Regeneration method of inactivated rhodium complex catalyst used for carbonyl reaction

A technology of carbonylation reaction and rhodium complexes, which is applied in the field of regeneration of deactivated or partially deactivated rhodium complex catalysts, to achieve the effects of improving catalyst activity, reducing dosage, and being easy to industrialize

Active Publication Date: 2013-03-06
CHINA PETROLEUM & CHEM CORP
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Problems solved by technology

[0007] The technical problem to be solved by the present invention is to provide a catalyst regeneration method that is easy to implement industrially for the deactivate

Method used

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  • Regeneration method of inactivated rhodium complex catalyst used for carbonyl reaction

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Example

[0032] Examples 1-8

[0033] In the butyraldehyde reaction liquid produced by the industrial butyraldehyde plant, the rhodium complex catalyst activity has been reduced from 100% to about 28% (compared with the fresh rhodium complex catalyst), and the rhodium content after removing part of the butyraldehyde is about 1000mg / kg , The content of triphenylphosphine is about 10%. Add 60g of the reaction solution containing partially deactivated catalyst to a 100ml reactor, purge the reactor with nitrogen, and then add acetylenic alcohols or esters containing 3-6 carbon atoms in different proportions as shown in Table 1. It reacts with carboxylic acid and regenerates under certain pressure and temperature. After the reaction is completed, a 10% triethanolamine aqueous solution is added to the reactor to neutralize the unreacted carboxylic acid or halide to generate a water-soluble salt.

[0034] After the neutralization reaction is completed, it settles into two obvious liquid phases a...

Example Embodiment

[0036] Example 5 was filled with hydrogen to 0.2 MPa, and other examples were all filled with nitrogen.

Example Embodiment

[0037] The carboxylic acid used in Example 8 was n-butyric acid, and the other examples all used acetic acid.

[0038] Table 1 Experimental conditions and catalyst activity evaluation table

[0039]

[0040] Note: The catalyst activity of fresh rhodium complex is 100%, and the catalyst activity of deactivated rhodium complex to be treated is 28%.

[0041] After testing, the reaction solution containing partially deactivated rhodium complex catalyst that has not been regenerated has a chlorine content of 29 mg / kg, and the chlorine content of the regenerated solution is 7 mg / kg. Therefore, compared with the prior art, the process method adopted by the present invention eliminates the poisoning caused by exogenous halide and carboxylic acid inhibitor in the regenerated reaction solution at the same time, and regenerates the reaction reagent (alkynes containing 3-6 carbon atoms). The amount of alcohol or ester) is low, the reaction conditions are mild, the process flow is simple, and th...

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Abstract

The invention belongs to the technical field of the catalyst regeneration, and particularly relates to a regeneration method of an inactivated rhodium complex catalyst used for a carbonyl reaction. The regeneration method of the inactivated rhodium complex catalyst comprises the steps of: firstly mixing a reaction liquid containing an inactivated rhodium complex catalyst with alkynol or ester containing 3-6 carbon atoms, and carboxylic acid, and carrying out the regeneration reaction in the existence of hydrogen or nitrogen at the reaction pressure of 0.1-1.0MPa; then adding an aqueous tertiary alkanol amine solution into the obtained reaction liquid, neutralizing unreacted carboxylic acid or halide to generate water soluble salt; then carrying out the settlement separation to obtain an organic phase containing a rhodium complex catalyst; and washing the organic phase with water to obtain a solution containing the rhodium complex catalyst, the catalytic activity of which is higher than the catalytic activity of the existing inactivated rhodium catalyst. The regeneration method of the inactivated rhodium complex catalyst solves the polymerization problem in the regeneration process of the alkynol or the ester containing 3-6 carbon atoms. The regeneration method of the inactivated rhodium complex catalyst has the advantages of low reagent dosage, mild reaction conditions, easiness in technological process, and high generated catalyst activity, and also has the advantage that the regeneration method of the inactivated rhodium complex can carry out online regeneration of the catalyst under the condition that the carbonyl reaction can be continuously carried out without any pauses.

Description

technical field [0001] The invention belongs to the technical field of catalyst regeneration, in particular to a method for regenerating a deactivated or partially deactivated rhodium complex catalyst used in a carbonylation reaction. Background technique [0002] The "OXO" reaction is the oxo synthesis reaction, also known as the hydroformyl reaction or hydroformylation reaction. In the low-pressure carbonylation process of aldehydes, the catalyst used in the reaction process is a rhodium-phosphine catalyst system. Using this catalyst, the reaction pressure is low and side reactions are few, which are well known in the art. However, as the continuous oxo reaction proceeds, the rhodium complex catalyst loses or partially deactivates even in the substantially absence of exogenous catalyst poisons. The comprehensive effect of reaction process conditions such as reaction temperature, reactant partial pressure, phosphine ligand / rhodium molar ratio, rhodium concentration, etc.,...

Claims

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Application Information

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IPC IPC(8): B01J31/40B01J31/24B01J38/62B01J38/52C07C45/50C07C47/02
CPCY02P20/584
Inventor 王申军菅秀君潘清刘淑芝何宗华马瑞杰
Owner CHINA PETROLEUM & CHEM CORP
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