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Method for recovering rhodium from rhodium-containing waste catalyst in hydroformylation through sulfur

A waste catalyst and rhodium sulfide technology, which is applied in the field of catalysis, can solve problems such as step lengthening, reduction of rhodium recovery process yield, difficulty in segmental control of ashing temperature, etc., and achieve the effect of reducing rhodium loss

Active Publication Date: 2013-11-06
CNOOC TIANJIN CHEM RES & DESIGN INST +1
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the addition of a large amount of additives makes the subsequent steps of the rhodium purification process longer, and the yield of the entire rhodium recovery process decreases
And the adding of additive solid salt is owing to being difficult to fully mix with pitch-like rhodium concentrated residue completely, makes its role in reducing the loss of rhodium limited
The temperature programming method disclosed in the patent ZL99106262.0 is to decompose and burn organic matter with different boiling point components in the rhodium-containing residue at different temperature ranges. Due to the complex composition of the rhodium-containing residue, it is difficult to control the ashing temperature in sections in operation
Moreover, due to the use of temperature programming, the heating rate is slow, and the time of ashing and incineration is relatively long; in addition, this invention needs to be strictly controlled between 200°C and 300°C, otherwise the loss of rhodium will increase, but the ignition point of many organic substances in the rhodium-containing residue is exactly In this range, it is difficult to control the ashing and incineration temperature when the organic matter is ignited in this temperature range, so it is difficult to avoid the loss of rhodium

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Put 201.2 grams of rhodium-containing catalyst waste liquid (0.0687% rhodium mass content) deactivated in the propylene hydroformylation industrial device into a 1-liter round bottom flask, add 2.2 grams of elemental sulfur, heat to 130 ° C under stirring, and keep for 1 Hour. After the reaction is completed, filter to obtain a rhodium-containing gray-black solid, add sodium bisulfate to mix, heat and melt in a muffle furnace, add water to dissolve the molten solid to obtain a rhodium-containing aqueous solution, and use ICP-OES to analyze the rhodium content of the solution. The rhodium recovery rate in this step was 85.6%. The filtrate treated with elemental sulfur was evaporated under reduced pressure to obtain 22.8 grams of rhodium-containing residue, heated to 500°C in a muffle furnace, kept for 2 hours, further heated to 800°C, kept for 2 hours to obtain rhodium-containing black metal powder, After hydrogen reduction, use sodium bisulfate to heat and melt in a mu...

Embodiment 2

[0032] Put 202.4 grams of rhodium-containing catalyst waste liquid deactivated in the propylene hydroformylation reaction industrial unit (mass content of rhodium 0.0687%, rhodium 0.1374 grams, 1.3353 mmol) into a 1-liter round bottom flask, add 21.4 grams of elemental sulfur, and stir Heat to 100°C for 3 hours. After the reaction is completed, filter to obtain a rhodium-containing gray-black solid, add sodium bisulfate to mix, heat and melt in a muffle furnace, add water to dissolve the molten solid to obtain a rhodium-containing aqueous solution, and use ICP-OES to analyze the rhodium content of the solution. The rhodium recovery rate in this step 90.2%. The filtrate was evaporated under reduced pressure to obtain 21.1 grams of rhodium-containing residue, heated to 500°C in a muffle furnace, kept for 3 hours, further heated to 1000°C, kept for 1 hour to obtain rhodium-containing black metal powder, hydrogen sulfate was used to reduce Sodium is heated and melted in a muffle ...

Embodiment 3

[0034] Put 201.5 grams of rhodium-containing catalyst waste liquid (0.0687% rhodium mass content) deactivated in the propylene hydroformylation reaction industrial device into a 1-liter round bottom flask, add 4.3 grams of elemental sulfur, heat to 150 ° C under stirring, and keep for 1 Hour. After the reaction is completed, filter to obtain a rhodium-containing gray-black solid, add sodium bisulfate to mix, heat and melt in a muffle furnace, add water to dissolve the molten solid to obtain a rhodium-containing aqueous solution, and use ICP-OES to analyze the rhodium content of the solution. The rhodium recovery rate in this step was 86.5%. The filtrate was evaporated under reduced pressure to obtain 20.7 grams of rhodium-containing residue, heated to 500°C in a muffle furnace, kept for 3 hours, further heated to 800°C, kept for 2 hours to obtain rhodium-containing black metal powder, washed with hydrochloric acid to remove impurity metals, After hydrogen reduction, use sodiu...

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Abstract

The invention provides a method for recovering rhodium from rhodium-containing waste catalyst in hydroformylation through sulfur. The method is characterized in that elemental sulfur is used for processing a rhodium-containing waste catalyst solution which is not concentrated, about 90% rhodium in the rhodium-containing waste catalyst solution is recovered in a polysulfide rhodium precipitation form, the remaining rhodium solution containing about 10% rhodium is concentrated and processed to obtain rhodium slag, the rhodium slag is burned in an electric furnace so as to enable most of rhodium in the rhodium-containing waste catalyst solution to be precipitated, and finally rhodium metal obtained in the two steps through processing is combined and processed to be made into a raw material hydrate rhodium chloride for preparing a rhodium phosphine complex catalyst.

Description

Technical field: [0001] The invention relates to the technical field of catalysis, and relates to a method for reclaiming rhodium from a rhodium-containing waste catalyst of olefin hydroformylation reaction, more precisely, a method for reclaiming rhodium from a rhodium-containing waste catalyst of hydroformylation reaction with sulfur, The rhodium contained therein can be recovered simply and efficiently. Background of the invention: [0002] Olefin hydroformylation is one of the most important reactions in the chemical industry for the production of aldehydes and alcohols, and rhodium-phosphine complex catalysts are the most commonly used catalysts for olefin hydroformylation. In industrial production operations, rhodium-phosphine complex catalysts are often deactivated due to the presence of various high-boiling by-products and impurities in the raw materials during the reaction. Because rhodium resources are scarce and expensive, it is extremely important in industry wh...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C22B11/00C22B7/00
CPCY02P10/20
Inventor 于海斌李晨蒋凌云郑书忠李继霞李俊郝婷婷
Owner CNOOC TIANJIN CHEM RES & DESIGN INST