Catalyst Modification with Alkaline Earth Metal Ions for Continuous Nitro Hydrogenation

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Solution Overview

Problem

Existing processes for the continuous hydrogenation of nitro compounds to amines face issues such as discontinuous operation, high catalyst consumption, metal corrosion, excessive heat release, secondary reactions, and catalyst deactivation due to the formation of high-boiling components, leading to reduced product yield and increased production costs.

Innovation Solution

The process involves continuous hydrogenation in the presence of a supported catalyst containing elements from groups 7 to 12, specifically using at least one salt of alkali metals, alkaline earth metals, or rare earth metals to maintain catalyst activity, reduce high-boiling component formation, and optimize reaction conditions.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Adaptability or versatility

If discontinuous batch process is used, then flexibility in operation is maintained, but productivity decreases and catalyst consumption increases

Engineering Contradiction:
Improveoperational flexibilityVSAvoidproduction efficiency
Core Design Contradiction:
Adaptability or versatilityVSProductivity

Solution Approach 1:

The patent implements continuous hydrogenation process where nitro compounds are continuously fed to the reactor and amines are continuously removed, eliminating batch downtime. The supported catalyst remains active throughout continuous operation, maintaining steady production rates without periodic shutdowns for catalyst replacement or reactor cleaning.

Inventive Principle:
Principle #20Continuity of useful action

Solution Approach 2:

The catalyst is pre-modified with alkaline earth metal ions before use to enhance its stability and activity for continuous operation. This preliminary modification ensures the catalyst maintains optimal performance throughout extended continuous running periods.

Inventive Principle:
Principle #10Preliminary action

2Manufacturing precision

If large amounts of metal salts are added to suppress side reactions, then selectivity improves, but production costs increase and metal corrosion is promoted

Engineering Contradiction:
Improveproduct selectivityVSAvoidmetal corrosion
Core Design Contradiction:
Manufacturing precisionVSObject-affected harmful factors

Solution Approach 1:

Alkaline earth metal ions (Ca²⁺, Sr²⁺, Ba²⁺) serve as intermediary substances that modify the catalyst surface properties to suppress dehydrohalogenation side reactions. These ions act as mediators between the substrate and catalyst, enhancing selectivity without requiring large amounts of corrosive metal salts in the reaction medium.

Inventive Principle:
Principle #24Intermediary (Mediator)

Solution Approach 2:

The patent changes the chemical environment around the catalyst by introducing alkaline earth metal ions that alter the local pH and ionic strength at the catalyst surface. This parameter modification suppresses side reactions involving halogenated compounds without needing excessive salt concentrations that would cause corrosion.

Inventive Principle:
Principle #35Parameter changes

3Loss of energy

If high reaction temperatures are used to manage heat of reaction, then energy recovery potential increases, but undesired secondary reactions increase

Engineering Contradiction:
Improveheat recovery potentialVSAvoidsecondary reactions
Core Design Contradiction:
Loss of energyVSObject-generated harmful factors

Solution Approach 1:

The patent optimizes reaction temperature parameters to operate at moderate temperatures (50-150°C) that balance heat management with selectivity. The modified catalyst enables efficient heat dissipation through optimized reaction kinetics, preventing local overheating that would cause secondary reactions while still allowing heat recovery.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The exothermic heat of reaction is managed by designing the continuous flow system with appropriate heat exchange surfaces. The reaction heat is efficiently removed and can be recovered for steam generation or process heating, converting what would be a harmful temperature rise into a useful energy source.

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

4Productivity

If reaction temperature is increased to maintain catalyst activity, then reaction rate improves, but formation of high-boiling components increases leading to catalyst deactivation

Engineering Contradiction:
Improvereaction rateVSAvoidcatalyst lifetime
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent introduces alkaline earth metal ions that modify the catalyst's electronic and geometric properties, enabling high reaction rates at lower temperatures. This parameter change in catalyst composition allows maintaining productivity while avoiding temperature-induced formation of high-boiling condensables that deactivate the catalyst.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The catalyst is designed as a composite material combining supported metal particles with alkaline earth metal ion modifications. This composite structure provides both the activity needed for high reaction rates and the stability required to prevent catalyst deactivation from high-boiling component formation.

Inventive Principle:
Principle #40Composite materials

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 approach significantly increases the product yield of amines, extends catalyst lifetime, and ensures consistent reaction performance without reducing feed rates or increasing temperatures, thereby improving process efficiency and reducing production costs.

Implementation Method 1

continuous hydrogenation of a nitro compound to the corresponding amine in a liquid reaction mixture containing the nitro compound in the presence of a supported catalyst which contains at least one element from groups 7 to 12 of the Periodic Table of the Elements as the active component

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

Catalyst modification with alkaline metal, alkaline earth metal or rare earth metal ions

Methodology Applied
Scientific EffectAdsorption: Adsorption

Implementation Method 3

continuous hydrogenation of a nitro compound to the corresponding amine

Methodology Applied
Scientific EffectHydrogenation: Hydrogenation

Data Source

PatentEP3523271B1Catalyst modification with alkaline metal, alkaline earth metal or rare earth metal ions in continuous liquid phase hydration of nitro compounds
Publication Date: 2020.12.09 BASF SE
  • EP3523271B1 patent drawingFigure 1~2
  • EP3523271B1 patent drawingFigure 3~4
  • EP3523271B1 patent drawingFigure 5~6

AI summary

The present invention relates to a method for continuously hydrogenating a nitro compound to give the corresponding amine in a liquid reaction mixture containing the nitro compound, in the presence of a supported catalyst which contains as the active component at least one element from groups 7 to 12 of the periodic table of the elements, the hydrogenation being carried out in the presence of at least one salt selected from the group consisting of the salts of the alkali metals, alkaline earth metals or rare earth metals. The invention also relates to a supported catalyst for continuously hydrogenating a nitro compound to give the corresponding amine in a liquid reaction mixture containing the nitro compound and, as the active component, at least one element from groups 7 to 12 of the periodic table of the elements and at least one salt of the alkali metals, alkaline earth metals or rare earth metals.