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Preparation method and application of oxidization modified carbon nanotube-loaded double-metal copper and magnesium co-doped nickel-based multi-metal catalyst

A technology of multi-metal catalysts and carbon nanotubes, which is applied in the direction of catalyst activation/preparation, preparation of organic compounds, physical/chemical process catalysts, etc., can solve problems such as insignificant economic benefits, low recycling rate, and easy deactivation. Achieve high conversion rate and total product selectivity, inhibit excessive hydrogenation, and promote synergistic effect

Active Publication Date: 2017-12-15
XIANGTAN UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the recovery rate of the catalyst is low, and a large amount of alkali is required to suppress the formation of by-products
[0009] In summary, the above catalysts for the hydrogenation of adiponitrile all have problems to a certain extent, or are difficult to separate and lead to recycling difficulties; or use a large amount of precious metals As an active component, it causes resource waste and high cost; or the activity of the catalyst is not very high; or the reaction conditions are very demanding
For example, Raney type catalysts, metal rhodium-based catalysts and other precious metal catalysts have high cost, low recycling rate, and are easy to deactivate. At the same time, due to the large amount of alkaline water (ammonia) used, the equipment is severely corroded, the amount of wastewater treatment is large, and the reaction pressure is very high. High, further increasing the production cost, the economic benefit is not significant; another example is the amorphous alloy catalyst, the hydrogen consumption in the gas phase method is extremely high, and the reaction temperature is high, resulting in higher production costs and more complicated processes

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0034] First weigh 4g of multi-walled carbon nanotubes and place them in a 350mL round bottom flask, add a corresponding volume of nitric acid mixed acid with sulfuric acid (V (nitric acid) / V (sulfuric acid) = 3) at a liquid-solid ratio of 50 mL / g. In a constant temperature oil bath at 100° C., condense and reflux at a stirring rate of 750 rpm for 10 hours. The carbon nanotubes after the reflux treatment were repeatedly washed 10 times with deionized water until neutral. The washed carbon tubes were put into a vacuum drying oven and dried at a constant temperature of 110° C. for 3 hours. Take 3g of the above-mentioned treated carbon nanotubes and place them in a 150mL round-bottomed flask, and prepare hydrogen peroxide H with a concentration of 1.5mol / L. 2 o 2 solution, add a corresponding volume of H at a liquid-solid ratio of 25 mL / g 2 o 2 , reflux at 40°C for 12 hours. The carbon nanotubes (O-MWCNT) after the oxidation treatment were washed 10 times with a large amount...

Embodiment 2

[0037] Weigh 0.55 g of the oxidation-modified carbon nanotube-supported nickel-based multimetal catalyst (MgO-Cu-Ni / O-MWCNT) catalyst obtained in Example 1 and place it in a 100 mL lining of a high-temperature reactor, add 25 mL of absolute ethanol, Put 2.5 grams of adiponitrile into the magnet, seal the autoclave, replace the air in the autoclave with nitrogen for 4 times, evacuate the autoclave to vacuum with a vacuum pump, and then place the autoclave in an oil bath. After rising to the set reaction temperature of 55°C, hydrogen was introduced to pressurize to 2 MPa, the magnetic stirring was started, the stirring rate was 750rpm, and the reaction timing started. After reacting for 6 hours, the reaction mixture was filtered, and the contents of each substance in the filtrate The content was analyzed by gas chromatography. The conversion rate of adiponitrile was 97.85%, the selectivity of 6-aminocapronitrile was 60.11%, the selectivity of hexamethylenediamine was 32.31%, and...

Embodiment 3

[0039] Weigh 0.55 g of the oxidation-modified carbon nanotube-supported nickel-based multimetal catalyst (MgO-Cu-Ni / O-MWCNT) catalyst obtained in Example 1 and place it in a 100 mL lining of a high-temperature reactor, add 25 mL of absolute ethanol, Put 2.5 grams of adiponitrile into the magnet, seal the autoclave, replace the air in the autoclave with nitrogen for 4 times, evacuate the autoclave to vacuum with a vacuum pump, and then place the autoclave in an oil bath. After rising to the set reaction temperature of 65°C, hydrogen was introduced to pressurize to 2 MPa, the magnetic stirring was started, the stirring rate was 750rpm, and the reaction timing started. After 6 hours of reaction, the reaction mixture was filtered, and the contents of each substance in the filtrate were The content was analyzed by gas chromatography. The conversion rate of adiponitrile was 100%, the selectivity of 6-aminocapronitrile was 20.31%, the selectivity of hexamethylenediamine was 62.98%, a...

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Abstract

The invention discloses a preparation method and application of an oxidization modified carbon nanotube-loaded double-metal copper and magnesium co-doped nickel-based multi-metal catalyst. A multi-wall carbon nanotube loaded multi-metal nickel-based catalyst subjected to hydrogen peroxide oxidization is utilized and Cu is introduced so that the reduction energy of a Ni precursor can be effectively reduced and the dispersion of Ni nanoparticles on the surface of the carbon nanotube is accelerated; meanwhile, more Ni<0+> can be formed under the synergistic effect of Cu and Ni. Mg is introduced so that a large quantity of alkaline sites are provided for the surface of the catalyst; meanwhile, a NiO-MgO co-solution is formed so that excessive hydrogenation of reactants is easy to inhibit and excessive byproducts are not formed. Oxidization treatment of the carbon nanotube can be used for further accelerating a strong mutual effect of the carbon tube and active components, so that the hydrogenation activity of the catalyst is greatly improved; the catalyst is used for adiponitrile hydrogenation reaction and relatively high conversion ratio and total selectivity of products can be obtained.

Description

technical field [0001] The invention relates to the field of material preparation, in particular to a preparation method and application of an oxidation-modified carbon nanotube-supported bimetallic copper-magnesium co-doped nickel-based multimetal catalyst. Background technique [0002] The hydrogenation of adiponitrile mainly produces 6-aminocapronitrile and hexamethylenediamine, wherein 6-aminocapronitrile is a very critical step in the new process of butadiene / adiponitrile synthesis of caprolactam. In the butadiene / adiponitrile process, the research on the hydrocyanation process of butadiene based on nickel phosphine homogeneous catalyst in the first step has been relatively mature. DuPont was the first to use this method to produce adiponitrile. Through the two-step reaction of butadiene hydrogenation and then cyanation, the yield of adiponitrile can reach 95.6%. For the research on the process of cyclization of 6-aminocapronitrile to caprolactam in the third step, com...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): B01J23/78B01J23/755B01J37/12B01J37/18B01J37/34B01J37/08C07C209/48C07C211/12C07C253/30C07C255/24
CPCC07C209/48C07C253/30B01J23/78B01J37/08B01J37/12B01J37/18B01J37/343C07C211/12C07C255/24
Inventor 刘平乐吕扬熊伟郝芳罗和安
Owner XIANGTAN UNIV
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