Recovery of Organic Acids From

Fermentation Broths

Southern Bio-Products Conference

March 4-6, 2004
Beau Rivage Resort
Biloxi, MS

Tim Eggeman, Ph.D., P.E.

Dan Verser, Ph.D.
ZeaChem Inc.
 Organic Acids - Today
Organic Acid Price, $/lb US Demand, Common
(100% Basis) MM lb/yr Route
Formic 0.46 50 Synthetic
Acetic 0.42 5,286 Synthetic
Oxalic 0.38 17 Synthetic
Propionic 0.49 202 Synthetic
Lactic 0.80 176 Fermentation
Tartaric 3.00 7 Fermentation
Succinic 1.00 3 Synthetic
Maleic 0.42 478 Synthetic
Adipic 0.70 1,725 Synthetic
Citric 0.75 600 Fermentation
 Points of View
Sugars:
Inexpensive
Under-Utilized
More Sustainable

Synthetic Routes will Eventually be Displaced

Platform Viewpoint is Under-Utilized

Biology plus = Better Technology and

Chemistry Market Diversification
 Generic Platform

O O O
RCR RCOH RCOR
Organic Ester
Ketone
Acid

O
RCH RCH2OH R CH2
Aldehyde Alcohol Olefin
 C2 Platform

O O O
CH3CCH3 CH3COH CH3COCH2CH3
Acetone Acetic Ethyl
Acid Acetate

O
CH3CH CH3CH2OH CH2 CH2
Acetaldehdye Ethanol Ethylene
 Issues in Recovery
pH of Broth
Unreactive Species at Near Neutral pH
Commodity Scale Production is Constrained by
Need to Avoid Salt Coproduction

Dilute Broths
Evaporating Water is Expensive
Prefer Selective Methods for Removing
Organic Acids from Water
 Effect of pH
O O
CH3COH CH3CO- + H+

Protonated Dissociated
Acid Acid
100

90
80 pKa = 4.75

70
% Dissociation

60

50 Protonated Acid Dissociated Acid

40

30
20

10
0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pH
Acidic Basic
Neutral
 pH Options

Low pH Fermentation

Neutral pH Fermentation
Direct Acidification
Amine Complex Formation
Other
Bipolar Electrodialysis
Esterases
 Lactic Acid - Traditional
Alcohol

Water
Sulfuric Hydrolysis
Ester
Lime Acid

Lactic
Acid
Fermentation Direct Esterification
Sugars Acidification

Water
Gypsum
 Direct Acidification

Fermentation: C6 H 12 O 6 Ca(OH) 2 Ca(Lac) 2 2 H 2 O

Re-acidification: Ca(Lac) 2 H 2SO4 2 HLac CaSO 4
Overall: C6 H 12 O 6 Ca(OH) 2 H 2SO 4 2 HLac CaSO 4 2 H 2 O

US Demand for Lactic Acid = 176 MM lb/yr,

Gypsum Coproduct = 252 MM lb/yr !!!
Lactic Acid Amine Extraction

(From: Baniel, A.M. et. al., US Pat. 5,510,526)

 Citric Acid Lime/Acid
Lime

Sugars Fermentation Precipitation Residue

Sulfuric
Acid Water
Calcium
Citrate

Acidification Crystallization Citric

Acid

Gypsum
 Citric Acid Amine Extraction
Water

Water

Forward Extraction

Back Extraction
Sugars Fermentation Crystallization Citric
Acid

Residue
 Formic Acid

Water

CO Formic
Carbonylation Methyl Formate Hydrolysis Acid
Methanol

Methanol

O
Carbonylation: CO + CH3OH HCOCH3
O O
Hydrolysis: HCOCH3 + H2 O HCOH

O
Net: CO + H2O HCOH
 Some Common Themes
Eliminating Salt Coproduction is Difficult
Microbiology
Careful Selection of Cations and Recovery
Scheme

Common Purification Methods

Amine Extraction
Esterification
 Routes to Ethanol
ZeaChem Indirect Route

Fermentation: Dextrose 3 Acetic Acid

Esterification: 3 Acetic Acid + 3 Ethanol 3 Ethyl Acetate + 3 H2O

Hydrogenation: 3 Ethyl Acetate + 6 H2 6 Ethanol

Net: Dextrose + 6 H2 3 Ethanol + 3 H2O

Direct Fermentation
Dextrose 2 Ethanol + 2 CO2
 Lab Status - Fermentation

Lab Scale Fermentation

Strain: Moorella Thermoacetica ATCC 39073
Media: Glucose+Corn Steep Liquor

Batch Results
First Run: 28 g/l acetate
Goal: 35-50 g/l acetate, yield = 85+% of theoretical
Lab Status - Recovery
Lab Scale
Amine Complex Formation
w/ CaCO3 Precipitation
Extraction of Amine
Complex
Esterification

Results to Date
97+% CaCO3 Recovery
Excellent Extraction
(KD > 2)
Ester Yield: 75% of
Theoretical
 Conclusions
Technical Issues
pH and Avoidance of Salt Coproduction
Dilute Broths

Advantages of Platform Viewpoint

New Routes Based on Biology and Chemistry
Market Diversification
 Acknowledgements

US Department of Energy - Inventions and

Innovation Program (Grant Number DE-
FG36-03GO13010)

Support by US DOE Does Not Constitute

an Endorsement by US DOE of the Views
Expressed in this Presentation