Ruthenium Catalyst CO2 Hydrogenation Formamide Synthesis

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Solution Overview

Problem

Current methods for synthesizing formamide compounds using carbon dioxide are inefficient, require harsh conditions, and produce by-products, necessitating a more environmentally friendly and cost-effective process with improved substrate applicability and catalyst convenience.

Innovation Solution

A method involving the reaction of an amine compound with carbon dioxide and hydrogen using a pincer ruthenium catalyst, which forms formamide compounds under moderate conditions with high efficiency and low energy consumption, producing only water as a by-product.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If supercritical carbon dioxide method is used with tetra (trimethylphosphine) dichloro ruthenium complex catalyst, then transformation efficiency is improved (TON reached 4.2 million), but total pressure reaches 210 atmospheric pressure leading to high energy consumption and harsh equipment requirements

Engineering Contradiction:
Improvetransformation efficiencyVSAvoidenergy consumption
Core Design Contradiction:
ProductivityVSUse of energy by moving object

Solution Approach 1:

The patent changes the pressure parameter from 210 atm to 30-50 atm, and temperature from supercritical conditions to 80-150°C, achieving high transformation efficiency while reducing energy consumption and equipment requirements

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent uses a readily available ruthenium complex catalyst that can be prepared from common precursors, replacing the expensive and difficult-to-handle tetra (trimethylphosphine) dichloro ruthenium complex, making the process more economically viable

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

2Productivity

If supercritical carbon dioxide method is used, then transformation efficiency is improved, but substrate applicability deteriorates due to different solubility of amine in supercritical carbon dioxide

Engineering Contradiction:
Improvetransformation efficiencyVSAvoidsubstrate applicability
Core Design Contradiction:
ProductivityVSAdaptability or versatility

Solution Approach 1:

The patent introduces a solvent as an intermediary medium to dissolve both the catalyst and various amine substrates, enabling the reaction to proceed under mild conditions with broad substrate scope including primary, secondary, and tertiary amines

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The catalytic system developed is universally applicable to multiple types of amine substrates (primary, secondary, tertiary) and different amine compounds, achieving both high efficiency and broad substrate applicability

Inventive Principle:
Principle #6Universality (Multi-functionality)

3Ease of manufacture

If polysilicate reagent is used to reduce CO2 and react with primary amine, then formamide compounds can be prepared, but equivalent amounts of expensive silicon reagent are required and over reduction occurs leading to poor reaction selectivity

Engineering Contradiction:
Improvesynthesis capabilityVSAvoidby-product pollution
Core Design Contradiction:
Ease of manufactureVSObject-generated harmful factors

Solution Approach 1:

The patent converts the harmful greenhouse gas CO2 into a useful chemical feedstock for formamide synthesis, while using a catalytic amount of ruthenium complex instead of stoichiometric silicon reagent, eliminating over-reduction by-products and achieving high selectivity

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

Solution Approach 2:

The patent replaces the stoichiometric polysilicate reduction method with a catalytic hydrogenation system using H2 gas and ruthenium complex catalyst, achieving cleaner reaction with water as the only by-product

Inventive Principle:
Principle #28Mechanics substitution (Replace mechanical system)

4Productivity

If conventional formic acid method or methyl formate method is used, then formamide production can be achieved, but environmental friendliness deteriorates due to non-renewable raw materials and by-product generation

Engineering Contradiction:
Improveproduction capabilityVSAvoidenvironmental impact
Core Design Contradiction:
ProductivityVSObject-affected harmful factors

Solution Approach 1:

The patent converts the harmful greenhouse gas CO2 into a valuable chemical feedstock for formamide production, replacing non-renewable raw materials with renewable CO2 and H2, achieving both productivity and environmental sustainability with water as the only by-product

Inventive Principle:
Principle #22Blessing in disguise (Convert harm into benefit)

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

This method achieves high transformation efficiency and catalyst stability, reducing production costs and environmental impact, with the ability to recycle the catalyst multiple times, thus enhancing industrial scalability and sustainability.

Implementation Method 1

reacting an amine compound of formula I with carbon dioxide and hydrogen under the action of catalyst III to form a formamide compound of formula II

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

formic acid obtained by hydrogen reduction of CO2 reacts with dimethylamine

Methodology Applied
Scientific EffectHydrogen reduction: Reduction

Data Source

PatentEP3260441B1Method for preparing formamide compound
Publication Date: 2021.03.03 SHANGHAI GREENCARBON HI TECH CO LTD
  • EP3260441B1 patent drawingFigure 1
  • EP3260441B1 patent drawing
  • EP3260441B1 patent drawing

AI summary

Disclosed is a method for preparing a formamide compound, the method uses carbon dioxide, hydrogen and an amine compound as raw materials and a transition metal complex as a catalyst, and the reaction is carried out in an organic solvent or in the absence of a solvent to form a formamide compound. The method of the present invention is an effective method of chemical utilization of carbon dioxide, which has the advantages of high reaction efficiency, a good selectivity, mild conditions, economic and environmental protection, being simple and convenient to operate and the like, and has a good popularization and application prospect.