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Enzyme Catalysis

 
for Biomass Based Diesel Fuels
     Department of Chemical Engineering,

North Carolina State University

CHE 596-16 Biodiesel Production Technology

February 20, 2014  

Rachel Burton

February 20, 2014


“People  don’t  buy  what  you  do,  they  buy  why  you  do  it.”  –Simon  Sinek  
Outline
•  Why  use  an  enzyma:c  approach  to  
biodiesel?
•  -­‐Benefit  over  chemical  catalysts

•  Overview  of  enzyma:c  biodiesel


•  -­‐Enzymes  for  commercial  produc:on
•  -­‐Transesterifica:on
•  -­‐Esterifica:on  

•  Enzyme  Reuse  
Quick Definitions
TAG = Triglycerides (fat/oil)

DAG = Diglycerides

FFA = Free fatty acids

FAME (or ME) = Fatty Acid Methyl Esters (biodiesel made using methanol)

Immobilized vs. Liquid Enzymes


CALB = Candida Antarctica Lipase B



Novozym 435 = CALB immobilized on a plastic support (.5mm beads)

TL = Thermomyces Lanuginosa lipase


Advantages of Enzymes for Biodiesel
Sustainability Profile
•  National Research Council s Committee on
Water Implications of Biofuels Production: 1
gallon of wastewater: gallon of biodiesel
produced. (Oct. 2007)
•  2007, Harding et al, LCA analysis between
enzymatic & chemical catalysis for biodiesel
•  Flammable and hazardous substance exposure
reduction
Improved  
performance  linked  
to  lower  energy  
requirements  for  
hea:ng  in  the  
process  
 
 
 Terrestrial  
ecotoxicity  levels  are  
reduced  by  40%  with  
the  removal  of  
mineral  acid  from  
the  process    
   
Hurdles to Enzymes for Biodiesel

• 15 years of research


• Hundreds of articles
• Many different
enzymes, reaction
conditions, etc.
• Overall conclusion in
most cases – too
expense
Why Now?
Chicken or the egg problem:
enzyme development vs. market
development.

Confluence of events:
•  Biodiesel industry is more mature
and more secure
•  Drive for lower cost feedstocks,
presence of high FFA virgin oils
•  Demand for increased fuel quality
•  Competition for fats/oil from
renewable diesel will push efficiency
•  Industry recognition of problems
with soaps, low quality glycerin, and
difficulty of acid esterification

http://www.channelshirt.com/product/13/208/Chicken-Or-Egg-
Tshirt.html

Causes process development:


•  Commercial enzyme reuse trials
•  Lower cost enzyme production
Commercial Viability!

Access to affordable
Feedstock prices rising for the 2nd time;
feedstocks now in accordance to petrol market

Soy oil

Tallow

Yellow Grease
Reusability
Enzymes used for biodiesel production lose
activity by:

High heat (>50C or >122F)


Excess alcohol

In addition, Immobilized enzymes can lose


activity by:

Any alcohol out of phase


Large excess of alcohol in phase (~5% or more)
Glycerol out of phase
High shear can cause immobilized enzymes to come
off of the carrier
Certain polar contaminants
Mineral acids

Temporary vs. Permanent activity loss


Reusability of
Temporary: physical blocking of active sites
Permanent: denaturing due to excess methanol enzymes is the key
to commercial
viability!
A brief history
Early Work (1987 - 1995)
•  Studied cosolvents like iso-octane, hexane, diesel fuel.
•  Evaluated aqueous, non aqueous, and solvent-free systems, different types of
alcohols, impact of water
•  Studied a wide variety of liquid enzymes
•  Mike Haas, Tom Foglia, Martin Mittelbach, and many others
•  No real biodiesel production, so these were interesting but not practical

Resurgence of interest (1999 - 2008)


•  Better immobilized enzymes
•  Solvent free systems, good enzyme reuse
•  First large scale plant in China using cosolvents ( tert-butanol )

Current Developments
•  Novozymes developing enzymes, immobilization techniques, lowering costs
•  Piedmont Biofuels
•  Transbiodiesel in Israel
•  Sunho in Taiwan
•  Blue Sun & Viesel
•  Renewed interest from universities and private biodiesel producers for lab and
pilot sized reactors
Summary Articles

• Haas, 2002 (review of early literature)


• Fjerbaek, 2009
• Ranganathan, 2007
• Basic components of reviews
• enzyme type
• liquid vs immobilized
• support type
• reaction conditions
• conversion
• number of reuses
• tolerance to water, methanol
Fjerbaek et al.: Biodiesel Production
Using Enzymatic Transesterification.
2009.

Cosolvents – Li (2006)
Tert-butanol as
cosolvent
Disadvantages
Advantages •  Large amount of co-solvent required
•  Can use more excess which must be removed at the end via
methanol without distillation
deactivation •  Still had high FFA at end of process
•  Deactivation due to •  Reaction rate still slow
glycerol (clogging) does
not occur
•  Impressive enzyme reuse

Built full scale


plant based on
this process
in China



Cosolvents – Zheng (2008)
•  Tert-Amyl Alcohol as cosolvent

Batch Reactions
•  1.78g soybean oil
•  2 – 6ml amyl alcohol
•  2% Novozym 435 (CALB)
•  reaction time ~ 15 hours

•  Add graph here

Excellent reuse, but same


problems as Li
Watanabe and Shimada (2001, 2005)

No cosolvent
Use multi-stage methanol addition
to avoid deactivation
Tested batch and continuous

Advantages
•  No cosolvents
•  Minimize methanol use
•  Excellent conversion (98%+)
•  Good enzyme reuse

Disadvantages
•  Still has long reaction times
•  Still had high FFA at end of
process
•  Enzyme reuse still not
commercially viable
Watanabe and Shimada (2001, 2005)

Packed

Bed

Reactors
Watanabe and Shimada (2001, 2005)
Esterification – very fast!

Determined maximum methanol


allowable before deactivation
•  6.3% by weight methanol

Performed Enzyme Reuse Trials


•  Excellent conversion (98%+)
•  Good enzyme reuse




Novozymes (2009)
Longevity trials: Esterification Still has deactivation

Reaction Conditions Relatively large excess methanol


•  20% by volume methanol, 2 stage use (~2:1)
reaction, 45C,
•  Majority of reaction finished in 60 Still high FFA content (3 – 5%) after
minutes 2nd stage
•  Blended FAME, MeOH, and PFAD to
address the high melting point
U.S. Dept. of Energy: Piedmont Biofuels –
Commercial Focus
Esterification

Achieving ASTM specifications

Commercial viability (enzyme reuse)

Real World Feedstocks

•  Yellow Grease (15% FFA)


•  Brown Grease (80%+FFA)
•  Palm, soy, and others
Enzymatic approach for Waste-Water Reduction

• Began investigation of enzyme catalysis for


biodiesel, 2009  

• Focus on esterification first  

•  2010---Lab working on Pilot scale (35 gal.)  


•  2011/2--- Pilot moving to Commercial  
•  2013---on-going Commercial Integration  

•  Validation for multi-feedstock production


scheme  

• First to demonstrate enzyme biodiesel to


meet full ASTM specification.  
CSTR system with alcohol metering,
• Economic analysis & Enzyme reuse patent pending
Enzymes For Biodiesel Production

Commercial
formulations:
Callera series
Commercial Build
Feed Tanks
How can you use this process?
•  Enzyma:c  Esterifica:on:
•  A.  Pretreatment    for  exis:ng  chemical  plants
•  B.  Full  conversion-­‐-­‐Esterifica:on  for  High  FFA  
feedstocks
•  C.  Enzyma:c  Polishing  for  TRANSESTERIFICATION  
followed  by  the  enzyma:c  esterifica:on  PROCESS  
•     -­‐-­‐100%  enzyme-­‐based  process  in  2  steps  
Replace Sulfuric Acid Pretreatment
• Esterification using Callera Ultra/L  
Immobilized CALB or Liquid CALB  

• Replaces traditional sulfuric acid


technology  

• Incoming Feedstocks: 2-100% FFA  

• Patent Pending, continuous process  

• Low temperature process  

• Maintains water balance  

• 6-12 times less methanol than acid


esterification  
FAeSTER Process:  
• No acidic methanol sidestream
Fatty Acid  
esterification
Feedstock Pretreatment
Esterification occurs quickly within 30 minutes

Achieves acid value specification by 90 minutes


Liquid enzyme transesterification
•  Heat/Circulate Feedstock (42 gallons, 40ºC)
•  Initial Batches
–  1%-2% enzyme by feedstock weight
–  Aqueous Phase of 20% by feedstock weight
•  40% water
•  60% glycerol
•  Methanol Dosing
–  1.7 molar excess of methanol to feedstock
–  25% initial
–  Remainder metered in over 5 hours
•  Sampling
–  1, 2, 4, 6, 8, 10hr
•  FAME Phase: Bound Glycerine & FFA
–  24 hr
•  Aq. Phase: Glycerol, Methanol, H2O, Enzyme
–  Determine Aq. Phase Removal & Methanol Dosing
–  Part II
Pilot Scale Results
Commercial scale
Results

In-spec Bound Glycerin 0.15%


1.5FFA%
Reaction complete in 6-8 hours
 
2700 gallon reactor, coil-heated,
SS, cone-bottom,
35-40C/95-104F,
20% water/glycerol,
1.7:1 methanol:FA

Reaction monitored:
1, 2, 4, 6, 8 hrs.
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NOVOZYMES PRESENTATION

NOVOZYMES PRESENTATION
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2/19/14

Alkaline wash reduce free fatty acids and glycerides


and make final biodiesel meet specifications.
The soap stock is acidified and sent back

BG = 0.17%

3  

2.5  

2  
TG  
%  in  FAME  

1.5   DG  

MG  
1  
FFA  

0.5  

0  
Before  CW   AXer  CW  

BG = 0.10%
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NOVOZYMES PRESENTATION

The enzyme works at the oil/water interface


Mixing is important – we need a an emulsion with a large
surface area between oil and glycerin/water phases

Mixing

Oil/FAME

Glycerin/water
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NOVOZYMES PRESENTATION

Enzyme process works well with any content


of free fatty acids
Reaction at interface
Glycerides + MeOH
glycerides/glycerin + FAME

Glycerides + H2O
glycerides/glycerin + FFA

FFA + MeOH
FAME + H2O

D
incr riving
d ec e p
rea asing roces
sing Met s by
Gly h
cer anol a
ol a nd
nd
Wa
ter
Balancing Act
 
Affect of Water:
Too  much  water  leads  to  reac:on  with    
FAME  back  to  FFA.  
Too  li\le  water  leads  to  enzyme  inac:vity.  
 
Affect of Methanol:  
Excess  methanol  inhibits  the  enzyme.  
Too  li\le  methanol  slows  reac:on.    

Loss of Active Enzyme:  


 Loss  of  Enzyme  =  slower  reac:on  rate.  
100% Enzyme-Based Fuel meets
ASTM D6751
– 
2010: ASTM D6751
achieved using only
immobilized enzymes  

2011: ASTM D6751


achieved using Liquid
TL & CALB  

2012 + :  
Commercial Scale
Integration
Glycerol from Enzymatic
Process
•  High purity Glycerol
99.6%

•  Economic Impact to Chemical glycerol vs. enzymatic glycerol


the producer:
•  40-50 cents/lb.
• 

Chemical FAME/glycerol vs. FAME/


 
enzymatic glycerol
YELLOW GREASE FEEDSTOCK
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Tsinghua China – Hunan plant


Lipase-mediated industrial scale production of biodiesel (20,000t/y) put
into operation Dec 8, 2006. Initially in a process with t-butanol;
Now restarting in solvent free process
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NOVOZYMES PRESENTATION

Blue Sun - USA.


3 enzyme reactors of 300 m3 each
Started early 2013

Final product
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NOVOZYMES PRESENTATION

Viesel Biofuels – Florida USA


Summary
Variables Type of Enzyme
Methanol use (minimize) Candida antarctica lipase B
Cosolvents (minimize) Thermomyces lanuginosa
Reaction time (minimize) Pseudomonas cepacia
Presence of water (minimize) Rhizomucor miehei
Ester conversion per minute (minimize)
Final ester conversion (minimum 98% esters) Carrier
Final FFA content (maximum 0.25% FFA) Polypropylene
Temperature (35 – 50) Polyethylene
Activated Carbon
System design Enzymes as a biodiesel catalyst Silica
PBR
CSTR
are extremely well studied
Form of enzyme
Continuous Liquid
Batch but also very complex. Immobilized
System robustness
multi-feedstock
tolerance to impurities Still, probably worth the effort...

Lower Energy Use Non-Toxic Scale Neutral


Low Methanol Use
High Quality Glycerin More Complete
Separations Esterify and Transesterify
No Soap Formation

A more competitive biodiesel industry

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