Polyoxymethylene Dialkyl Ether Production via Trioxane Reaction

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Solution Overview

Problem

Existing processes for preparing polyoxymethylene dimethyl ethers often result in the predominantly formation of dimers, which have a low boiling point and lower the flash point of diesel fuel, making them unsuitable as additives, and are prone to hydrolysis by acidic catalysts, leading to unstable hemiacetals that further impair fuel quality.

Innovation Solution

A process involving the reaction of dialkyl ethers with trioxane in the presence of an acidic catalyst, minimizing water formation, and employing a recirculation and separation method using multiple distillation columns to achieve a higher proportion of trimer and tetramer polyoxymethylene dialkyl ethers, which are more suitable as diesel fuel additives.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Quantity of substance

If conventional processes are used to prepare polyoxymethylene dimethyl ethers, then the reaction produces polyoxymethylene ethers, but the dimer is predominantly formed which has a low boiling point and lowers the flash point of diesel fuel

Engineering Contradiction:
Improvepolyoxymethylene ether productionVSAvoidflash point reduction
Core Design Contradiction:
Quantity of substanceVSObject-affected harmful factors

Solution Approach 1:

The patent changes the reaction parameters by using trioxane instead of formaldehyde, operating at elevated temperatures (100-200°C) and controlled pressures (1-50 bar), and using specific acid catalysts to shift the product distribution toward higher polymers (trimer and tetramer) rather than dimer, thereby avoiding flash point reduction

Inventive Principle:
Principle #35Parameter changes

Solution Approach 2:

The patent selectively promotes the formation of specific polymer degrees (trimer and tetramer) over others by optimizing reaction conditions, effectively creating a localized quality improvement in the product distribution to achieve the desired balance between production efficiency and fuel quality

Inventive Principle:
Principle #3Local quality

2Productivity

If acidic catalysts are used in the reaction process, then the polyoxymethylene ethers can be formed, but water is formed as a by-product which hydrolyzes the polyoxymethylene ethers and forms unstable hemiacetals

Engineering Contradiction:
Improvereaction rateVSAvoidproduct stability
Core Design Contradiction:
ProductivityVSReliability

Solution Approach 1:

The patent converts the potentially harmful effect of water formation into a benefit by using trioxane as the carbonyl source instead of formaldehyde, which does not produce water during the reaction. This eliminates the hydrolysis problem while maintaining the catalytic activity needed for productive reaction

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

Solution Approach 2:

The patent uses trioxane as an intermediary carbonyl source that mediates the reaction between methanol and the polymerization process without generating water as a by-product, thereby preventing the harmful hydrolysis reaction while still enabling the formation of polyoxymethylene ethers

Inventive Principle:
Principle #24Intermediary (Mediator)

3Object-affected harmful factors

If the reaction is carried out to produce higher polymers, then the flash point is improved, but the separation and purification becomes more complex

Engineering Contradiction:
Improveflash pointVSAvoidseparation process
Core Design Contradiction:
Object-affected harmful factorsVSDevice complexity

Solution Approach 1:

The patent segments the product mixture into different fractions based on their boiling points and polymer degrees, using fractional distillation to separate the desired trimer and tetramer from unreacted starting materials and other by-products, thereby achieving purification without excessive complexity

Inventive Principle:
Principle #1Segmentation

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 effectively produces polyoxymethylene dialkyl ethers with a higher trimer content, avoiding the issues of low boiling points and instability, thereby enhancing the quality and compliance of diesel fuel additives by maintaining a higher flash point and meeting DIN standards.

Implementation Method 1

reaction of dialkyl ethers with trioxane in the presence of an acidic catalyst

Methodology Applied
Scientific EffectCatalysis: Catalysis

Implementation Method 2

employing a recirculation and separation method using multiple distillation columns

Methodology Applied
Scientific EffectDistillation: Distillation

Data Source

PatentEP1902009B1Method for the production of polyoxymethylene dialkyl ethers from trioxan and dialkylethers
Publication Date: 2010.07.28 BASF SE
  • EP1902009B1 patent drawingFigure 1
  • EP1902009B1 patent drawingFigure 2
  • EP1902009B1 patent drawingFigure 3

AI summary

The invention relates to a method for production of polyoxymethylene dialkyl ethers of formula H2m+1CmO(CH2O)nCmH2m+1, where n = 2 - 10, m independently = 1 or 2, in which a dialkyl ether selected from dimethyl ether, methyl ethyl ether or diethyl ether and trioxan are fed into a reactor and reacted in the presence of an acid catalyst, whereby the amount of water introduced into the reaction mixture with the dialkyl ether, trioxan and/or the catalyst is < 1 wt. %, with relation to the reaction mixture.