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Nickel-additive-aluminum oxide-zirconium oxide catalyst, preparation method and application

A catalyst, alumina technology, applied in the direction of metal/metal oxide/metal hydroxide catalyst, physical/chemical process catalyst, hydrogenation preparation, etc., can solve the problem of catalyst activity decline and other problems, and achieve improved hydrogenation activity and activity. , the effect of high dispersion

Active Publication Date: 2017-06-20
SHANXI UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

These catalysts all use alumina as a carrier, and the strong L acid sites on the surface of alumina have a strong adsorption effect on C=O in the reaction material, and then make the reaction species condense and dehydrogenate each other to form carbon deposits, which will lead to a significant increase in catalyst activity. decline

Method used

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  • Nickel-additive-aluminum oxide-zirconium oxide catalyst, preparation method and application
  • Nickel-additive-aluminum oxide-zirconium oxide catalyst, preparation method and application

Examples

Experimental program
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Effect test

Embodiment 1

[0031] (1) Weigh 190g of sodium metaaluminate, add deionized water to prepare a 500mL aqueous solution; weigh 4.5g polyethylene glycol and 90g of aluminum chloride, add deionized water to prepare a 500mL solution. The above two solutions were co-currently mixed at 50°C to form a gel, and hydrochloric acid was added to adjust the pH of the system to 6. (2) Take 40 g of zirconium oxynitrate, add deionized water, and prepare a 500 mL aqueous solution, add it to the material in step (1) at 50° C. under agitation, add sodium carbonate to adjust the pH value to 7, and let it stand for aging for 3 hours. Filter, wash with water 3 times, replace with ethanol 3 times, and dry at 100°C for 12 hours to obtain zirconium-containing dry rubber powder. (3) Take 100g of dry rubber powder, weigh 90g of nickel nitrate and 3g of copper nitrate hexahydrate, and mix them evenly with the dry rubber powder. (4) Weigh 0.7 g of formic acid, add 17 g of deionized water to dilute to obtain a dilute aci...

Embodiment 2

[0034](1) Weigh 200g of potassium metaaluminate, add deionized water to make a 500mL solution; weigh 11g of sucrose and 110g of aluminum sulfate, add deionized water to make a 500mL solution. The above two solutions were co-currently mixed at 75°C to form a gel, and sulfuric acid was added to adjust the pH of the system to 7. (2) Take 50g of zirconium oxychloride, add deionized water, and prepare 500mL of aqueous solution, add it to the material in step (1) at 75°C with stirring, add ammonium carbonate to adjust the pH value to 9, and let it stand for aging for 5h , filtered, washed 5 times with water, replaced with ethanol 5 times, and dried at 150°C for 3 hours to obtain zirconium-containing dry rubber powder. (3) Take 100g of dry rubber powder, weigh 100g of nickel nitrate and 5g of copper nitrate, and mix evenly with the dry rubber powder. (4) Weigh 1.5 g of glacial acetic acid, add 20 g of deionized water to dilute to obtain a dilute acid solution, add the dilute acid so...

Embodiment 3

[0037] (1) Weigh 190g of sodium metaaluminate, add deionized water to make a 500mL solution; weigh 8g of polyvinylpyrrolidone and 100g of aluminum nitrate, add deionized water to make a 500mL solution. The above two solutions were co-currently mixed at 60°C to form a gel, and nitric acid was added to adjust the pH of the system to 7.5. (2) Take 50g of zirconium oxynitrate, add deionized water, and prepare 500mL of aqueous solution, add it to the material in step (1) at 60°C under stirring, add sodium hydroxide to adjust the pH value to 8, and let it stand for aging for 4h , filtered, washed 3 times with water, replaced with ethanol 4 times, and dried at 120°C for 8 hours to obtain dry rubber powder containing zirconium. (3) Take 100g of dry rubber powder, weigh 150g of nickel nitrate and 8g of cerium nitrate, and mix evenly with the dry rubber powder. (4) Weigh 2.5 g of citric acid, add 22 g of deionized water to dilute to obtain a dilute acid solution, add the dilute acid so...

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Abstract

The invention relates to a nickel-additive-aluminum oxide-zirconium oxide catalyst which comprises aluminum oxide, zirconium oxide, nickel and additive at mass ratio of 100:(10.5-18.8): (12-21.3):(0.5-1.8). The pore volume of the catalyst is 0.4mL / g-0.6mL / g; the specific surface area is 120m<2> / g-180m<2> / g; the pore with the pore diameter within 30nm-45nm is 25%-35% of the total pore volume fraction; the pore with the pore diameter within 7nm-12.5nm is 20%-25% of the total pore volume fraction. The nickel-additive-aluminum oxide-zirconium oxide catalyst has the advantages of high stability and long service life.

Description

technical field [0001] The invention relates to a nickel-promoter-alumina-zirconia catalyst as well as a preparation method and application. Background technique [0002] Synthesize 1,4-butynediol with formaldehyde and acetylene as raw materials, and finally obtain 1,4-butanediol product after hydrogenation. The chemical reactions involved in this process are not only the process of hydrogenation of C≡C in 1,4-butynediol to obtain 1,4-butanediol, but also unsaturated by-products, such as 1,4-butanediol Chemical reaction for further hydrogenation conversion of enediol, 4-hydroxybutyraldehyde and other aldehyde species. Usually a fixed bed reactor is used, with supported nickel as the hydrogenation catalyst. [0003] US patents US 3950441 and US 3759845 disclose silicon-containing γ-Al 2 o 3 Support Ni-Cu-Mn catalyst. Chinese patent CN 1081174A reports the Al 2 o 3 The supported nickel catalyst is used in fixed bed high pressure hydrogenation reaction. These catalysts ...

Claims

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Application Information

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IPC IPC(8): B01J23/755B01J23/83C07C29/17C07C31/20
CPCC07C29/172B01J23/755B01J23/83B01J35/635B01J35/633B01J35/647B01J35/615C07C31/207
Inventor 赵永祥李海涛张鸿喜张因
Owner SHANXI UNIV
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