Full Contact Cobalt Catalyst Nitrile Hydrogenation Selectivity

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Solution Overview

Problem

Current processes for hydrogenating nitriles to primary amines face challenges such as the formation of undesirable secondary and tertiary amines, catalyst deactivation due to water presence, and high energy costs associated with ammonia separation, particularly when using Raney cobalt or LiCoO2 catalysts.

Innovation Solution

A process involving the hydrogenation of nitriles in the presence of a full contact cobalt catalyst, with continuous or repeated addition of an alkali metal compound like lithium hydroxide, allowing for high yield and selectivity of primary amines without ammonia, under milder conditions and at lower pressures.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If ammonia is added to suppress formation of secondary and tertiary amines, then selectivity to primary amine is improved, but separation and recycling costs increase significantly

Engineering Contradiction:
Improveselectivity to primary amineVSAvoidseparation and recycling costs
Core Design Contradiction:
Manufacturing precisionVSLoss of energy

Solution Approach 1:

The invention changes the chemical parameter by substituting ammonia with alkali metal hydroxides (such as LiOH, NaOH, KOH) as the additive to suppress secondary and tertiary amine formation. This parameter change eliminates the need for ammonia separation and recycling while maintaining high selectivity to primary amines, thereby resolving the contradiction between selectivity improvement and energy loss reduction

Inventive Principle:
Principle #35Parameter changes

2Power

If Raney cobalt catalyst is used for hydrogenation, then catalytic activity is improved, but catalyst separation and recycling becomes difficult

Engineering Contradiction:
Improvecatalytic activityVSAvoidcatalyst separation and recycling
Core Design Contradiction:
PowerVSEase of operation

Solution Approach 1:

The invention employs supported cobalt catalysts with porous structures (such as cobalt on activated carbon, cobalt on alumina, or cobalt on silica) instead of Raney cobalt. These porous supported catalysts maintain high catalytic activity while allowing easy separation and recycling through filtration or decantation, thus resolving the contradiction between catalytic activity and ease of operation

Inventive Principle:
Principle #31Porous materials

Solution Approach 2:

The invention creates composite catalyst materials by supporting cobalt particles on inert carriers (activated carbon, alumina, silica). This composite structure combines the high activity of cobalt with the ease of handling and separation of the supported material, solving both the activity and separability requirements simultaneously

Inventive Principle:
Principle #40Composite materials

3Power

If LiCoO2 catalyst precursor is reduced with hydrogen, then catalytic activity is improved, but water causes catalyst deactivation

Engineering Contradiction:
Improvecatalytic activityVSAvoidcatalyst stability in presence of water
Core Design Contradiction:
PowerVSReliability

Solution Approach 1:

The invention uses alkali metal hydroxides (particularly lithium hydroxide) as additives that can be continuously supplied in small amounts to maintain catalyst activity. These hydroxides compensate for water-induced deactivation without requiring the catalyst to be completely water-resistant, allowing the system to maintain high activity even in the presence of water through continuous replenishment of the active species

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

4Stability of the object's composition

If up to 10% by weight lithium is bound in LiCoO2 catalyst, then catalyst structure is stabilized, but catalytic activity decreases due to lithium not reaching active zone

Engineering Contradiction:
Improvecatalyst structure stabilityVSAvoidcatalytic activity
Core Design Contradiction:
Stability of the object's compositionVSProductivity

Solution Approach 1:

The invention extracts excess lithium from the catalyst structure by using alkali metal hydroxides as additives during the hydrogenation process. The hydroxides provide lithium ions that are readily available in the reaction medium, allowing the catalyst to maintain optimal lithium content for structural stability while avoiding lithium overload that would reduce catalytic activity. The excess lithium is taken out and supplied controllably from the additive

Inventive Principle:
Principle #2Taking out (Extraction)

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 process achieves high conversion and selectivity of nitriles to primary amines with reduced formation of secondary amines, maintains catalyst activity over long periods, and operates economically without significant ammonia usage, even in the presence of water.

Implementation Method 1

a nitrile is hydrogenated in the presence of a full contact cobalt catalyst to obtain the corresponding primary amine

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

The hydrogenation is carried out in a device (V1), for example in a reactor

Methodology Applied
Scientific EffectHydrogenation: Hydrogenation

Data Source

PatentEP3186221B1Method for the preparation of primary amines using a full contact cobalt catalyst
Publication Date: 2022.02.23 BASF SE
  • EP3186221B1 patent drawingFigure 1
  • EP3186221B1 patent drawingFigure 2
  • EP3186221B1 patent drawingFigure 3

AI summary

The invention relates to a method for producing primary amines, characterized in that at least one nitrile is hydrogenated in a device (V1) in the presence of a cobalt-based full contact catalyst while obtaining at least one primary amine, at least one compound (I) being added repeatedly or continuously to the device (V1) and said compound (I) comprising at least one component selected from the group including alkali metal, alkaline-earth metal or rare earth metal.