Cobalt Catalyst Reductive Carbonylation Methyl Iodide Control

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Solution Overview

Problem

Current methanol carbonylation processes require iodide co-catalysts, which lead to the formation of undesirable byproducts like dimethyl ether and methyl iodide, making it difficult to separate the desired aldehyde and alcohol products and posing toxicity issues, while also being costly and inefficient in producing methyl iodide-free crude reductive carbonylation products.

Innovation Solution

A process using a catalyst complex composed of cobalt, iodide, and an onium cation or alkali metal cation, specifically formulated to minimize methyl iodide presence, facilitating the reductive carbonylation of low molecular weight alcohols to produce homologous aldehydes and alcohols with improved selectivity and reduced byproduct formation.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If iodide co-catalysts are used in methanol carbonylation processes, then reaction rate and conversion are optimized, but dimethyl ether and methyl iodide formation increases making separation difficult and causing toxicity issues

Engineering Contradiction:
Improvereaction rate and conversionVSAvoiddimethyl ether and methyl iodide formation
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The patent changes the chemical parameters of the catalyst system by replacing traditional iodide co-catalysts with a cobalt carbonyl catalyst system modified by phosphine ligands. This parameter change maintains optimized reaction rate and conversion while eliminating the formation of harmful byproducts like dimethyl ether and methyl iodide, thus resolving the contradiction between productivity and harmful factor generation.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent employs a cobalt-based catalyst system that is less expensive than traditional rhodium or iridium catalysts. The catalyst system uses phosphine ligands that can be easily adjusted and replaced, representing a cost-effective approach that maintains high productivity without generating toxic byproducts, thereby resolving the contradiction between economic efficiency and harmful factor reduction.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

2Productivity

If methyl iodide is used as co-catalyst, then reductive carbonylation reaction proceeds, but separation of aldehyde and alcohol products becomes difficult and toxicity increases

Engineering Contradiction:
Improvereductive carbonylation reactionVSAvoidtoxicity and separation difficulty
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The patent extracts and removes methyl iodide from the catalyst system by employing a cobalt carbonyl catalyst system modified with phosphine ligands. This extraction eliminates the source of methyl iodide formation, thereby eliminating toxicity concerns and simplifying product separation while maintaining reductive carbonylation reaction efficiency.

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

The patent introduces phosphine ligands as intermediary compounds that modify the cobalt carbonyl catalyst system. These ligands act as mediators that enable the reductive carbonylation reaction to proceed efficiently without requiring methyl iodide, thus preventing toxicity and separation difficulties while maintaining productivity.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Productivity

If traditional rhodium or iridium/ruthenium catalysts are used, then catalytic activity is high, but cost increases

Engineering Contradiction:
Improvecatalytic activityVSAvoidcost
Core Design Contradiction:
ProductivityVSEase of manufacture

Solution Approach 1:

The patent replaces expensive traditional catalysts (rhodium, iridium, ruthenium) with a cobalt-based catalyst system that is significantly cheaper. The cobalt carbonyl catalyst modified with phosphine ligands maintains high catalytic activity for reductive carbonylation reactions while dramatically reducing manufacturing costs, thus resolving the contradiction between productivity and ease of manufacture.

Inventive Principle:
Principle #27Cheap short-living objects (Disposable)

Solution Approach 2:

The patent changes the metallic component parameter of the catalyst system from precious metals (rhodium, iridium, ruthenium) to base metal cobalt. This parameter change, combined with phosphine ligand modification, maintains high catalytic activity while reducing cost, thereby resolving the contradiction between productivity and manufacturing ease.

Inventive Principle:
Principle #35Parameter changes

Applied Scientific Principles

This section explains which scientific principles are used to turn an abstract innovation direction into a practical engineering solution.

Function Achieved in This Case

The process achieves higher yields of desired aldehydes and alcohols with minimal methyl iodide in the crude product, enhancing product separation and reducing toxicity concerns, while offering a cost-effective alternative to traditional rhodium or iridium/ruthenium catalysts.

Implementation Method 1

The catalyst comprises a complex of cobalt, iodide, and an onium cation or an alkali metal cation... contacting hydrogen, carbon monoxide, and an alcohol having 1 to 3 carbon atoms in the presence of a catalyst to form the crude reductive carbonylation product

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentUS9718754B2Methyl-iodide-free carbonylation of an alcohol to its homologous aldehyde and/or alcohol
Publication Date: 2017.08.01 EASTMAN CHEM CO
  • US9718754B2 patent drawing
  • US9718754B2 patent drawing
  • US9718754B2 patent drawing

AI summary

Disclosed is a process for the reductive carbonylation of a low molecular weight alcohol to produce the homologous aldehyde and/or alcohol. The process includes conducting the reaction to produce the aldehyde in the presence of a single component catalyst complex composed of cobalt, an onium cation and iodide in a ratio of 1:2:4 without additional promoters. A ruthenium co-catalyst is used in the production of the homologous alcohol. The reductive carbonylation reaction does not require an additional iodide promoter and produces a crude reductive carbonylation product substantially free of methyl iodide.