Introduction to a Disruptive Bio-butanol Technology Tong.pdf · 2013-08-07 · Market in need of Advanced Bio-fuel US Renewable Fuel Standard (RFS) caps corn ethanol at 15 bgy due

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


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%


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


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


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


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


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


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


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%


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


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


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


Enable Technology to Meet RFS2

14

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


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


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%


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.


Thank you

for your attention


Backup Slides

19


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

Documents

Introduction to a Disruptive Bio-butanol Technology Tong.pdf · 2013-08-07 · Market in need of Advanced Bio-fuel US Renewable Fuel Standard (RFS) caps corn ethanol at 15 bgy due