Recovery method for rhodium from deactivated catalyst used in formylation of propenyl hydrogen

A propylene hydroformylation catalyst and oxidation treatment technology, applied in the rhodium phosphine complex RhCl2 field, can solve the problems of cumbersome process steps, unfavorable industrial promotion and application, etc., and achieve simple process, reduce high environmental pollution treatment process, The effect of little pollution

Active Publication Date: 2014-01-15
CHINA PETROLEUM & CHEM CORP +1
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  • Abstract
  • Description
  • Claims
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Problems solved by technology

However, the process steps of this method are too cumbersome,

Method used

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  • Recovery method for rhodium from deactivated catalyst used in formylation of propenyl hydrogen

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Embodiment 1

[0041] The used catalyst waste liquid is the deactivated catalyst in the process of producing butyraldehyde by the hydroformylation reaction of propylene, carbon monoxide and hydrogen, and its activity is reduced to below 30% of the fresh catalyst. The catalyst waste liquid was concentrated on a scraped thin film evaporation device. The concentration of rhodium in the gained concentrated waste liquid is 4900ppm.

[0042] Under normal pressure, add 8.45 g of the above-mentioned concentrated catalyst waste liquid and 50 ml of absolute ethanol into a 500 ml three-neck flask, stir to fully dissolve them, then add 50 ml of 1mol / L nitric acid ethanol solution, and mix well. Add 2ml of hydrogen peroxide to the flask, slowly heat to 70°C, and react for 5h. Then 50 ml of an ethanol solution containing 1.92 g of NaOH was added. Feed nitrogen into the reaction system, the flow rate of nitrogen is 100ml / min, after staying for 30min, add 50ml ethanol solution containing 2.50g triphenylph...

Embodiment 2

[0044] Under normal pressure, in the 500ml there-necked flask, add the concentrated catalyst waste liquid 9.04g and 50ml dehydrated alcohol with embodiment 1, stir to make it fully dissolve, then add the ethanol solution of 50ml 1mol / L nitric acid, and mix homogeneously. Air is introduced into the mixed solution in the flask, and the air is bubbled through the bottom of the liquid through an immersion tube, so that the oxygen and the catalyst waste liquid can fully contact and react, and the flow rate of the air is 100ml / min. Stir and slowly raise the temperature to 90°C, stop feeding air after 24 hours of reaction. Then 50 ml of ethanol solution containing 1.97 g of NaOH was added and the temperature was lowered to 80°C. Feed nitrogen gas into the reaction system, the flow rate of nitrogen gas is 100ml / min, after staying for 30min, add 50ml ethanol solution containing 2.48g triphenylphosphine, 20ml ethanol solution of 1M hydrochloric acid, 10ml 37% formaldehyde aqueous soluti...

Embodiment 3

[0046] Under normal pressure, in 500ml there-necked flask, add 8.55g of concentrated catalyst waste liquid and 50ml dehydrated ethanol in the same embodiment 1, stir to make it fully dissolve, then add the ethanol solution of 50ml 1mol / L hydrochloric acid, and mix homogeneously. Air is introduced into the mixed solution in the flask, and the air is bubbled through the bottom of the liquid through an immersion tube, so that the oxygen and the catalyst waste liquid can fully contact and react, and the flow rate of the air is 100ml / min. Stir and slowly raise the temperature to 90°C, stop feeding air after 24 hours of reaction. Then 50 ml of ethanol solution containing 2.79 g of KOH was added and the temperature was lowered to 80°C. Feed nitrogen into the reaction system, the flow rate of nitrogen is 150ml / min, after staying for 30min, add 50ml ethanol solution containing 2.48g triphenylphosphine, 20ml ethanol solution of 1M hydrochloric acid, 10ml 37% formaldehyde aqueous solutio...

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Abstract

The invention discloses a recovery method for rhodium from a deactivated catalyst used in formylation of propenyl hydrogen. The method realizes high efficiency recovery of rhodium by directly preparing RhCl(CO)(TPP)2 with a rhodium phosphine complex-containing waste liquid of a catalyst used in formylation of propenyl hydrogen as a starting raw material. The method comprises the following steps: subjecting the catalyst waste liquid to oxidation treatment under an acidic condition so as to break a rhodium cluster; synthesizing rhodium triphenylphosphine carbonyl chloride in a nitrogen atmosphere; and carrying out filtering, washing and drying so as to obtain rhodium. According to the invention, process conditions are mild, equipment used in the method is simple, burning or high temperature treatment is not needed, and little pollution is posed to the environment; the method has the advantages of high yield, simple process and mild conditions, substantially simplifies process flow from catalyst waste liquid to catalyst and reduces treating procedures generating high environmental pollution, e.g., burning, so the method has considerable economic benefits and social benefits.

Description

technical field [0001] The invention relates to a method for recovering rhodium from deactivated rhodium catalysts, specifically using the deactivated rhodium-containing catalyst waste liquid of propylene hydroformylation reaction as raw material to directly prepare rhodium-phosphine complex RhCl(CO) with catalytic activity (TPP) 2 , so that rhodium can be efficiently recovered. Background technique [0002] The hydroformylation process of reacting olefins with hydrogen and carbon monoxide to form aldehyde products using a rhodium-tertiary organophosphorus complex as a catalyst is well known in the art. In the long-term continuous industrial production process, rhodium-phosphine complex catalysts are often deactivated by various high-boiling by-products and impurities carried by raw materials during the reaction process. Even if there is basically no impurity entrained in the raw material, the catalyst will generate inactive rhodium cluster complexes under the comprehensiv...

Claims

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Application Information

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IPC IPC(8): C07F19/00C07F15/00
Inventor 李彤吕顺丰王世亮刘博秦燕璜
Owner CHINA PETROLEUM & CHEM CORP
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