Professional Documents
Culture Documents
for Biomass Based Diesel Fuels
Department of Chemical Engineering,
North Carolina State University
CHE 596-16 Biodiesel Production Technology
February 20, 2014
Rachel Burton
• 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)
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
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Soy oil
Tallow
Yellow Grease
Reusability
Enzymes used for biodiesel production lose
activity by:
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
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
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!
Novozymes (2009)
Longevity trials: Esterification Still has deactivation
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
Reaction monitored:
1, 2, 4, 6, 8 hrs.
32
2/19/14
NOVOZYMES PRESENTATION
NOVOZYMES PRESENTATION
33
2/19/14
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%
34
2/19/14
NOVOZYMES PRESENTATION
Mixing
Oil/FAME
Glycerin/water
35
2/19/14
NOVOZYMES PRESENTATION
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.
2012 + :
Commercial Scale
Integration
Glycerol from Enzymatic
Process
• High purity Glycerol
99.6%
Final product
41
2/19/14
NOVOZYMES PRESENTATION