Biofuel Synthesis from Fermentation Carboxylic Acids

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Solution Overview

Problem

The high production costs and complex downstream processing associated with recovering carboxylic acids from fermentation broths as salts hinder the cost-competitiveness of bio-based production methods for biofuels like ethanol and biodiesel, as they require additional steps for neutralization and purification, leading to significant waste generation and operational inefficiencies.

Innovation Solution

A process involving the conversion of free carboxylic acids from fermentation broths into their corresponding esters under supercritical or critical conditions using a CO2 atmosphere without additional acid catalysts, followed by hydrogenation or hydrogenolysis to produce biofuels, which simplifies the recovery and recycling of by-products and reduces waste.

Engineering Contradictions & Design Principles

VSEngineering Contradiction Analysis

1Manufacturing precision

If carboxylic acids are recovered from fermentation broths as salts through neutralization, then the acids can be isolated and purified, but additional processing steps are required including base addition, salt removal, and waste disposal

Engineering Contradiction:
Improveacid recovery purityVSAvoidprocessing steps
Core Design Contradiction:
Manufacturing precisionVSDevice complexity

Solution Approach 1:

The patent extracts carboxylic acids from fermentation broths directly in their free acid form without converting to salts. This is achieved by adjusting pH to below the pKa of the carboxylic acid, causing the acid to precipitate or be easily separable from the broth, thereby eliminating the need for neutralization and subsequent salt removal steps

Inventive Principle:
Principle #2Taking out (Extraction)

Solution Approach 2:

Instead of the conventional approach of converting free acid to salt for recovery, this patent inverts the process by directly recovering the free acid form. The method adjusts pH in the opposite direction (acidic rather than basic) to maintain carboxylic acid in its protonated, separable form, thereby simplifying the overall recovery process

Inventive Principle:
Principle #13The other way round (Inversion)

2Quantity of substance

If base is added to neutralize fermentation broth for salt formation, then carboxylic acid salts are generated, but equivalent amounts of base reagent are consumed and waste is produced

Engineering Contradiction:
Improveacid recovery yieldVSAvoidreagent consumption
Core Design Contradiction:
Quantity of substanceVSLoss of substance

Solution Approach 1:

The patent employs a self-service approach where the carboxylic acid itself serves as the pH indicator and the fermentation broth's natural buffering capacity is utilized. By adjusting pH to below the acid's pKa, the system automatically favors the free acid form without requiring external base addition for neutralization, thereby eliminating reagent consumption and associated waste

Inventive Principle:
Principle #25Self-service

3Ease of manufacture

If calcium salts of C4 diacids are formed, then the salts have low solubility and can be separated, but they are unsuitable for chemical conversion applications requiring free acid species

Engineering Contradiction:
Improvesalt separationVSAvoidapplication suitability
Core Design Contradiction:
Ease of manufactureVSAdaptability or versatility

Solution Approach 1:

The patent applies local quality control by adjusting the pH of specific regions or batches of fermentation broth to below the pKa of the carboxylic acid. This creates localized conditions where the free acid form predominates, making the recovered acid suitable for diverse applications including chemical conversions that require free acid species, while maintaining ease of separation through controlled precipitation

Inventive Principle:
Principle #3Local quality

4Manufacturing precision

If multiple operational units are used for salt dissolution, filtration, and waste disposal, then complete acid recovery is achieved, but operational costs increase

Engineering Contradiction:
Improveacid recovery completenessVSAvoidoperational efficiency
Core Design Contradiction:
Manufacturing precisionVSProductivity

Solution Approach 1:

The patent merges multiple operational units into a single integrated process step. By adjusting pH to below pKa and directly recovering free acid through filtration or centrifugation, the process combines what would traditionally require separate steps for neutralization, salt formation, dissolution, and waste disposal into one efficient operation, thereby maintaining complete acid recovery while significantly improving operational efficiency

Inventive Principle:
Principle #5Merging (Combining)

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 enhances the efficiency and cost-effectiveness of biofuel production by eliminating the need for neutralization and purification steps, allowing for direct use of free carboxylic acids and recycling of by-products, thereby reducing waste and operational costs while achieving high yields and purity of biofuel products.

Implementation Method 1

drying said fermentation broth containing free carboxylic acids into a powder

Methodology Applied
Scientific EffectDrying: Evaporation

Implementation Method 2

reacting said carboxylic acids in said powder with an alcohol solvent or mixture of at least one alcohol under a CO2 atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for the alcohol or CO2 to synthesize the corresponding ester or esters

Methodology Applied
Scientific EffectSupercritical fluid: Supercritical Fluid

Implementation Method 3

subjecting the esters formed to either hydrogenolysis or hydrogenation to form one or more biofuels

Methodology Applied
Scientific EffectHydrogenation: Hydrogenation

Data Source

PatentUS10118886B2Biofuels production from bio-derived carboxylic-acid esters
Publication Date: 2018.11.06 ARCHER DANIELS MIDLAND CO
  • US10118886B2 patent drawing
  • US10118886B2 patent drawing
  • US10118886B2 patent drawing

AI summary

A process for producing biofuels compounds directly from carboxylic acid esters recovered from a fermentation system is described. The process involves taking a fermentation broth that has been reduced to a dry powder containing free organic acids; reacting the carboxylic acid in the powder with an alcohol solvent under a CO2-containing atmosphere in substantial absence of any other acid catalyst at a reaction temperature and pressure that corresponds to supercritical, critical or near critical conditions for at least one of the alcohol or CO2 to synthesize an ester, then subjecting the ester to either hydrogenolysis or hydrogenation to form a biofuel.