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Preparation method of catalyst for synthesizing hexanediamine by carrying out hydrogenation on hexane dinitrile

An alloy catalyst and catalyst technology, applied in the field of petrochemical catalysis, can solve the problems of poor catalyst uniformity, small catalyst performance improvement, large catalyst dosage, etc., and achieve the effect of uniform distribution

Active Publication Date: 2014-08-27
CHINA TIANCHEN ENG +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

At present, the main problems of this catalyst are low activity and selectivity, large amount of catalyst, serious environmental pollution, etc. Therefore, it is necessary to develop new and more efficient catalyst materials to improve the yield of hexamethylenediamine products and achieve atom economy.
[0003] At present, there are mainly the following methods for modifying the Raney catalyst: one is to add a modifier to melt during the preparation of the parent alloy, and then crush and activate it, such as the amorphous prepared by Chinese invention patents 01134263.3, 02150722.8 and 201210212109.2 State alloy catalyst, its shortcoming is high temperature melting preparation alloy consumes a lot of energy; the second is that after the modifier is added in the preparation process, the catalyst is modified by means of ultrasonic treatment, such as Chinese invention patent 201310467071.8, etc., its shortcoming lies in the simple use The performance improvement of ultrasonic treatment catalyst is small; the third is to use the impregnation method to modify the prepared catalyst, such as Japanese patent 03249946A and Chinese invention patent 97102713.7, etc. The uniformity of the catalyst prepared by this method is poor

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0022] 1. Preparation of catalyst powder:

[0023] Using 500ml of 5wt% ammonia water as a complexing agent and 100ml of 5wt% nickel nitrate as raw materials, the mixed reaction produces a nickel-ammonia complex solution; under stirring conditions, 0.1wt% ferric nitrate solution is added at a speed of 1ml / min to form a mixed solution. The molar ratio of iron to nickel ions is 0.01:1; under stirring conditions, 60-80 mesh powder ground from porous aluminum is added as a carrier, and the mass ratio of porous aluminum powder to nickel is 0.5:1; the mixed solution is heated , Hydrothermal aging at 20°C for 1 hour, filtration and separation to obtain solid particles, and after drying and roasting, hydrogen gas is introduced for reduction at 0.1MPa and 300°C for 1 hour to obtain catalyst powder.

[0024] 2. Catalyst activation

[0025] 10g of the above catalyst powder was slowly added to the 0.2mol / l NaOH solution under ice-water bath and stirring conditions, wherein the mass ratio of the ...

Embodiment 2

[0027] 1. Preparation of catalyst powder:

[0028] Using 200ml of 7wt% ammonia water as a complexing agent and 100ml of 10wt% nickel nitrate as raw materials, the mixed reaction produces a nickel-ammonia complex solution; under stirring conditions, 0.5wt% ferric nitrate, chromium nitrate and bismuth nitrate solutions are mixed in a certain proportion Add at a speed of 2ml / min to form a mixed solution, in which the molar ratio of chromium, bismuth and iron ions is 0.5:0.5:1, and the ratio of their total moles to nickel ions is 0.05:1; under stirring conditions, add the The 60-80 mesh powder made from porous aluminum is used as the carrier, and the mass ratio of porous aluminum powder to nickel is 1:1; the mixed solution is heated, hydrothermally aged at 50°C for 1 hour, filtered and separated to obtain solid particles, which are dried and roasted , Hydrogen was introduced for reduction at 0.1MPa400°C for 4h to obtain catalyst powder.

[0029] 2. Catalyst activation

[0030] The abov...

Embodiment 3

[0032] 1. Preparation of catalyst powder:

[0033] Using 300ml of 10wt% ammonia water as a complexing agent and 100ml of 20wt% nickel nitrate as raw materials, the mixed reaction produces a nickel-ammonia complex solution; under stirring conditions, 2wt% of ferric nitrate and molybdenum nitrate are mixed in a certain proportion and then the solution is 3ml / min Add at a speed to form a mixed solution, where the molar ratio of molybdenum to iron ions is 3:1, and the ratio of their total moles to nickel ions is 0.1:1; under stirring conditions, add 60-80 mesh ground from porous aluminum The powder is used as a carrier, and the mass ratio of porous aluminum powder to nickel is 1.5:1; the mixed solution is heated, hydrothermally aged at 80℃ for 1h, filtered and separated to obtain solid particles, after drying and roasting, hydrogen gas is introduced at 0.1MPa 500℃ Reduce for 2h to obtain catalyst powder.

[0034] 2. Catalyst activation

[0035] The above catalyst powder was slowly adde...

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PUM

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Abstract

The invention discloses a preparation method of a catalyst for synthesizing hexanediamine by carrying out hydrogenation on hexane dinitrile. The catalyst is an amorphous state nickel alloy catalyst, and is prepared by the method comprising the steps of (1) preparation of catalyst powder: firstly, preparing ammonia water and nickel nitrate into nickel-ammonium complex solution, mixing the nickel-ammonium complex solution with modifying agent water solution, stirring, carrying out hydrothermal aging, filtering separation and drying calcination on the mixture, filling hydrogen, and reducing at high temperature to obtain the catalyst powder; (2) activation of the catalyst: slowly feeding the catalyst powder into NaOH solution, heating and stirring for a certain period of time under the condition of microwave; after the reaction is completed, removing the upper-layer alkali liquor, washing the product to be neutral with deionized water, and washing with absolute ethyl alcohol for later use. The activity of the obtained amorphous state nickel alloy catalyst is evaluated by the conventional reaction conditions. The catalyst is uniform in distribution of active components, and the conversion rate of the hexane dinitrile and the selectivity of the hexanediamine are higher.

Description

Technical field [0001] The invention belongs to the technical field of petrochemical catalysis, and in particular relates to a method for preparing a catalyst for the hydrogenation of adiponitrile to synthesize hexamethylene diamine, and specifically to a method for preparing an amorphous nickel alloy catalyst. Background technique [0002] Raney catalyst is a widely used reduction catalyst, mainly used in the catalytic hydrogenation of organic compounds. According to different metal active centers, Raney iron, Raney cobalt, Raney nickel, etc., among which Raney nickel catalysts with nickel as the active center are the most used. For example, hexamethylene diamine is used as a monomer for the production of nylon-66. Currently, it is mainly prepared with adiponitrile as a raw material, using Raney nickel catalyst, in a tank reactor or a fluidized bed reactor. At present, the main problems of this catalyst are low activity and selectivity, large amount of catalyst, serious environ...

Claims

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Application Information

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IPC IPC(8): B01J23/755B01J23/86B01J23/883B01J23/889C07C211/12C07C209/48
Inventor 耿玉侠杨克俭刘文杨琦武李树华屈阁
Owner CHINA TIANCHEN ENG
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