Titanium Ether Catalyst for Ethylene Dimerization

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Solution Overview

Problem

Catalytic systems for selectively dimerizing ethylene to 1-butene, particularly those based on titanium, face significant challenges due to the formation of high molecular mass polyethylene, which deactivates the catalyst and complicates operability, despite previous attempts to improve selectivity and productivity.

Innovation Solution

A catalytic composition comprising alkoxy or aryloxy titanium compounds, ether-type additives, and aluminium compounds with specific molar ratios greater than 10 and 4, respectively, is used to achieve high selectivity for ethylene dimerization to 1-butene while minimizing or eliminating polyethylene production.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If traditional titanium-based catalytic systems are used for ethylene dimerization, then the catalyst shows high activity, but high molecular mass polyethylene is formed which deactivates the catalyst and complicates operability

Engineering Contradiction:
Improveethylene dimerization activityVSAvoidcatalyst stability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent changes the chemical parameters of the catalytic system by introducing specific ether-type additives (diethyl ether, diisopropyl ether, tetrahydrofuran, 2-methoxy-2-methylpropane) and controlling their molar ratios relative to titanium and aluminum compounds. This parameter optimization suppresses polyethylene formation while maintaining high dimerization activity, resolving the contradiction between productivity and reliability

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

Ether-type compounds are introduced as intermediary substances that mediate between the titanium catalyst and ethylene substrate. These ethers coordinate with the titanium center, modifying its reactivity to favor dimerization over polymerization, thus maintaining catalyst stability while preserving high activity

Inventive Principle:
Principle #24Intermediary (Mediator)

2Manufacturing precision

If the molar ratio of ether additive to titanium compound is increased to improve selectivity, then polyethylene formation is reduced, but the reaction rate slows down considerably

Engineering Contradiction:
Improveselectivity to 1-buteneVSAvoidreaction rate
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent optimizes the molar ratio parameters within a specific range (10-50, preferably 15-30) rather than using excessive amounts. This controlled parameter change achieves high selectivity to 1-butene while maintaining acceptable reaction rates, avoiding the trade-off between precision and productivity

Inventive Principle:
Principle #35Parameter changes

3Productivity

If the molar ratio of alkyl aluminium to alkyl titanate is increased to improve productivity, then dimerization activity increases, but operability deteriorates due to increased polymer formation

Engineering Contradiction:
Improvedimerization activityVSAvoidprocess operability
Core Design Contradiction:
ProductivityVSEase of operation

Solution Approach 1:

Ether-type additives serve as intermediary ligands that modulate the reactivity of the titanium-aluminum catalytic system. They allow higher aluminum-to-titanium ratios to be used for improved productivity while the ethers prevent excessive polymerization, thus maintaining good operability despite increased activity

Inventive Principle:
Principle #24Intermediary (Mediator)

4Productivity

If reaction temperature is increased to improve reaction rate, then productivity increases, but catalyst stability decreases and polymer proportion increases

Engineering Contradiction:
Improvereaction rateVSAvoidcatalyst stability
Core Design Contradiction:
ProductivityVSStability of the object's composition

Solution Approach 1:

Ether-type compounds act as thermal stabilizers and ligand intermediaries that protect the titanium catalyst from deactivation at elevated temperatures. They maintain catalyst stability even at higher reaction temperatures while allowing increased productivity, thus decoupling the usual trade-off between rate and stability

Inventive Principle:
Principle #24Intermediary (Mediator)

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 results in a process with very high selectivity for 1-butene production and significantly reduced or zero polyethylene formation, enhancing the operability and stability of the catalytic system.

Implementation Method 1

a catalytic composition comprising at least one alkoxy or aryloxy titanium compound, at least one additive selected from ether type compounds and at least one aluminium compound

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentUS9499455B2Process for the selective dimerisation of ethylene to 1-butene
Publication Date: 2016.11.22 IFP ENERGIES NOUVELLES

AI summary

The invention concerns a process for the selective dimerization of ethylene to 1-butene employing a catalytic composition comprising at least one alkoxy or aryloxy titanium compound, at least one additive selected from ether type compounds and at least one aluminium compound.