introduction to a disruptive bio-butanol technology tong.pdf · 2013-08-07 · market in need of...
TRANSCRIPT
Copyright 2013 ITRI 工業技術研究院
Introduction to a Disruptive
Bio-butanol Technology
BIT’s 3rd Annual World Congress of Bioenergy-2013
Nanjang, China, April 25-27 2013
Alex Tong
Vice President and General Director
GEL/ ITRI
2013. 05. 26
1
Copyright 2012 ITRI 工業技術研究院
Introduction to ITRI
� Non-profit research organization with more than 6,000
researchers generating over 1,000 US patents a year
2
� Global leading organization
in developing new businesses
and technologies
� Won six R&D 100 Awards in
2012
Copyright 2012 ITRI 工業技術研究院 3
Market in need of Advanced Bio-fuel
� US Renewable Fuel Standard (RFS) caps corn ethanol at 15 bgy due to limited GHG reduction (~20%)
� EU Renewable Energy Directives (RED) requires GHG Savings >35%, and 50-60% by 2017
GHG reduction requirementAdvanced Biofuel: 50%Cellulosic Biofuel: 60%
Copyright 2012 ITRI 工業技術研究院 4
Advanced Bio-fuels Still in Small-Scale Trial
� Cellulosic ethanol stalled at the moment
�Gevo cut back its iso-butanol production and
instead produced more ethanol on its demo plant in
Luverne, Minnesota
US Actual production significantly below allotment:
8.65 Mgal vs. 500 Mgal in 2012
Copyright 2012 ITRI 工業技術研究院 5
ITRI’s Solution – “ButyFix”--Highest carbon yield worldwide--
� Hydrolysis
� Eco-solvent: lower processing cost
� High reaction rate: lower equipment cost
� Mild operation condition: less energy consumption
� Fermentation
� No CO2 release : fully-utilized feedstock and better GHG
reduction
� Immobilized cell: easy to operate and reduce pre-culture cost
� C5 and C6 sugars fermentable: lignocellulose feedstock
� Less heat and gas generation: easy to scale-up
PretreatmentHydrolysis
FermentationProduct
Recovery
Lignocellulose Sugars ButanolButyric
Acid
Copyright 2012 ITRI 工業技術研究院
Challenges of Lignocellulose Pretreatment
6
Cellulose & Lignin(Solid Phase)
Hemicellulose(23-32%)
Hemicellulose(23-32%)
Cellulose(38-50%)Cellulose(38-50%)
Lignin(15-25%)Lignin
(15-25%)
Pretreatment/Conditioning
Hydrolysis Fermentation
Fermentation
� Extend of reaction� Inhibitor formation� Lignin degradation
� Detoxification needed� Wastewater treatment� Reactor design for high
loading
� Feedstock selective Enzyme
� Slow reaction� Sugar yield� Lignin suspend in the
solution
C5 Sugars solution(mainly from hemicellulose)
~10% sugar syrup result in ~5% EtOH
Copyright 2012 ITRI 工業技術研究院
Challenges of Enzymatic Hydrolysis Process
7
Require different pretreatment for different feedstock�Control of cellulose de-crystallization and lignin degradation�Enzyme activity and Inhibitors (HMF, FF, Phenol)
Component Percent Dry
Weight
Cellulose 40-60%
Hemicellulose 20-40%
Lignin 10-25%
Typical composition of biomass
Pretreatment Hydrolysis
1 2 3
GlucoseGlucan
Active siteEnzyme XyloseXylose
GlucanGlucan
LigninLignin1 2 3
Active siteEnzyme
Lignin Glucan
Cellulase
Xylose
Copyright 2012 ITRI 工業技術研究院
ITRI’s Eco-Solvent Process
8
Eco-solvent: lower processing cost
Homogeneous reaction: high reaction rate and lower equipment cost
Mild operation condition: less energy consumption
RCOOH +
heat, metal salt cat.
+ H2O
EsterificationSoluble
Hydrolysis
+ RCOOH
Using organic acid to hydrolyze ester to glucose
The crystalline structure of cellulose is destroyed by forming soluble ester
Copyright 2012 ITRI 工業技術研究院
Typical Experiment Results
9
Cellulose in ionic solution (II)
� 10 wt.% of microcrystalline cellulose tested
� Hydroxymethylfurfural (HMF) concentration lower than 0.03 g/L
� Total sugar yield determined by using 3,5-dinitrosalicylic acid (DNS) method
Optical microscope images of cellulose (100x): (a) before dissolving, (b) after dissolving
(a) (b)
Ionic solution
Esterification HydrolysisTotal sugar yield (wt.%)
Temp.
(℃)
Time
(hr)
Water content
(%)
Temp.
(℃)
Time
(hr)
Metal salt /organic acid
60 3 33 100 1.5 89
Copyright 2012 ITRI 工業技術研究院
Benchmarking of Hydrolysis Tech.
10
Advantages of ITRI hydrolysis technology:�Fast hydrolysis�High total sugar yield >95% (including sugar oligomers) �Low cost of pretreatment
Items Enzyme hydrolysis
H2SO4
hydrolysisHCl
hydrolysis
ITRI Ionic Solution
Biomass 17% corn stover 14.6% straw 10% wood10% sugarcane
bagasse
Pretreatment6% H2SO4 (aq), 6 atm, 158℃, 3~7 min
70% H2SO4(aq), 1 atm, 60-80℃, 1 min43% H2SO4, 80-100℃, total reaction time 2-6 hr
≧≧≧≧39% HCl(aq), 1 atm, 20-50℃, reaction time 8-16 hr
Salt/organic acid , 1 atm, 55℃, 3 hr100℃, reaction time~2hrHydrolysis
20 mg protein/g cellulose,48℃, reaction time
84 hr
Products
Yield
Total sugar 1
- - >90% 95% 3
Glucose 2 86% 70-80% >50% 68%
Xylose 2 80% 60-70% 90% 83%
1. Wt%.2. Mole%3. Theoretical yield≈111 wt%, ex.: glucan → glucose, 180/162=111%
Copyright 2012 ITRI 工業技術研究院 11
Fermentation
� Proprietary technology
fixes carbon in the product
during fermentation
�World-leading carbon
conversion efficiency to
butyrate
� 94% from glucose
� 61% from xylose
� Regulation of metabolic
pathway
Copyright 2012 ITRI 工業技術研究院
Carbon Fixation
12
13C-acetate12C-butyrate
13C-butyrate
12C-acetate
Butyrate
Acetate
13CO2
13C
Pyruvate
13C13C
Pyruvate
13C
Lactate
13C13C
Lactate
Acetyl-CoAH
m/e = 73
Copyright 2012 ITRI 工業技術研究院 13
World-Leading Yield
Butyrate/Butanol Carbon yield (%)
Solvent Yield (g/g-sugar)Reference
Current StatusTheoretical Maximum
ITRI94%
0.70 g Butyrate100%
UCLA 57%
0.35 g-Butanol67% Nature, 2008
UCB45%
0.28 g-butanol67% Nat Chem Biol., 2011
OSU62%
0.50 g-butyrate67% DOE Program
Commercial ABE Process
34%
0.21 g-butanol 67%
Current Opinion in Biotech., 2011
30% increase in solvent yield over cutting-edge technology
Copyright 2012 ITRI 工業技術研究院
Enable Technology to Meet RFS2
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Ref:1. M. Q. Wang et al., biomass and bioenergy, 2011, 35, 1885.2. M. Q. Wang et al., The Lifecycle Carbon Footprint of Biofuels, Proceedings of a conference January 29, 2008, in Miami
Beach, FL.3. J. Sheehan et al., 2003, V.7, No. 3–4, 117.
-20
0
20
40
60
80
100
Gasoline Corn EtOH ITRI CornBuOH
ITRI CellulosicBuOH
Gasoline
Fuel Distribution
Conversion
Feedstock transport
Feedstock Production
71(24.3%)
57.6(38.6%)
GH
G e
mis
sio
ns (
g C
O2
eq./
MJ) GHG Reduction
-1.3(101.4%)
93.8
Copyright 2012 ITRI 工業技術研究院 15
0
5
10
15
20
25
30
Corn EtOH ITRI Corn BuOH ITRI Cellulosic BuOH
Le
ve
lize
d C
ost ($
/GJ)
Operation
Capital cost
Feedstock cost
Cost Projection
Corn: $6.5/Bu (25.6 cent/kg)Corn stalk: 6.45 cent/kg
Copyright 2012 ITRI 工業技術研究院 16
Value Proposition
1. Reference: SRI PEP Report, 20082. Capacity: 150,000 MT/y3. Project life: 20 yrs4. Ethanol price 2.5 $/gal, , , , Butanol price 3.271 $/gal,Plant life 20yrs, Federal tax 35%, 200%
declining balance5. Interest: 1%
Copyright 2012 ITRI 工業技術研究院 17
Summary
� The mega trend in biofuel development is on non-food
feedstock, improved GHG savings and drop-in fuel
quality; Cost competitiveness against petro-fuel is the
ultimate goal.
� None of cellulosic bio-fuel facilities have reached
healthy operation at the moment.
� ITRI proprietary ButyFix technology, with world-leading
carbon conversion efficiency, can be a winner.
Copyright 2012 ITRI 工業技術研究院
Cost Estimation Baseline
20
� Baseline::::
� Capacity:150,000 metric ton/a
� Butyric acid conc. In fermentor:5 wt%
� Carbon yield from glucose to butyric:94.0%
� Carbon yield from C5 sugar to butyric:61.0%
� Butyric yield ( kg butyric/ kg sugar) :0.70 (corn), 0.61 (corn stover)
� Fermentation time:6.6 hrs/batch
� Yield of Methyl Butyrate:98 mole%
� Yield of Butanol via hydrogenation:99 mole%
� Aspen plus simulation based on cost in 2012 dollar
Corn Butanol Process– Starch content:62 wt%– Sugar yield:1.103 kg sugar/kg starch– Ref: SRI PEP Report 149A (2008)
Corn-stover Butanol Process– Corn stover:Cellulose 50.3wt%,
Hemicellulose 24.4 wt%,lignin 19.7wt%– Hydrolysis yield:Cellulose 90wt%,
Hemicellulose 90 wt% (Total sugar yield:0.67kg sugars/kg stover)
– Corn stover in hydrolysis tank:20 wt%– Butyric yield from sugars:61wt%– Lignin combustion for steam generation