Development of Cellulosic Ethanol Process and Utilization

Copyright©2019 NIPPON STEEL ENGINEERING CO., LTD. All Rights Reserved.

August 15, 2019

NIPPON STEEL ENGINEERING CO., LTD. (NSE)

Kenichi Ogawa

Development of

Cellulosic Ethanol Process and

Utilization of

Process Residues (Lignin)


1. Nippon Steel Engineering (NSE)’s Bioethanol

Technologies

2. 2nd-Gen: Cellulose-to-Ethanol Technology

3. Byproduct: Lignin-to-Chemicals

Contents

2



Technologies



Contents

3


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


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


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


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


Characteristics

- Integrated production system for cellulosic ethanol

(from biomass cultivation to ethanol conversion)

- Energy saving technology at distillation

Supported by NEDO


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


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



Technologies



Contents

9


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


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)


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


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


- 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


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


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


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.


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


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


20

2.11 Cultivation Test

- Evaluation of Culture Conditions (Cultivation Time, Fertilizer Type and Quantity)

- Optimization of Collection and Transportation.



Technologies



Contents

21


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


- 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


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.


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.


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

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Documents

Development of Cellulosic Ethanol Process and Utilization