Method of regenerating metal oxide industrial catalysts for organic synthesis

FIELD: chemistry.

SUBSTANCE: invention relates to regeneration of spent metal-containing catalysts for organic synthesis. Described is a method of regenerating metal oxide industrial catalysts for organic synthesis, comprising a support with oxides of Cu and Bi or Cu, Ni and Cr, the method involving treatment of the spent catalyst with salicylalaniline solution in dimethyl formamide with concentration between 0.1 and 0.5 mol, filtration of the solution of the complex compound, which is adsorbed directly on the cleaned support which is silica gel or zeolite obtained after filtration, and the obtained adsorbent undergoes thermal decomposition on the surface of the support at temperature 150-200°C.

EFFECT: described catalyst regeneration method enables multiple regenerations, lowers power consumption of the regeneration process while simplifying the process and without aggressive and toxic media.

2 ex

 

The invention relates to the regeneration of spent metal oxide catalysts in organic synthesis, consisting of the oxides of copper, bismuth, Nickel, chromium and their ORGANOMETALLIC compounds, and can be used in the chemical industry (for example, methanol synthesis), oil refining (cracking), neutralization of exhaust gases industry and transport.

The known method of regeneration modificatore catalyst for the synthesis of butynediol from acetylene and formaldehyde, comprising calcining the spent catalyst at 400-800°C, then processing it with nitric acid to convert oxides of copper and bismuth in nitric acid salts used for preparation of fresh catalyst (patent 274094).

The disadvantage of this method is that the nodes and setup used to implement the method, complex and power-consuming, multistage and complex installations and process control, the use of aggressive acid solutions.

The prototype of the present invention is a method of regenerating spent catalyst hydrogenation, including the processing of 22-27%solution of nitric acid at elevated temperatures, drying and calcining the washed carrier at a temperature of 360-400°C, the carrier impregnated with the aqueous solution of metal salts followed by drying and roasting the ri 360-400°C (RF patent 2100071).

The disadvantages of this method is a slight degree of transition metal in the solution, the intensity and complexity of technological systems, the use of aggressive fluids.

The task of the invention to create a method for regenerating catalyst with a high yield of metal, the possibility of repeated regeneration, to reduce the energy intensity of the regeneration process with the simplicity of the technological scheme and the absence of corrosive and toxic environments.

This object is achieved in that the regeneration process of the industrial metal oxide catalysts in organic synthesis, representing the carrier with the metal oxide of Cu and Bi or Cu, Ni, Cr, and processing of spent catalyst spend solution salicylanilide in dimethylformamide to a concentration of from 0.1 to 0.5 mol, filtering the solution of complex compounds, the adsorption of complex compounds is carried out directly on the cleaned media, representing a silica gel, or zeolite obtained after filtration and carry out thermal decomposition of the obtained adsorbent on the surface of the carrier at a temperature of 150-200°C.

Technical result: a High degree of regeneration of the catalyst is achieved by transition metal ions in a solution of SA in DMF and education ORGANOMETALLIC complex compounds, thermal R is sloanie which at low temperatures can reduce the energy consumption of the process. High dispersion of the obtained metals allows to increase the output of the finished product, and the use of the solvent solution of SA in DMF to exclude aggressive solvents

The catalyst used in organic synthesis, is often a film of the metal oxide deposited on the surface of inert carrier (silica gel, zeolite). The first stage of the developed technology - dissolution of the catalyst solution of SA in DMF, and the metals of the oxides are converted into a solution in the form of complex ions. The second stage is filtering the solution of complex compounds. In the process of filtration from the solution removes the solvent (CA DMF) and again returns to the stage of dissolution of the catalyst solution of SA in DMF and purified carrier is used for the manufacture of the catalyst. The third phase adsorption complex compounds on purified media. The fourth stage thermal decomposition of complex compounds at a temperature of 150-200°C, resulting in highly dispersed metals.

Example 1, on the basis of Cu-Bi-catalyst.

In 60 ml DMF-SA with a concentration of 0.25 mol fit exhaust Cu-Bi catalyst mass 100, the Transition components of the metal phase of the catalyst is expressed by the dependence of the concentration of copper in solution of SA in DMF from time to time. The saturation state DOS is ikaetsya in 1 hour for ground and 3 hours for unground catalyst. The change in mass fraction of metals corresponds to the extraction of 83% copper and 76% of bismuth from Cu-Bi-catalyst. Then the carrier is silica gel impregnated with a solution of the complex compound in a mixture of CA in DMF to gain 12% and spend thermal decomposition of complex compounds on silica gel at a temperature of 180°C.

Example 2, on the basis of Cu-Ni-Cr-catalyst.

In 60 ml DMF-SA with a concentration of 0.25 mol fit exhaust Cu-Ni-Cr catalyst mass 100, the saturation State is reached in 1 hour for ground and 3 hours for unground catalyst. The change in mass fraction of metals corresponds to the extraction of 77% copper, 81% Nickel and 84% of chromium Cu-Ni-Cr-catalyst. Next, the silica gel is impregnated with a solution of the complex compound in a mixture of CA in DMF to gain 12% and spend thermal decomposition of complex compounds on the carrier at a temperature of 200°C.

The activity of the solution of SA in DMF) in respect of dissolution of oxides is not affected and it can be reused for the extraction of metals from new portions of the catalyst. The concentration of the working solution of SA in DMF) is in the range from 0.1 to 0.5 mol. When the regeneration of the Cu-Bi and Cu-Ni-Cr-catalyst, there is no need to allocate each metal individually. The outputs of the metals make up about 80% and the ratio of the metals in the mixture does not differ from them with the relationship in the original catalyst. The use of a solution of SA in DMF as solvent eliminates side recovery processes stronger oxidants and reduces the corrosion rate of product recovery.

Method of regeneration of industrial metal oxide catalysts in organic synthesis, representing the carrier with the metal oxide of Cu and Bi or Cu, Ni and Cr, wherein spend processing spent catalyst solution salicylanilide in dimethylformamide to a concentration of from 0.1 to 0.5 mol, filtering the solution of complex compounds, the adsorption of complex compounds is carried out directly on the cleaned media, representing a silica gel, or zeolite obtained after filtration and carry out thermal decomposition of the obtained adsorbent on the surface of the carrier at a temperature of 150-200°C.



 

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1 dwg, 3 tbl, 8 ex

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FIELD: industrial organic synthesis.

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1 cl, 1 tbl, 7 ex

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3 cl, 3 tbl, 1 ex

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3 cl, 5 tbl, 2 ex, 2 dwg

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9 cl, 27 ex, 2 tbl

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