Zirconium Amide Catalyst for Ethylene Oligomerization

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Solution Overview

Problem

Existing catalyst systems for ethylene oligomerization face challenges such as poor solubility, high production of wax and high molecular weight polyethylene, low selectivity, and polymer formation, which affect the purity and distribution of linear alpha-olefins.

Innovation Solution

A catalyst composition comprising a zirconium amide compound, an organoaluminum compound, and an additive, specifically tetrachlorobis(N,N-diisobutylacetamide)zirconium and trialkylaluminum, is used for ethylene oligomerization, with the zirconium amide compound prepared by reacting a zirconium component with a substituted amide in the presence of an organic solvent, to achieve high activity and broad weight percent distribution of linear oligomers.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Productivity

If zirconium halide or zirconium tetrachloride is used as catalyst, then catalytic activity is achieved, but solubility in hydrocarbon solvent is poor and wax/high molecular weight polyethylene is produced in large amount

Engineering Contradiction:
Improvecatalytic activityVSAvoidwax and high molecular weight polyethylene production
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The patent changes the chemical parameters of the zirconium catalyst by replacing halide ligands with amide ligands having specific steric and electronic properties. The amide ligands with bulky alkyl groups modify the catalyst's solubility characteristics and control the oligomerization selectivity, reducing wax and high molecular weight polyethylene production while maintaining catalytic activity.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent creates a composite catalyst system combining zirconium amide compound with specific organoaluminum compounds and additives. This composite approach enhances solubility in hydrocarbon solvents and provides synergistic effects that improve selectivity for desired oligomers while minimizing unwanted by-products.

Inventive Principle:
Principle #40Composite materials

2Quantity of substance

If zirconium tetrachloride is used with aluminum sesquichloride and triethyl aluminum, then linear alpha-olefins are produced, but selectivity for light alpha-olefins is relatively low and reaction temperature is high

Engineering Contradiction:
Improvelinear alpha-olefins productionVSAvoidselectivity for light alpha-olefins
Core Design Contradiction:
Quantity of substanceVSManufacturing precision

Solution Approach 1:

The patent modifies the catalyst composition by using zirconium amide compounds instead of zirconium tetrachloride, combined with specific organoaluminum compounds. This parameter change in catalyst chemistry enables higher selectivity for light alpha-olefins (C4-C10) and allows operation at lower temperatures while maintaining high production rates.

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent introduces specific organoaluminum compounds and additives as intermediaries that mediate the oligomerization process. These intermediaries control the catalyst's interaction with ethylene, directing the reaction pathway toward light alpha-olefins and improving overall selectivity.

Inventive Principle:
Principle #24Intermediary (Mediator)

3Productivity

If zirconium alkyl alkanoates are used as catalyst, then catalytic system is formed, but undesirable quantity of high molecular weight polyethylene is produced

Engineering Contradiction:
Improveoligomerization activityVSAvoidhigh molecular weight polyethylene production
Core Design Contradiction:
ProductivityVSObject-generated harmful factors

Solution Approach 1:

The patent changes the ligand type from alkanoate to amide on the zirconium center. This parameter change fundamentally alters the catalyst's behavior, reducing the production of high molecular weight polyethylene while preserving oligomerization activity. The amide ligands provide better control over chain growth and termination.

Inventive Principle:
Principle #35Parameter changes

4Manufacturing precision

If alcohol is used as third component in zirconium based catalyst system, then high purity alpha-olefin is produced, but polymer formation increases and C20+ fraction yield is high

Engineering Contradiction:
Improvealpha-olefin purityVSAvoidpolymer formation and C20+ fraction
Core Design Contradiction:
Manufacturing precisionVSObject-generated harmful factors

Solution Approach 1:

The patent replaces the alcohol component with a specifically designed zirconium amide compound. This parameter change eliminates the need for alcohol additives while achieving high purity alpha-olefins. The amide ligands inherently provide better control over product distribution, reducing polymer formation and C20+ fraction.

Inventive Principle:
Principle #35Parameter changes

5Manufacturing precision

If zirconium compound is mixed with ketals, acetals and hydrocarbyl-aluminum halide, then selectivity for light alpha-olefins is good, but activity is low and polymer traces accumulate causing reactor plugging

Engineering Contradiction:
Improveselectivity for light alpha-olefinsVSAvoidcatalyst activity
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent creates an optimized composite catalyst system using zirconium amide compound combined with specific organoaluminum compounds and additives. This composite approach maintains high selectivity for light alpha-olefins while significantly improving catalytic activity and preventing polymer accumulation that causes reactor plugging.

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

The catalyst system achieves high purity and broad weight percent distribution of linear alpha-olefins from C4 to C16, with minimal polymer formation and improved reactor stability, enhancing the efficiency of ethylene oligomerization.

Implementation Method 1

reacting a zirconium component having formula ZrX m .nTHF with a substituted amide of formula RCONR'R'' to obtain a zirconium amide compound having formula ZrX m .n(RCONR'R'')

Methodology Applied
Scientific EffectChemical reaction: Chemical Bonding

Implementation Method 2

catalyst composition for use as catalyst system for ethylene oligomerization, providing high activity and produce linear oligomer product

Methodology Applied
Scientific EffectCatalysis: Catalysis

Data Source

PatentEP3834932B1Process for preparation of ethylene oligomerization catalyst and oligomerization thereof
Publication Date: 2022.10.05 INDIAN OIL CORP LTD

AI summary

The present invention describes a catalyst composition for use as a catalyst system for an ethylene oligomerization, providing high activity and produce linear oligomer product having broad weight percent distribution i.e. C4 to C16. The catalyst composition comprises a zirconium amide compound, an organoaluminum compound and an additive. The present invention also provides a process for preparation of the zirconium amide compound comprising reacting a zirconium component having formula ZrXm.nTHF, wherein X is halogen atom; m is an integer having value equal or less than 4 and n is a number equal or less than 2, and a substituted amide of formula RCONR'R", wherein R, R' and R" are saturated or unsaturated aliphatic C1-C10 hydrocarbon or aromatic C6-C14 hydrocarbon, in the presence of an organic solvent.