U.S. Department of Energy (DOE)Bioenergy Technologies Office (BETO)

2017 Project Peer Review Production of , diols from Biomass

March 9, 2017Denver, CO

PI: George W HuberCo-PIs: William Banholzer, James Dumesic, Ive Hermans, Christos Maravelias, Chris Marshall, Ilja Siepmann, Michael TsapatsisPost-doctoral Researchers: Jiayue He, Kefeng Huang, Bahman Elyassi (through 1/17)Graduate Students: Kevin J. Barnett, Zachary Brentzel, Samuel P. Burt, Robert DeJaco, Pranav U. Karanjkar (graduated), Siddarth H. Krishna, Nitish Mittal, Insoo Ro, Theodore Walker Project Dates: 2/1/2015- 01/31/2018

This presentation does not contain any proprietary, confidential, or otherwise restricted information1

http://images.google.com/imgres?imgurl=http://physics.usc.edu/%7Ewiphys/conference/logo_doe.gif&imgrefurl=http://physics.usc.edu/%7Ewiphys/conference/conference_main.html&usg=__n9rcZAj-bgJuGlBx1ETgUrYaoH8=&h=480&w=480&sz=110&hl=en&start=1&sig2=rEh21lNt8oL8Q181JYUZqA&tbnid=eNwGoopXENjl8M:&tbnh=129&tbnw=129&prev=/images?q=Department+of+Energy&gbv=2&hl=en&sa=G&ei=wMclSuXWCoaaMr6zxJEF

Catalytic Processes for Production of ,-diols from Lignocellulosic Biomass

2

Project Goal: Develop an economically viable approach (using inorganic catalysis) for conversion of biomass into 1,5 pentanediol(PDO) and 1,6 hexanediol (HDO) which will lower cost of cellulosic biofuels.Project Outcome: Experimental data, process and technoeconomicmodel for conversion of biomass (white birch, corn stover) into 1,5 pentanediol and 1,6 hexanediol.

3

Quad Chart Overview

Project start date: 2/1/2015 Project end date: 1/29/2018 Percent complete: 51%

Ct-E. Efficient Low-Temperature Deconstruction

Ct-H. Efficient Catalytic Upgrading of Sugars/Aromatics, Gaseous and Bio-Oil Intermediates to Fuels and Chemicals

Ct-J. Process Integration

Timeline

Budget

Barriers

Argonne National Lab: 9%Minnesota: 21%GlucanBio: 4%

Partners

Total Costs FY 12 FY 14

FY 15 Costs

FY 16 Costs

Total Planned Funding(FY 17-Project End Date)

DOE Funded 0 464,559 1,255,513 1,614,059

Project Cost Share(UW Madison) 0 107,212 256,439 342,150

Project Cost Share(Minnesota) 0 0 55,240 72,510

High value infrastructure compatible oxygenated commodity chemicals from biomass

4Source: Lux Research, Bio-based Materials and Chemical Intelligence Service, www.luxresearchinc.com, 2013 market prices

Volume (Million MT/yr.)

Pric

e ($

/MT

)

1,6-Hexanediol(~130,000 MT/yr)

Pric

e ($

/MM

BT

U)

10

20

30

140

150

0Natural gas

Crude oil ($50/bbl)

Biomass ($80/ton)

1,6-hexanediol ($4,400/ton)

Gasoline ($2.5/gal)

Source: ICIS, IEA

1,4 Butanediol(2,100,000 MT/yr)

http://www.luxresearchinc.com/

,-diols have many uses in the polymer industry

6

Particular 1,6-Hexanediol 1,5-Pentanediol 1,4-Butanediol

Applications

Polyurethanes Coatings Acrylates Adhesives Polyester Resins Plasticizers Others

Polyester plastics Polyurethanes Pharmaceuticals Inks and coatings Plasticizers Solvent and industrial

chemicals Others

Biodegradable plastics Hot melt polyesters Coatings Polyurethanes Adhesives Pharmaceuticals Fiber particle and

composite

Major players

BASF Ube Industries Lanxess Perstorp AB Lishui Nanming Chemical Fushun Tianfu Chemicals

BASF Ube Industries Marubeni Corporation Lishui Nanming Chemical

BASF Dairen Chemicals Lyondell Chemicals Shanxi Sanwei Group ISP Invista Mitsubishi Chemicals

Current market size (2013) $524 Million < $10 Million $5,550 Million

1,5-PDO and 1,6-HDO are produced from dicarboxylic acid as byproducts of caprolactam.

Approach for Conversion of Lignocellulosic Biomass to PDO and HDO

6

GVL/W Extraction

Lignocellulosic Biomass

R6Dehydration

R1Dehydration

Xyl

ose

R2Hydrogenation

THFA

LGO+HMF

R7Hydrogenation

THFD

MLe

vogl

ucos

enol

H2

H2 recyclepurge

1,5-PDOWastewaterBy-products

GVL/WaterH2SO4

H2

HMFSEP

1,6-HDOWastewaterBy-products

H2 recycle

By-products(purification to remove

acids)

purge

Furfural

GVL recycle

R3DEH

R9HYD

Lignin to Process Heat

H2SO4

SEPCellulose

LGO R8HYD

THFD

M

Solvent removal

THFD

M

Task A (Glucanbio) Task B (C5 route, UW)

Task C (C6 route, UW)Task DMembraneSeparation, Minnesota

Task EProcess design and economic analysis, UW

DHP R4HDR

2-HY-THP R5HYD

PDO

H2

H2 recycleH2O

THF recycle

H2 recycle

H2

SEP THFA

H2O

SEP

SEP

By-products

Task B and C High throughput Studies at ArgonnePhase II Task F: Integration All

Management Approach UW lead and all partners report to PI Each institutions responsible for own tasks Follow workplan and make sure we can complete

milestones Work with DOE review team to make sure workplan is

consistent with goals UW in charge of process integration One senior post-doc is in charge of economic modeling

which incorporates all the data Have regular phone calls (bimonthly to monthly) with

partners Quarterly reports to DOE

7

Technical Approach: The chemistry from Lignocellulosic Biomass to PDO and HDO

8

OHO OH O

OH

OHOOH O

OHn

O

O

O

+

O O

H

HO

OOHOH

HOOH

OHHO

OHH2SO4 Metal Metal-H2O H2 H2

1,6-hexanediol1,2,6-hexanetriol

LGO

HMF

Tetrahydrofuran-dimethanol(THFDM)Cellulose

O

O

OH

OH

O

O

OH OH

O

O

HO HO

O OHO

OH

OH

HO

OH

O

HO OH

OOH

OOH

OHHO

OO OH

1,5-pentanediol

Ni-Pd/SiO2

Xylose Furfural Tetrahydrofurfural Alcohol(THFA)

2-Hydroxytetrahydropyran(2-HY-THP)Dihydropyran

(DHP)

H2

RhRe/C

H 2

+H 2O-H

2 O

+H2

Hemicellulose

H2SO4 H2SO4-H2O

Lignocellulose biomass

C5 ro

ute

C6 route

MetalH2

Results: Conceptual process design based on laboratory data

9

A100FEEDSTOCK STORAGE

& HANDLING

RAW FEEDSTOCKA200

PRETREATMENT

RECYCLE WATER

A700WASTEWATER TREATMENT

XYLOSELIGNIN

A300FURFURAL

PRODUCTION & SEPARATION

A4001,5-PDO

PRODUCTION & RECOVERY

FURFURAL

PROCESS WATER

A500LGO+HMF

PRODUCTION

CELLULO

SE

THFDM PRODUCTION &

RECOVERY

LGO+HMF

A800STORAGE

A900BOILER & TURBO

GENERATORLIG

NIN

WWT CHEMICALS

A1000UTILITIES

EVAPORATION

ELECTRICITY

FEEDSTOCK

H2SO4

100 200 300 400

500

600

900

H2 610

1,5-PDO PRODUCT800

1,6-HDO PRODUCT810

GVL

PROCESS WATER H2 410GVL RECYCLE

THF

STILLAGE

230

210

H2SO4 220

240

HEAVY OIL

320LIME

310KCL 330

420

510

520

LIME 530

1,6-HDO PRODUCTION &

RECOVERY

250

450

540THF RECYCLE

620

H2650

PROCESS WATER 660

A600

COKE ON CATALYSTS430

VENT440910OFF-GAS710

720

STILLAGE

920C6 HUMINS

GVL

WASTE DISPOSAL340

930O

FF-GAS

730

630

VENT

640WASTE

THFA

940

HEAVY C6 740

670 VENT

960FGD LIME

950AIR

970PROCESS WATER

980STACK FLUE GAS

750BOILER BLOWDOWN

ASH990A

BLOWDOWN VENT990A

10

Minimum selling price is lower than current market price of 1,6 HDO and 1,5 PDO

Produce more 1,5 PDO than 1,6 PDO

Largest operating cost is steam cost.

Steam price assumes natural gas $5.6/MMBTU

(Current US natural gas price $3.0/MMBTU)

Feedstock costs not a very large expense

Results: Economic summary for base case process (all values in 2015$)Minimum Selling Price (MSP): $4,089 /ton

1,6-HDO Production 22,743 ton/yr 1,5-PDO Production 40,291 ton/yr

1,6-HDO Yield 0.063 ton/dry U.S. ton feedstock 1,5-PDO Yield 0.111 ton/dry U.S. ton feedstock

Feedstock + Handling Cost $80.00 /dry U.S. ton feedstock Internal Rate of Return (After-Tax) 10% Equity Percent of Total Investment 40%

Installed Equipment Costs Manufacturing Costs ($/ton HDO) Pretreatment $75,600,000 Feedstock + Handling $460 Furfural Production and Separation $18,700,000 GVL Solvent $59 PDO Production and Recovery $12,300,000 THF Solvent $199 LGO+HMF Production $106,600,000 Hydrogen $153 HDO Production and Recovery $37,600,000 Catalyst Recycling $89 Wastewater Treatment $37,300,000 Other Raw Materials 172 Storage $3,600,000 Purchased Steam $1,025 Boiler and Turbo Generator $60,300,000 Waste Disposal $18 Utilities $9,400,000 Net Electricity -$130 Total Installed Equipment Cost $361,400,000 Fixed Costs $282

Capital Depreciation $408 Added Direct + Indirect Costs $449,000,000 Average Income Tax $244 (% of TCI) 55% Average Return on Investment $1,111

Manufacturing Costs ($/yr) Total Capital Investment (TCI) $810,400,000 Feedstock + Handling $29,000,000

GVL Solvent $3,700,000 Installed Equipment Cost/Annual Ton