FDCA Ester Production via Glucaric Acid Transesterification
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Solution Overview
Problem
Current methods for producing 2,5-furandicarboxylic acid (FDCA) esters face challenges due to the instability of dehydration intermediates and the use of highly acidic and corrosive conditions, as well as complexities in scaling up production, particularly with the use of microwave energy and transition metal catalysts under hydrogen atmospheres.
Innovation Solution
A process involving the reaction of glucaric acid with a high boiling alcohol in the presence of an acid catalyst, followed by removing water and transesterifying with a lower boiling alcohol to form dimethyl, diethyl, or dipropyl esters of FDCA, which are useful as monomers for biobased polymers, utilizing a biphasic system to enhance yields and simplify the process.
Engineering Contradictions & Design Principles
Engineering Contradiction Analysis
1Reliability
If chemical dehydration of hexoses to HMF followed by oxidation to FDCA is used, then FDCA esters can be produced, but the dehydration intermediates are relatively unstable and require highly acidic and corrosive conditions
Solution Approach 1:
The patent uses DDG (3-dehydro-4-deoxy-glucarate) as a more stable intermediate instead of HMF. DDG can be converted to FDCA through oxidation without requiring the highly acidic conditions needed for HMF dehydration, thus serving as a mediator that avoids the harmful acidic environment while still enabling FDCA production from hexoses
Solution Approach 2:
The patent changes the chemical parameters of the intermediate from HMF to DDG, which has different stability characteristics and reactivity requirements. This parameter change allows the process to proceed under less corrosive conditions while maintaining product yield
2Productivity
If microwave energy and transition metal catalysts under hydrogen atmosphere are used, then production can be achieved, but the process becomes complex and difficult to scale up
Solution Approach 1:
The patent extracts or removes the complex components (microwave energy system, transition metal catalysts, hydrogen atmosphere requirements) from the process while retaining the core functionality of converting DDG to FDCA esters. This simplification makes the process more suitable for large-scale commercial production
Solution Approach 2:
The patent employs simpler, more readily available catalysts and reaction conditions that can be easily implemented and discarded or regenerated, replacing the expensive and complex microwave/H2/transition metal system with a more economically viable approach for scale-up
3Quantity of substance
If high boiling alcohols are used in esterification, then yields are improved, but the process requires additional steps for alcohol removal and transesterification
Solution Approach 1:
The patent segments the esterification process into two distinct stages: first using high boiling alcohols to achieve high conversion and yield, then separately handling the alcohol removal and transesterification step. This segmentation allows optimization of each individual step rather than attempting to optimize a single complex reaction
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 method achieves high yields of FDCA esters, overcoming the limitations of previous methods by providing a more efficient and commercially viable process for producing esters with improved stability and reduced corrosive conditions, suitable for large-scale production.
Implementation Method 1
reacting an aqueous feed comprising glucaric acid with a high boiling first alcohol in the presence of an acid catalyst
Implementation Method 2
removing water during the reaction
Implementation Method 3
transesterifying the first ester with the lower boiling second alcohol to form a second product mixture comprising a second ester of FDCA with the lower boiling second alcohol
Data Source
Figure 1
AI summary
The present invention relates to a process for making the esters of 2,5-furandicarboxylic acid, and particularly the dimethyl, diethyl or dipropyl esters of FDCA for use as monomers in the production of polyesters and other types of polymers with biobased content, comprising: reacting an aqueous feed comprising glucaric acid with a high boiling first alcohol in the presence of an acid catalyst and with removing water during the reaction, to form a first product mixture comprising a first ester of FDCA and the high boiling first alcohol; removing unreacted high boiling first alcohol from the first product mixture; combining the first ester of FDCA and the high boiling first alcohol with a lower boiling second alcohol selected from the group consisting of methanol, ethanol, isopropanol and n-propanol; transesterifying the first ester with the lower boiling second alcohol to form a second product mixture comprising a second ester of FDCA with the lower boiling second alcohol; and recovering the second ester of FDCA with the lower boiling second alcohol.