Chromium Catalyst Selective Ethylene Oligomerization

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Solution Overview

Problem

There is a challenge in developing alpha olefin oligomerization techniques that do not use triethylaluminum (TEA) as part of the catalyst system, particularly in achieving efficient and economic production of linear alpha olefins, as alternative techniques often require extensive secondary processing to recover desired products from undesired fractions like butene or waxes.

Innovation Solution

The use of a chromium-based catalyst system comprising N2-phosphinyl amidine, formamidine, or guanidine chromium compound complexes in combination with aluminoxane, in the presence of an organic reaction medium and optionally hydrogen, to selectively oligomerize ethylene and produce linear alpha olefins without forming ethylene oligomers in situ.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Reliability

If alternative catalyst systems are used to avoid TEA, then the drawbacks of homogeneous catalyst systems are avoided, but polymer formation occurs during startup and operation

Engineering Contradiction:
Improvecatalyst system performanceVSAvoidpolymer formation
Core Design Contradiction:
ReliabilityVSObject-generated harmful factors

Solution Approach 1:

The patent introduces a C3+ olefin before introducing ethylene to the reaction zone. This preliminary action of having C3+ olefin already present in the reaction zone prevents polymer formation during startup by ensuring that when ethylene is subsequently introduced, the catalyst system is already engaged in productive oligomerization rather than forming unwanted polymers.

Inventive Principle:
Principle #10Preliminary action

Solution Approach 2:

The C3+ olefin acts as an intermediary substance that mediates between the catalyst system and ethylene. By being present in the reaction zone first, it facilitates the catalyst's selective oligomerization of ethylene while preventing harmful polymer formation, thus serving as a protective intermediary in the catalytic process.

Inventive Principle:
Principle #24Intermediary (Mediator)

2Object-generated harmful factors

If C3+ olefin is introduced before ethylene, then polymer formation is reduced, but process complexity increases

Engineering Contradiction:
Improvepolymer formationVSAvoidprocess steps
Core Design Contradiction:
Object-generated harmful factorsVSDevice complexity

Solution Approach 1:

The patent maintains continuous presence of C3+ olefin in the reaction zone throughout the oligomerization process. This continuous action ensures that the catalyst system remains engaged in productive oligomerization pathways, preventing polymer formation during both startup and normal operation without requiring additional processing steps.

Inventive Principle:
Principle #20Continuity of useful action

3Object-generated harmful factors

If ethylene is diluted with organic reaction medium, then polymer formation is reduced, but productivity decreases

Engineering Contradiction:
Improvepolymer formationVSAvoidoligomer production rate
Core Design Contradiction:
Object-generated harmful factorsVSProductivity

Solution Approach 1:

The patent changes the compositional parameter of the reaction zone by introducing C3+ olefin, which alters the reaction kinetics and catalyst behavior. This parameter change enables selective oligomerization of ethylene while suppressing polymer formation, achieving both reduced harmful factors and maintained productivity through optimized reaction conditions.

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

This approach enables the selective production of ethylene oligomers with reduced polymer formation during startup and normal operation, improving productivity and preventing fouling of reaction zone components, thus enhancing the efficiency and stability of the oligomerization process.

Implementation Method 1

a catalyst system comprising (a) a chromium component comprising an N2-phosphinyl amidine, formamidine, or guanidine chromium compound complex

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

a catalyst system comprising (a) a chromium component comprising an N2-phosphinyl amidine, formamidine, or guanidine chromium compound complex in combination with aluminoxane

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3464303B1Reduced polymer formation for selective ethylene oligomerizations
Publication Date: 2022.12.14 CHEVRON PHILLIPS CHEMICAL COMPANY LP
  • EP3464303B1 patent drawingFigure 1
  • EP3464303B1 patent drawingFigure 2
  • EP3464303B1 patent drawingFigure 3

AI summary

Disclosed are processes, systems, and reaction systems for the oligomerization of ethylene to form an ethylene oligomer product in a reaction zone using a catalyst system comprising (a) a chromium component comprising an N2-phosphinyl amidine chromium compound complex, an N2-phosphinyl formamidine chromium compound complex, an N2-phosphinyl guanidine chromium compound complex, or any combination thereof, and (b) an aluminoxane. A C3+ olefin can be present in the reaction zone for a period of time, where the C3+ olefin is not an ethylene oligomer formed in-situ within the reaction zone.