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August 15, 2019
NIPPON STEEL ENGINEERING CO., LTD. (NSE)
Kenichi Ogawa
Development of
Cellulosic Ethanol Process and
Utilization of
Process Residues (Lignin)
Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.
1. Nippon Steel Engineering (NSE)’s Bioethanol
Technologies
2. 2nd-Gen: Cellulose-to-Ethanol Technology
3. Byproduct: Lignin-to-Chemicals
Contents
2
Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.
1. Nippon Steel Engineering (NSE)’s Bioethanol
Technologies
2. 2nd-Gen: Cellulose-to-Ethanol Technology
3. Byproduct: Lignin-to-Chemicals
Contents
3
Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.
1st
Gen
era
tio
n
2n
d G
en
era
tio
n
Feedstock
Food Waste
Orange Pomace
Woody Biomass
Capacity
400 L/day Completion of Pilot Test (2006 - 2009 Kitakyushu)
Status
5,000 L/day Completion of Commercial Operation (2008 - 2017 Ehime)
250 L/day Completion of Pilot Test (2009 - 2013 Hiroshima)
Herbaceous Biomass
270 L/day Pilot Test (2015 - 2018 Philippine)
1.1 NSE’s Bioethanol Technologies
4
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Feedstock
- Food waste from industry / households
Capacity
- 10 wet-ton-biomass / day
- Ethanol production: 400 L/day
Characteristics
- High fermentation yield (Sterilization of bacteria in waste)
- Fuel oil recovery (700 L/day)
700L fuel oil
High fermentation yield
1.2 1st-Gen: Food Waste to Ethanol
5
Saccharification
Supported by NEDO
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Feedstock
- Citrus press liquor of orange pomace from juice industry
Capacity
- 100 wet-ton-biomass/day
- Ethanol production: 5,000 L/day
Characteristics
- Unique yeast with limonene tolerance
- Energy saving technology (Utilization of waste heat)
1.3 1st-Gen: Orange Pomace to Ethanol
6
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7
Chipping Pretreatment Solid-liquid Separation
Saccharification & Fermentation
Distillation Pentose Fermentation Ethanol
Steam
Alkali, Water
1.4 2nd-Gen: Woody Biomass to Ethanol
Feedstock
- Woody biomass (Eucalyptus)
Capacity
- 1 dry-ton-biomass/day
- Ethanol production: 250 L/day
Characteristics
- Integrated production system for cellulosic ethanol
(from biomass cultivation to ethanol conversion)
- Energy saving technology at distillation
Supported by NEDO
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8
1.5 2nd-Gen: Herbaceous Biomass to Ethanol
Enzyme
Air
Saccharification Fermentation
Chemical
Feed
stock
Raw Material Processing Pretreatment Separation
Yeast Culture
Feedstock
- Sugarcane bagasse
- Other herbaceous biomass
Capacity
- 1 dry-ton-biomass/day
- Ethanol production: 270 L/day
Characteristics
- High ethanol yield (World’s highest level)
- Process technology broadly applicable to various types of feedstocks
Ethanol
Process residue
Supported by “Financing programme to demonstrate advanced low-carbon technology innovation for further deployment
in developing countries” of the Ministry of the Environment, Government of Japan
Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.
1. Nippon Steel Engineering (NSE)’s Bioethanol
Technologies
2. 2nd-Gen: Cellulose-to-Ethanol Technology
3. Byproduct: Lignin-to-Chemicals
Contents
9
Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.
Asia is a Fast-Growing Ethanol Market.
(Annual growth of Asian market is more than 8%.)
Changes in Global ethanol production Ref: F.O. Licht, cited in Renewable Fuels Association, Ethanol Industry Outlook reports.
0
20,000
40,000
60,000
80,000
100,000
120,000
20
07
20
08
20
09
20
10
20
11
20
12
20
13
20
14
20
15
20
16
20
17
Million L/year Rest ofWorldPhilippines
Thailand
China
India
Canada
Europe
Brazil
USA0
1,000
2,000
3,000
4,000
5,000
6,000
7,000
2007 2010 2012 2014 2016 2017
Million L/year
Philippines
Thailand
China
India
Changes in Asian Ethanol Production
10
2-5% More than 8%
2.1 Global Ethanol Market
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2.2 Philippine Ethanol Market
11
87.50%
12.50%
Bioethanol
Others
- The Philippines is an attractive market. (Developed laws, Large amount of biomass,
etc.)
- Cellulosic ethanol from various types of feedstocks can increase production volume.
- Low cost feedstocks can reduce cellulosic ethanol production cost.
Molasses consumption
in the Philippine
Cost conception diagram
0
50
100
MolassesEthanol
CellulosicEthanol
Rela
tive P
rod
ucti
on
Co
st
CAPEX
OPEX(ExceptFeedstock)
Feedstock
Ref: SRA (The Sugar Regulatory Administration)
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Optimization of
Pretreatment conditions
Pretreatment Saccharification Fermentation
Key Technologies for High Ethanol Yiled
Low Enzyme Dosage High Performance Yeast
Bench Scale Facility in Japan Laboratory in Japan
12
Technology Application to
Various Types of Feedstocks
2.3 Cellulose-to-Bioethanol Technology
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Pilot Plant
4. Saccharification
Control Room
Laboratory
2. Cutter
3. Pretreatment
1. Feedstock
▼ Manila
CADPI ▼
5. Culture,
Fermentation
Tank
13
2.4 Cellulose-to-Bioethanol Pilot Plant
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- Reliable operation data was acquired from one and a half years of operation
at the pilot plant in CADPI.
- More than one hundred runs improved the process adaptable to various type
of feedstocks.
14
2.5 Long-term Operation with Various Feedstocks
0
20
40
60
80
100
120
0
2
4
6
8
10
12Ja
n
Feb
Mar
Ap
r
May Jun
Jul
Au
g
Sep
Oct
No
v
Dec Jan
Feb
Mar
Ap
r
May Jun
Jul
2017 2018
Cu
mu
lati
ve R
un
Nu
mb
er
Mo
nth
ly R
un
Nu
mb
er
Monthly Run Number
Cumulative Run Number
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0
50
100
150
200
250
300
350
Eth
ano
l Yie
ld (
L/T-
Bio
mas
s)
World’s highest level
of ethanol yield
2.6 High Ethanol Yield
- Ethanol yield of the pilot plant was the highest level in the world.
- Energy conversion efficiency from herbaceous biomass to ethanol is approx.
35% (Lignin Residues are recycled as boiler fuel in the ethanol plant.)
0
10
20
30
40
50
60
70
80
90
100
Re
lati
ve E
ne
rgy
(%
)
Cellulose Hemicellulos
Lignin
Glucose Xylose
Lignin Residue
Ethanol
Lignin Residue
Loss Loss
Feedstock Saccharifi-
cation
Fermen-
tation
15
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Hemicellulose is converted into xylose with sulfuric-acid and steam heating
- Crush into suitable size
- Select catalyst suitable for feedstock
- Control pre-treatment conditions (pH, time, temperature)
16
H Xylose
Hemicellulose Furfural (Fermentation Inhibitor)
C5
[%]
C6
[%]
CSI
Sacch
ari
ficati
on
Yie
ld
Cellulose Glucose
2.7 Key Processes - Pretreatment
Optimal Pre-treatment Conditions for:
- Efficient enzymatic saccarification
- Suppression of fermentation
inhibitor’s growth
CSI: Combined Severity Index
CSI = log (Time * exp{(Temp-100)/14.75)}-pH
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Pretreat- ment
Enzyme Dosage
Standard 100%
Standard 25%
NSE 25% 0
25
50
75
100
0 12 24 36 48
Rela
tive S
ug
ar
Co
nc.
(%)
Saccharification Time (h)
17
2.8 Key Processes - Saccharification
Cellulose is converted into glucose by enzyme. - Process the optimally pretreated biomass (in “2.7”) with hemicellulose
already dissolved. - Select the enzyme best-suitable for pretreated biomass
- Control saccharification conditions (pH, time, temperature)
NSE achieved 90% saccharification yield at 25% enzyme dosage.
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Glucose and xylose are converted into ethanol by special yeast.
- Special yeast with two abilities of converting xylose and inhibitor tolerance.
- Control fermentation conditions.
18
2.9 Key Processes - Fermentation Technology
50%
60%
70%
80%
90%
100%
Standard NSE
Ferm
en
tati
on
yie
ld (
%)
NSE achieved 95% fermentation yield
even without the COSTLY inhibitor removal process.
H
Tolerant Yeast
Inhibitor
Ethanol Detoxification
Sugar
NSE
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19
2.10 Handling Various Feedstocks
- Analysis of physical properties and components for other herbaceous biomass .
- Pretreatment process was adjusted as per analysis results.
NSE established the technology to enable 270 L/t of ethanol yield
using various types of herbaceous biomass
0
50
100
150
200
250
300
Sugar CaneBagasse
Other HerbaceousBiomass
Eth
an
ol Y
ield
(L
-Et/
t-D
M)
Other Herbaceous Biomass
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20
2.11 Cultivation Test
- Evaluation of Culture Conditions (Cultivation Time, Fertilizer Type and Quantity)
- Optimization of Collection and Transportation.
Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.
1. Nippon Steel Engineering (NSE)’s Bioethanol
Technologies
2. 2nd-Gen: Cellulose-to-Ethanol Technology
3. Byproduct: Lignin-to-Chemicals
Contents
21
Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.
Cellulose
Hemi
cellulose
Lignin
↓
Co-products
Biomass
↓
High
value-added
products
Ethanol
22
3.1 Extending the Cellulose-to-Ethanol Process
Pretreatment Saccharifi-
cation
Fermenta-
tion Distillation
Glucose
Xylose
Pilot Plant in Philippines
Crude
Lignin
Herbaceous
Biomass Fuel
Products
Lignin
Chemical
Products
Bio-
Chemical
Products Sugar
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- Main residue from the cellulosic ethanol production plant (By-product) Currently: Direct burning for heat energy use ONLY - Residual Lignin enhancement with High Added-Value Potentially: Establishment of production technology for New Bio-based Products
Residual Lignin from Cellulosic Ethanol Conversion Process
Saccharification
& Fermentation Ethanol
Chemical
Materials Separation
《The Cellulosic Ethanol Production Process》
Residual Lignin
Study on Converting Cellulosic Ethanol Residual Lignin into High Value Added Co-products
⇒NEDO’s project
Biomass Pretreatment
LIGNIN
23
3.2 Strategy of Residual Lignin Utilization
Boiler
Fuel
Establishment of Lignin Utilization
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Fractionation 1. Solid-Fractionated
Lignin
2. Solvent-Insoluble-
Solids Lignin
4. Solvent-Soluble
(Extracted)-Liquid
Lignin
4. Centrifuge-
Supernatant
Lignin
Solvent
Solubility -
Insoluble in organic
solvent
Soluble in organic
solvent Water-Soluble
Molecular
Weight - 3,000 ~ 10,000 3,000 or less 1,000 or less
Characteristics
High Calorific Value
High Ash-Melting
Point
Low Sulfur,
Low Salt
Low Denaturalization
Low Condensability
Affinity for Solvent
High Dispersion,
High Reactivity
Hydrophilic Lignin
Fractionation
Distillated
Liquor
Centrifugation
& Drying Solvent
Extraction
Ethanol
Herbaceous
Biomass
4. Liquid
Fractionation
Solid
Fractionation
3. Solvent-Soluble-
Liquid Lignin
2. Solvent-Insoluble-
Solids Lignin
3.3 Separation of Lignin Fraction
24
Lignin can be separated into 4 fractions by centrifugation and solvent
extraction.
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3. Solvent-Soluble Lignin
1. Solid-Fractionated Lignin
Low-Sulfur
Low-Salt
High Dispersion
High Reactivity
High Calorific Value
High Ash Melting Point
Low Sulfur
Characteristics Industry
Power Plant
Chemical
Application
2.Solvent-Insoluble Lignin
Low-Sulfur
Low-Salt
Low-Denaturability
Low-Condensability
25
Solid Fuel
Activated Carbon
Electrode(Additional Reforming)
Cement
Agrichemicals Additive Cement
Granular Wettable Powder
Chemicals
Cement
Ink
Phenolic Resin
Epoxy Adhesive
Concrete Admixture
Inkjet
Dispersant
3.3 Application of Lignin
Application test using lignin is ongoing with user companies.
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Non-edible Biomass to Resource
- with Advanced Technology
The projects were supported by
Roxas Holdings, Inc.
The Ministry of the Environment and
The New Energy and Industrial Technology
Development Organization
26