donald glatz
TRANSCRIPT
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Extraction of Chemicals from Fermentation Broths using a KARR® Column
Don Glatz
2014 Bio World CongressPhiladelphia, PA
May 2014
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What We DoSpecialists in Process Design and Construction of Modular Mass Transfer Systems for Solvent Recovery, Wastewater Stripping, Product Purification, Organic Chemical Separations, Acid Gas Treating and Environmental Applications. KMPS also provides engineered components and engineering services, including equilibrium data development, process development and pilot plant testing.
Objective:
Provide economic solutions to separation problems.
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Introduction for Presentation
• Recently – large emphasis on production of chemicals from biomass (fermentation, algae)
• LLE is logical preliminary step because chemicals are low concentration & higher‐boiling than water
• KARR® Column provides high efficiency and is ideal for these systems because of high tendency towards emulsification
• Presentation outlines LLE for biomass and advantage of the KARR® Column
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Fermentation Process with LLE
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Fermentation
Additional Dist.Product(s) Purification
Distillation (Solvent Recovery)
Broth TreatmentFiltrationCentrifuge
Cell Disruption
Liquid‐Liquid ExtractionSolvent Stripping
Recycle Solvent
Spent Broth Recycle
Solvent
Extract
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Liquid-Liquid Equilibrium Data
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4.07.929950MF
SE
7.9299
0.250
0.8
Raffinatein SoluteConc.Extractin SoluteConc.M
0.21.00.2
FeedinSoluteRaffinateinSoluteU
Fraction Unextracted
Distribution Coefficient
Extraction Factor
A – 99
B – 0
C – 1
100
Feed (F)
A – 0
B – 50
C – 0
50
Solvent (S)
A – 0
B – 50
C – 0.8
50.8
Extract (E)
A – 99.0
B – 0
C – 0.2
99.2Raffinate (R)
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Solvent Selection and Generation ofLiquid-Liquid Equilibrium Data
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Variable Speed Drive
ThermometerBaffle
Tempered Water In
Drain
1 – Liter Flask
Tempered Water Out
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LLE Curve for Extraction of Dicarboxylic Acids from a Fermentation Broth
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0.00
0.01
0.02
0.03
0.04
0.05
0.06
0.07
0.08
0.09
0.000 0.005 0.010 0.015 0.020
Extract C
omp. (W
t. Frac., Solute Free)
Raffinate Composition (Wt. Frac., Solute Free)
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Broths Require Many Theoretical Stages
• E = m (S/F)• Chemicals in broth typically
have low distribution coefficient (m)
• High number of theoretical stages required
• Example:E =m(S/F) = 0.8(1.63) = 1.310 stages require for 98% recovery
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1.00.80.6
0.40.3
0.2
0.10.080.06
0.040.03
0.02
0.010.0080.006
0.0040.003
0.002
0.0010.00080.00060.0005
1 2 3 4 5 6 7 8 10 15 20Number of Ideal Stages
X BR/X B
F= Fractio
n Une
xtracted
E = 0.3
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Selection of Extractor
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Used primarily in the metals industry due to:‐ Large flows‐ Intense mixing‐ Long Residence time‐ Corrosive fluids‐ History
Used primarily in thepharmaceutical industry due to:‐ Low Volume‐ Short Residence time‐ Handles Small Gravity Diff.‐ History
Static Agitated
Spray Packed Tray Pulsed Rotary Reciprocating
Rarely usedUsed in:‐ Refining‐ Petrochemicals
Example:‐ Random‐ Structured‐ SMVPTM
Used in:‐ Refining‐ Petrochemicals
Example:‐ Sieve
Used in:‐ Nuclear‐ Inorganics‐ Chemicals
Example:‐ Packed‐ Tray‐ Disc & Donut Example:
‐ RDC‐ SCHEIBEL®
Example:‐ KARR®
Used in:‐ Chemicals‐ Petrochemicals‐ Refining‐ Pharmaceutical
KARR® and SCHEIBEL® are registered trademarks of Koch‐Glitsch, LP.
Mixer Settlers Column Contactors Centrifugal
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Centrifugal Extractor – NOT IDEAL
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Centrifugal force is good for phase separation
Disadvantages for Fermentation Broths:• Insufficient efficiency:
typically need too many theoretical stages
• Susceptible to fouling and plugging due to small clearances
• High speed device requires maintenance
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Packed or Sieve Tray Column – NOT IDEAL
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Feed (F)
Solvent (S)
Extract (E)
Raffinate (R)
Disadvantages for Fermentation Broths:• Poor efficiency due to poor
phase contact: biochemical processes typically require many theoretical stages to achieve product recovery
• Sometime agitation is required to achieve phase separation
• Broths have high tendency to foul and plug
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Agitated Columns with Rotating Internals- NOT IDEAL
Characteristics with Fermentation Broths:• High shear causes emulsification –
RDC with rotating discs is especially problematic
• Turbine type impellers (e.g. SCHEIBEL® Column) – less shear than RDC but still prone to emulsification
• Non‐uniform shear of rotating internals – tip speed creates finer droplet size
• Columns tend to flood before small droplets can be produced and sufficient dispersed phase hold‐up is generated
• Not recommended for highly fouling systems
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LightPhase In
HeavyPhase In
LightPhase Out
HeavyPhase Out
Variable SpeedDrive
InterfaceControl
Interface
VesselWalls
RotatingShaft
TurbineImpeller
HorizontalInner Baffle
HorizontalOuter Baffle
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KARR® Reciprocating Column - IDEAL
Characteristics:• Reciprocating plate stack
imparts uniform shear mixing• Narrow droplet size
distribution – does not generate “fine droplets”
• Internals can be metal or plastic to create the proper wetting conditions
• Year of experience show that this type of mixing is best for systems that emulsify
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LightPhase Inlet
Sparger
HeavyPhase Inlet
Sparger
LightPhase Out
Interface
Baffle Plate
Tie Rods& SpacersPerforated
Plate
DriveAssembly
InterfaceControl
HeavyPhase Out
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KARR® Column Plate Stack Assembly
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Recovery of Carboxylic Acids fromFermentation Broth
• Broth generated by fermenting cellulosic materials – ~5% acids
• LLE Goal: >95% recovery (high purity) and minimal solvent use
• Ethyl acetate solvent – but emulsified easily
Preliminary Data in RDC Columns• Difficult operation due to
emulsification• < 90% acid recovery • High S/F ratio – 2.0KARR® Column Required
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Pilot KARR® Column for Carboxylic Acids1” diameter x 12’ Plate Stack
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Hot Oil
Whole Broth Feed Ethyl Acetate
Variable Speed Drive
Aqueous Out
(Raffinate)
Organic Out (Extract Phase)
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Pilot Plant Data forFermentation Broth Extraction
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RUN Plate Stack Ht. Capacity Temp. S/F Ratio Agitation Acid Recovery# (feet) GPH/ft2 C SPM %1 12 700 23 1.7 30 95.02 12 700 23 1.7 40 97.53 12 700 23 1.7 50 Flooded4 8 700 23 1.7 30 93.35 8 700 23 1.7 40 Flooded6 10 700 23 1.7 30 96.37 12 650 23 1.5 30 96.58 12 500 23 1.5 40 97.69 12 700 23 1.5 30 94.310 12 650 45 1.5 30 98.311 12 650 45 1.5 50 98.712 12 650 45 1.5 60 Flooded
NOTE: All runs performed in a 25 mm diameter KARR® Column
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Extraction Testing Results
• KARR® Column is correct design for this process which failed in RDC column
• S/F ratio improved to 1.5 (client expected 2)• 96‐97% recovery at room temperature and 98‐
99% recovery at 40‐45 C. Approximately 7 theoretical stages generated.
• Design capacity 650 GPH/ft2
• Complete system (LLE + distillations) designed, fabricated, and installed including KARR® Column installed on right
• LLE testing identified “unknown” component
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Recovery of Carboxylic Acids from BrothsUsing a Low Boiling Solvent
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FermentationBroth
5 % carboxylicacids
Solvent:Ethyl Acetate
Extraction
Raffinate Stripping
Solvent Recovery
Raffinate
RecycledEthylAcetate
Extract
Carboxylic Acids
Aqueous Raffinate
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Application: Extraction of Algae Oil
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Recovery of “oil” from broth generated in algae pondRequirement ‐ >95% recovery of oilMinimization of solvent usage critical to economics (solvent recovery)Preliminary Data in Mix‐Decant (Batch)• Extremely prone to emulsification• Large solvent usage due to multiple
mix‐decant steps• Poor phase separation caused large
solvent loss and generation of waste
KARR® Column required
Extraction Technology Groupwww.modularprocess.com
Extraction Technology Groupwww.modularprocess.com
Pilot Plant Data for Algae Broth Extraction
All runs performed in a 25 mm diameter, KARR® Column
RUN Plate Stack Ht. Capacity Temp. S/F Ratio Agitation Oil Recovery
# (feet) GPH/ft2 C SPM %
1 12 500 65 1.0 30 88.3
2 12 500 65 1.0 50 97.8
3 12 500 65 1.0 75 99.0
4 12 500 65 2.0 30 96.3
5 12 500 65 2.0 75 89.3
6 12 500 65 1.0 50 98.4
7 8 500 65 2.0 50 93.1
8 8 500 65 1.0 50 90.8
9 12 700 65 1.0 50 85.1
10 12 900 65 1.0 40 Flooded
11 12 500 65 0.8 50 98.2
12 12 500 65 0.5 50 97.6
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Summary – Algae Oil Extraction
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• KARR® Column is the correct design for this process – good phase separation.
• At 500 GPH/ft2 & 12’ plate stack height, 98% recovery achieved for S/F ratio = 0.5 ‐1.0
• Product recovery decreased for plate stack height of 8’
• Product recovery decreased at 700 GPH/ft2 and column was unstable at 900 GPH/ft.
• Demonstration plant column designed with fabrication pending.
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Conclusions
• LLE is excellent first step for recovery and purification of chemicals from broths created by fermentation, algae or other biomass processing
• Agitated columns are required in order to generate sufficient theoretical stages for high product recovery and minimization of solvent usage which is important for process economics.
• Agitation via reciprocation (KARR® Column) is the optimal choice for system that emulsify.
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Thank You!
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QUESTIONS???
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Pilot Plant
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LLE Equilibrium and Operating Lines
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Solute Free Basis
R’
E’
F’
S’
XBF
Graphical Solution
Y
X
YBE
YBS
XBR
∗
∗
DistributionCoefficientonSoluteFreeBasis
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DCA Extraction – Theoretical stage calculation for 98% extraction at solvent to feed ratio of 1.0
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0.00
0.02
0.04
0.06
0.08
0.10
0.12
0.000 0.020 0.040 0.060 0.080 0.100 0.120
Extract C
omp (W
t Frac., Solute Free)
Raffinate Composition (Wt Frac., Solute Free)
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456
(0.136, 0.118)
1