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Process for preparing Cu-Zn-Al vapor hydroformylation catalyst and products therefrom

A hydrogenation catalyst, copper-zinc-aluminum technology, applied in chemical instruments and methods, metal/metal oxide/metal hydroxide catalysts, physical/chemical process catalysts, etc., can solve the problem of poor selectivity and stability, and low mechanical strength , poor product selectivity and other problems, to achieve the effect of inhibiting esterification and etherification side reactions, improving crystallization state, and improving selectivity

Active Publication Date: 2006-12-27
PETROCHINA CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] The purpose of the present invention is to solve the complex preparation process of the aldehyde hydrogenation catalyst in the above-mentioned prior art, poor repeatability, uneven grain size of the catalyst obtained, low dispersion of active metal copper, low mechanical strength, and poor product selectivity. Poor, especially when the reaction temperature is increased by increasing the reaction speed and thermal energy efficiency, the problems of poor activity, poor selectivity and poor stability provide a method for preparing a copper-zinc-aluminum gas-phase aldehyde hydrogenation catalyst and its product

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0029] Catalyst preparation method of the present invention is as follows:

[0030] 117g copper nitrate and 171g zinc nitrate are made into 1200ml of copper and zinc mixed solution; Sodium solution, and flow into a neutralization tank with heat preservation and stirring for neutralization and aging, control the neutralization temperature at about 80°C, adjust the pH value to 7.0-8.0 through sodium carbonate solution, and then mix the copper and zinc mixed solution with 100% by weight The sodium carbonate solution with a content of 15.7% was added to the same neutralization tank concurrently, neutralized and aged under stirring, washed four times with deionized water at 40-50°C, and after drying the obtained filter cake, put it at 360 Calcined at ~400°C for 4-5 hours, and then added 2% of the total mass of the obtained material into graphite pellets to form catalyst sample 1.

[0031] In the product, copper oxide is 38.3%, zinc oxide is 58.1%, aluminum oxide is 1.6%, graphite ...

Embodiment 2

[0033] 117g copper nitrate and 202g zinc nitrate are made into 1200ml of copper and zinc mixed solution; The sodium solution is added into a neutralization tank with heat preservation and stirring for neutralization and aging, and the neutralization temperature is controlled at about 80°C, and the pH value is 7.0 to 8.0, and then the mixed solution of copper and zinc is mixed with 15.7% by weight of carbonic acid Add the sodium solution into the same neutralization tank in parallel, neutralize and age under stirring, wash four times with deionized water at 40-50°C, dry the obtained filter cake, and roast at 360-400°C for 4- After 5 hours, 2% of the total mass of the obtained material was added into a graphite tablet to form a catalyst sample 2.

[0034] In the product, copper oxide is 34.2%, zinc oxide is 62.3%, and aluminum oxide is 1.4%.

Embodiment 3

[0036] 117g copper nitrate and 218g zinc nitrate are made into 1200ml of copper and zinc mixed solution; The sodium solution is added into a neutralization tank with heat preservation and stirring for neutralization and aging, and the neutralization temperature is controlled at about 80°C, and the pH value is 7.0 to 8.0, and then the mixed solution of copper and zinc is mixed with 15.7% by weight of carbonic acid Add the sodium solution into the same neutralization tank in parallel, neutralize and age under stirring, wash four times with deionized water at 40-50°C, dry the obtained filter cake, and roast at 360-400°C for 4- After 5 hours, 2% of the total mass of the obtained material was added to form a graphite tablet to obtain catalyst sample 3. The neutralization reaction includes primary neutralization reaction and second neutralization reaction.

[0037] In the product, copper oxide is 31.8%, zinc oxide is 64.1%, and aluminum oxide is 2.1%.

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Abstract

The invention belongs to catalyst technique field, concretely relates to a preparation method of catalyst for copper-zinc-aluminum gas phase aldehyde hydrogenation and product thereof, which solves the problems in existing technique that the preparation process of aldehyde hydrogenation catalyst is complex, repeatability is bad, catalyst crystal-size is heterogeneous, dispersion degree of active copper is not high, mechanical strength is small, selectivity to product is bad, especially when rising reactive temperature to enhancing reactive speed and heat energy efficiency, activity, selectivity and stability are bad. The method modifies the intermittent feeding mode to continuous feeding mode by step continuous coprecipitation method, specific surface and pore volume of catalyst is large, dispersion degree of active metal is high, catalytic activity is good, selective and stability have more improvement, and side reaction of esterification and etherification is reduced.

Description

technical field [0001] The invention belongs to the technical field of catalysts, and in particular relates to a preparation method of a copper-zinc-aluminum gas-phase aldehyde hydrogenation catalyst and a product thereof. Background technique [0002] Gas-phase aldehyde hydrogenation to produce alcohol is a relatively mature process at present. The catalyst is mainly a mixture of copper oxide-zinc oxide-alumina or its improved system. Due to different catalyst preparation methods or treatment methods, the performance of the obtained catalyst varies greatly. Using the grinding method, copper and zinc oxide are mechanically mixed, and the interaction is weak, and copper is easy to sinter and aggregate during use, resulting in the rapid deactivation of the catalyst. Therefore, the preferred method for preparing copper oxide-zinc oxide catalyst is co-precipitation method, that is, adding a precipitant to co-precipitate the insoluble salt of copper and zinc in the aqueous soluti...

Claims

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Application Information

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IPC IPC(8): B01J23/80B01J21/04B01J21/18C07B35/02
Inventor 张志华王刚迟克彬张全国张文成谭明伟王路海李淑杰彭文敏吴显军丛丽茹
Owner PETROCHINA CO LTD
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