Japanese National treasurethe World Cultural Heritage in 1993 Himeji Castle in spring(Himeji City HP)

Dr.Takashi Arai 　　　　　　　and

Yuichirou Hirai

Daicel Corporation,JAPAN

Technologies and Market Outlook on Bio-Chemical Extraction from　Biomass

Started from CelluloidStarted from Celluloid Celluloid was Bio-based product

Incorporated Sept. 8, 1919Employees ca. 1,972Head Office TokyoConsolidated Sales US$ 3.86 billion

DAICEL was established under the name of

through a merger of eight celluloid producers in 1919

Fiscal year ending March 31, 2010. 1US$=¥83

DAI nippon CEL luloid CO. Ltd.DAICEL Corporation

AboutDAICEL Corporation

was renamed

Since 1979, our company name has long contained the phrase “chemical industry.” However, the nature of our business has now expanded beyond this exclusive industry to encompass businesses related to assembly processes, as represented by the automotive airbag inflator segment, which has grown to become a core business.We changed our trade name to "Daicel Corporation" in order to demonstrate our company’s intention to continue expanding beyond the chemical industry segment by employing the proprietary technologies and unique expertise that evolved from the chemical-based foundation of our business.We are striving to become a truly global company in harness the energy of all members of our group worldwide.

Our company was renamed Daicel Corporation on October 1, 2011.

Principal Affiliates (Overseas)

Zhejiang, ChinaNingbo Da-an Chemical Industries Co., Ltd.

TaiwanPolyplastics Taiwan Co., Ltd.

Pennsylvania, U.S.AChiral Technologies, I

Kentucky, U.S.A.Daicel Safety Systems Topas Advanced Polym

New JeDaicel (U

Jiangsu, ChinaDaicel Safety Systems (Jiangsu) Co., Ltd.PTM Engineering Plastics (Nantong) Co., Ltd.

Shanghai, ChinaDaicel (China) Investment Co., Ltd.Shanghai Daicel Polymers, Ltd.Daicel Trading (Shanghai) Ltd.Polyplastics Trading (Shanghai) Ltd.Polyplastics (Shanghai) Ltd.Daicel Chiral Technologies (China) Co., Ltd.Shanghai Da-shen Cellulose Plastics Co., Ltd.

Hong KongDaicel Polymer (Hong Kong) Ltd.Polyplastics (China) Ltd.

SingaporeDaicel (Asia) Pte. Ltd.Polyplastics Asia Pacific Singapore Pte. Ltd.

Guangxi, ChinaDaicel Nanning Food Ingredients Co., Ltd.

Shaanxi, ChinaXi’an Huida Chemical Industries Co., Ltd.

ThailandDaicel Safety Systems (Thailand) Co., Ltd.Polyplastics Marketing (T) Ltd.

MalaysiaPolyplastics Asia Pacific Sdn Bhd

Mumbai, India Polyplastics Marketing (India) Pvt. Ltd. 　

Hyderabad, India Daicel Chiral Technologies (India) Pvt. Ltd. 　

KoreaDaicel Safety Systems Korea, Inc.Germany

Daicel (Europa) GmbHTopas Advanced Polymers GmbH

PolandDaicel Safety Systems Europe Sp. z o. o.

FranceChiral Technologies Europe S.A.S.

New Oxidation Catalyst Technology

Intellectual and IntegratedProduction System

Incombustible Celluloid

Celluloid & Cellulose Nitrate

Expanding Core Technologies

Chiral Technology

Fine Chemicals

C1 Chemicals

Peracetic Acid

Petrochemistry

Water-soluble Polymers

Spun Acetate Tow

TAC photographic film Base

Cellulose Acetate

Cellulose

Organic Chemicals

Polymer Chemicals

Explosives Engineering

Gunpowder & Propellants

Pyrotechnic Systems Acetate Plastics

Pilot Emergency-escape Systems

Plastics Processing

Assembly Processing

Engineering Plastics

Polymer Alloys Inflators

TAC for LCD Optical Films

Cellulose Acetate for LCD Optical Films 　TAC (Tri-Acetyl Cellulose) (No.1 maker in Japan)　

Cellulosic Derivatives

Cellulose Company

Tri-Acetyl Cellulose is used in protective films for LCD polarizing panels, which are an indispensable component of LCD TVs, notebook computers, cell phones, and other LCD applications.The potential scope of application for Tri-Acetyl Cellulose is expected to grow as the market for high-performance LCDs undergoes greater expansion in the future.

HOME PAGE

Social and Environmental Initiatives

Social and Environmental Initiatives②

Using Bio-ethanol as a Raw Material in Chemical Manufacturing

We are developing a sustainable chemical industry that does not depend on fossil fuels. At Daicel, our approach is to manufacture chemicals from raw materials derived from bio-ethanol, which is produced from biomass.

In 2007, Raw material of ethyl amines was converted to bio-ethanol. In 2009, Begins production of ethyl acetate using esterification process.

Ethyl amines

Ethyl acetate

Sugarcane

DAICEL Corporation　Target Domains

Copyright © DAICEL CHEMICAL INDUSTRIES,LTD. All rights reserved.

Himeji Research Center The Himeji Research Center, the nucleus of our R&D initiatives, undertakes basic research while also developing products and technologies for each industry. It

conducts research on elemental technologies for the entire company.

Ohtake Plant

Himeji Research Center

Aboshi Plant

Harima Plant

Himeji Technology Head Office

Hyogo prefecture

Green Sustainable ChemistryWith　Biomass

C3 chemicals and C4 chemicals

Break away from petroleum-dependent societyto a more sustainable society with biomass resources

Not a one-way carbon flow But a carbon cycling

NatureKey step;development of this route

Carbon Neutral and Biomass Conversion Catalyst

Development of Conversion Item from Biomass-derived Resources into Existing Chemical Products for General-Use　・Target: Reduction, Hydrogenation. 　　　　　　Petrochemistry is oxidation chemistry　・Demand for High Selectivity

Convert only target OH group

OH

HO

H

HO

H

OHOHH H

OH

HO OHOH HO

OH

OHOHOH

PetrochemicalsGasolinePlasticsOrganic solvents Consume

Waste

Glucose　　　bio-ethanol　　　glycerol　　　　erythritol

Biomass-derived Resources

Consume

Waste

Biomass resources

Photosynthesis

Biomass energyBiomass products

Derived Oil Biodiesel Fuel(BDF)

Antifreeze LiquidFor Airplane

NPR, IPA

n-propyl acetate(alternative for toluene)

1,3-PD

1,2-PD

Feedstock forEngineering-Plastic

C OOO OC C H23

n

MoisturizerFor Cosmetics

10,000t/y

Strategy for Glycerol Conversion Business

Surplus GLYCEROL

Palm

with

Chemical / Biological ProcedureUnder Development in Daicel

O

CO/H2

OH O OH OH

Shell

DuPont

Glucose OH OHOH

OH O OH OHCorn starch

Degussa

O

Acrolein

OH O OH OH

3-HPA

BIO

CHEM CHEM

CHEM CHEM

1,3-PD

Lab. (Klebsiella pneumoniae, etc.)

OH OHOH

OH O OH OH

13PD: Production Methods

Discontinued

Recombinant Coli

Anaerobic Bacteria

Discontinued

Chemical Procedure

Biological Procedure

There is no production of 13PD with chemical procedure at this moment.

DuPont Bio-13PD （Zemea, Susterra） High Grade：　Purity 99.98%

１，３ＰＤ ＰＴＴMakers Plant

Procedure Capacity Plan CapacityRemarks

Shell Chemicals USA EO （73,000） （20,000） Discontinued in 2009

German Acrolein （ 9,000） Discontinued in 2006Evonik,　Degussa

USA Acrolein （45,000）

Plan aborted

DuPont Tate & Lyle USA Bio 　45,000 Running since 2006

DuPont USA 　42,000 Enhancement +30,000t （2008）

Glory China 　30,000 Running since 2007

Sum Total 　45,000 　72,000

１，３ＰＤ、ＰＴＴ Current Capacity and Enhancement Plan　（order：T）

Enhancement

Withdrawn

13PD Makers in the World

Withdrawn

グリセリン輸入実績

0

2,000

4,000

6,000

8,000

10,000

12,000

14,000

16,000

2000 1

Q

2001 1

Q

2002 1

Q

2003 1

Q

2004 1

Q

2005 1

Q

2006 1

Q

2007 1

Q

2008 1

Q

2009 1

Q

2010 1

Q

数量

［T]

-

20

40

60

80

100

120

140

160

180

200

単価

[円/kg

]

GL輸入(数量)

GL輸入(単価)

粗グリセリン輸入実績

-

500

1,000

1,500

2,000

2,500

3,000

3,500

4,000

2000 1

Q

2001 1

Q

2002 1

Q

2003 1

Q

2004 1

Q

2005 1

Q

2006 1

Q

2007 1

Q

2008 1

Q

2009 1

Q

2010 1

Q

数量

[T]

-

10

20

30

40

50

60

70

80

90

100

単価

[円/kg

]

粗GL輸入(数量)

粗GL輸入(単価)

Purified-Glycerol　　：　Malaysia＞Philippines＞Indonesia　

Raw-Glycerol ：　Indonesia＞Malaysia, Singapore,　EU countries (Spot)

Ref. Foreign trade statistics (Japan Finance Ministry)　

Raw- and Purified-Glycerol Import Trend

Purified-Glycerol Import Experience Raw-Glycerol Import Experience

Quantity (T) Quantity (T)

Cost (¥/kg)Cost (¥/kg)

Quantity (T)Cost (¥/kg)

Quantity (T)Cost (¥/kg)

HO OH

HO

OH

HO OH

OH

1,2-Propanediol

1,3-Propanediol

internal OHhydrogenolysis

terminal OHhydrogenolysisConventional Technology

Cu catalyst(Cu-Cr, Raney Cu, Cu/Al2O3)

Rare metal composite catalyst

HO OH

OH

with >95% selectivity

~200℃

120℃

with ~70% selectivity

Technical Platform for 13PD Production

Innovation Technology

Our Technology possesses;

・High selectivity for internal OH hydrogenolysis・Higher reactivity than Cu catalyst at the same temp.

China,

Nanjing Univ.

Tendency of GLY Conversion Research

Korea,

Yonsei Univ.

Green Chem., 2011, 13, 2004–2007

Green Chem., 2010, 12, 1466～1472．

GlycerolBy-product of BiodieselProduced about 1,000,000T/YNo application for use

1,3PDProduction goal; 10,000T/YMonomer of Polytorimethylen-telephtalate (PTT)

1,3PDProduction goal; 10,000T/YMonomer of Polytorimethylen-telephtalate (PTT)

HOOH

HOOH

Our Work

+ H2 + H2OOH OHOH

OH OHSolid Catalyst

Our Technical Superiority　 ・High Selectivity for 13PD

　・Accomplishable production with reasonable catalyst cost　・Applicable to high concentration reaction (Small solvent)

Realization of Industrial Continuous Process!!　　・Scale-up about 108 times step-by-step　　・Ensuring of catalyst life over 1 years　　・Construction of purification process

Catalyst Activity with various GLY Sources

Less impurity in GLY source, longer the catalyst life.

GlycerolConversion

Continuous Reaction Time

Containing less impurities

Containing more impurities

We need…high-grade GLYCEROL resource following;・Containing less mineral salt (K, Na, Mg, Cl…)

　　・Containing less amino acid-derived compounds(-COOH, -NH2, -SH…)

C2 Frac.ethylene

C3 Frac.propylene

C4 Frac.Butadiene

PetroleumNaphtha

Benzene

Toluene

Xylene

Fractionating Tower

Although materials of petroleum product is naphtha fraction,　　　　　it comes to be altered with biomass-derived materials.

・Bio-ethanol

・Bio-glycerol (from bio-diesel)

・Bio-propanol

We are also trying development of switch of C4 material from naphtha fraction to biomass.

Practical Application of C4-Chemistry with Biomass

OH

HO

H

HO

H

OHOHH H

OHHO

OHOH

OH

HOOH

HOOH

O

O

Mitsubishi Chemical　Problems in cost and production efficiency.

14BD already available from butadiene.

Genomatica（USA）　　Collaboration with Mitsubishi Chemical for

commercialization since 2011.

HOOH

HOOH

OH

OH +

+

H2

OH

HOOH

O

OHO

OHO

Overview of a C4-tree from Glucose

Glucose Erythritol

Fermentation

14BD is also useful for engineering plastic monomer.(PBT; Polybutylene Telephtalate)

Daicel

OH

HO

H

HO

H

OHOHH H

OHHO

OHOH

OH HOOH

OH

OH +

+

OHGlucose Erythritol

Novelty and Superiority of Our Business

Novelty and Superiority

　①AccessibilityAs fermentation technique of glucose is ensured, erythritol iscommercially available.

　②Bi-product is also valuable; 1,3-Butanediol　　　Our existing product for moisturizer in cosmetics or shampoo.　　　We are Japanese No. 1 maker, and enhanced the production equipment

in 2009.　　③Variety of use application

Plastics ・Cosmetics ・Solvents ・Paint etc.

Daicel

Fermentation(Available)

①Promotion　　　②Suppression　

　　

percent conversion　55%

11%

11%36%

16%

21%

2% 1%

4%

Regulation of Production Selectivity

Target Products

Future outlook・The expansion of novel catalysts in combination with

the ability to design the chemical catalyst to fit the process.

・We believe that the industrial production of as many chemicals as possible with a catalyst using the assemblyarrangement techniques will result in decreased production cost, thereby leading to the construction of an innovative substance production system that can save energy in harmony with the environment.

This study was supported by a NEDOGrant for Innovation Promotion Program.※NEDO=New Energy and Industrial Technology　　　　　　　Development Organization

I would like to receive any question by email.　　　　ta_arai@jp.daicel.com　　　　　　　　　Thank you!