The sol was filtered and washed until the filtrate pH was 7 and Cl-free - , and then dried to obtain a mixed precursor oxide. The mixture of mixed precursor oxide and aluminum fluoride powder was ground to 3 ) 2 Soluble in 0.5mol / L H 2 SO 4 A sulfuric acid solution of 0.1mol / L nickel ni...

Embodiment 2

[0032] Catalyst is prepared by the method of embodiment 1, difference is that concentration is 1wt% TiCl 4 The aqueous solution and the zirconium oxychloride aqueous solution with a concentration of 1wt% are mixed according to the ratio of 1:2, and the AlF in the mixture of the precursor oxide and the aluminum fluoride powder is mixed. 3 The content is 3wt%, and the calcination temperature of the catalyst is 700°C. The impregnating solution is a certain amount of Ni(NO 3 ) 2 Soluble in 0.5mol / L H 2 SO 4 A sulfuric acid solution of 0.5mol / L nickel nitrate was made in the medium. The ground mixture is put into a sulfuric acid solution containing transition metal ions for immersion, and the immersion time is 10 hours. Mixture with Ni 2+ The weight ratio of sulfuric acid solution is 1:20, figure 1 It is the IR spectrogram of the composite type solid superacid catalyst containing rare earth of the present invention, and the character of gained catalyst and product yield are ...

technical field

[0001] The present invention relates to a kind of composite solid superacid catalyst and preparation method thereof, more specifically relate to a kind of modified ZrO containing sulfate ion 2 Supported solid superacid catalyst and its preparation method. Background technique

[0002] A solid superacid is a solid acid with a stronger acidity than 100% sulfuric acid, expressed by the Hammett acidity function, the H of 100% sulfuric acid 0 =-11.93, while the H of the solid superacid 0 <-11.93. Compared with traditional catalysts, solid superacids have the following characteristics: (1) high catalytic efficiency, less dosage, less side reactions, and less by-products; (2) can be used at high temperatures, reusable, and the separation of catalysts and products is simple ; (3) non-corrosive, not polluting the environment; (4) the preparation method is simple and can be prepared by general metal salts. Due to the above advantages, the research and applicatio...

Examples

preparation example Construction

[0017] The preparation method of above-mentioned composite solid superacid catalyst comprises the following steps:

[0018] a. Under ice-water bath conditions, the titanium tetrachloride aqueous solution with a concentration of 1 to 5wt% and the zirconium oxychloride aqueous solution with a concentration of 1 to 5wt% are mixed, the weight ratio of the titanium tetrachloride aqueous solution to the zirconium oxychloride aqueous solution 1:0.5~2, add ethanol as a dispersant, then add ammonia water and stir to make the pH value of the mixed solution in the range of 9~10, generate zirconium hydroxide and titanium hydroxide precipitation, add 0.1~0.5mol / L nitric acid solution to generate the sol of zirconium hydroxide and titanium hydroxide;

[0019] b. Filter and wash the sol until the pH of the filtrate is 6.9-7.1 without Cl - ions, followed by drying to obtain ZrO 2 and TiO 2 mixed precursor oxides;

[0020] c. Mix the above-mentioned mixed precursor oxide with aluminum hali...

Embodiment 1

[0028] Under the condition of ice-water bath, the concentration of 1wt% TiCl 4 The aqueous solution and the zirconium oxychloride aqueous solution with a concentration of 1 wt% are mixed according to the ratio of 1:0.5, and ethanol is added as a dispersant, and the volume ratio of the mixed liquid to ethanol is 1:5. Use ammonia water to adjust the pH value of the solution to the range of 9-10, and stir when adding the ammonia water to form zirconium hydroxide and titanium hydroxide precipitates. Then add 0.1mol / L nitric acid solution to the precipitate to generate zirconium hydroxide and titanium hydroxide sol, and the relative ratio of the precipitate to the nitric acid solution is 1:0.1. The sol was filtered and washed until the filtrate pH was 7 and Cl-free - , and then dried to obtain a mixed precursor oxide. The mixture of mixed precursor oxide and aluminum fluoride powder was ground to 3 ) 2 Soluble in 0.5mol / L H 2 SO 4 A sulfuric acid solution of 0.1mol / L nickel ni...

Embodiment 2

[0032] Catalyst is prepared by the method of embodiment 1, difference is that concentration is 1wt% TiCl 4 The aqueous solution and the zirconium oxychloride aqueous solution with a concentration of 1wt% are mixed according to the ratio of 1:2, and the AlF in the mixture of the precursor oxide and the aluminum fluoride powder is mixed. 3 The content is 3wt%, and the calcination temperature of the catalyst is 700°C. The impregnating solution is a certain amount of Ni(NO 3 ) 2 Soluble in 0.5mol / L H 2 SO 4 A sulfuric acid solution of 0.5mol / L nickel nitrate was made in the medium. The ground mixture is put into a sulfuric acid solution containing transition metal ions for immersion, and the immersion time is 10 hours. Mixture with Ni 2+ The weight ratio of sulfuric acid solution is 1:20, figure 1 It is the IR spectrogram of the composite type solid superacid catalyst containing rare earth of the present invention, and the character of gained catalyst and product yield are ...

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