emerging forest-based products and processes...wood chemistry med byrd associate professor process...

59
Emerging Forest-based Products and Processes Richard A. Venditti Forest Biomaterials (formally Wood and Paper Science) North Carolina State University January 20, 2011 Center on Global Change Duke University

Upload: others

Post on 18-Jan-2020

1 views

Category:

Documents


0 download

TRANSCRIPT

Page 1: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Emerging Forest-based

Products and Processes

Richard A. Venditti

Forest Biomaterials

(formally Wood and Paper Science)

North Carolina State University

January 20, 2011

Center on Global Change

Duke University

Page 2: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

[email protected]

• PhD, Chemical Engineering, Polymer Physics, 1994

Princeton University

• Taught at NCSU in Forest Biomaterials Department for

17 years

• Research (papers)

– Separation (Solid-Solid) Processes, Recycling (45)

– Novel materials from wood (plastics, gels, foams) (50)

– Biofuel production (10)

– Life Cycle analysis (0)

• On sabbatical, Duke University, January-July, 2011,

hosted by Robert Jackson and the Center for

Global Change

– Goal: learn LCA, energy/environment, others

– Goal: interact with all those interested, develop

collaborations

Page 3: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Outline

• Challenges in biofuels

• Forest Biomaterials Biofuels Research

• Examples of biofuels research

– Biomass procurement analysis

– Harvesting products as byproducts from wood

– LCA of biofuel production

• Summary

Page 4: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Sustainable Biofuel Industry?

• One should expect that, within a few thousand years of

its entering the stage of industrial development, any

intelligent species should be found occupying an

artificial biosphere which completely surrounds its

parent star. --Freeman Dyson, 1978.

• The notion that science will save us “is the sedative that

allows civilization to march so steadfastly towards

environmental catastrophe” --Kenneth Brower,

Science, 2010.

• Biofuels?

Page 5: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Global Carbon Cycle and Forests?

• Atmospheric concentration of CO2 has

increased by 31% since 1750 (to 390

from 280 ppm) and by 1.5 ppm/yr for

1980-2000 (IPCC 2001)

• Forests are significant in global GHG

(Landsberg & Gower, 1997):

– Cover 65% of the total land

– Contain 90% of the total vegetation

carbon

– 80% of total soil carbon in terrestrial

ecosystems

– Assimilate 67% of the total CO2 removed

from the atmosphere by all terrestrial

ecosystems

Page 6: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Global Carbon Cycle and Forests?

• Gower 2003

Page 7: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Global Carbon Cycle and Forests?

• Lal, 2008

Page 8: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

• The black numbers indicate how much carbon is stored in various reservoirs, in billions of tons ("GtC"

stands for GigaTons of Carbon and figures are circa 2004). The dark blue numbers indicate how much

carbon moves between reservoirs each year. The sediments, as defined in this diagram, do not include

the ~70 million GtC of carbonate rock and kerogen.

Page 9: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

State of Biofuels relative to US Energy Demands

• Biomass as a Feedstock for a Bioenergy Industry, USDA, 2005.

Page 10: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

2007 Energy Independence and Security Act

• Replace 30% of petroleum

consumption by 2022

• 36 Billion Gallons of

Renewable Fuel

• 15 Billion Gallons from

Corn Ethanol

• 16 Billion Gallons from

Cellulosic Biofuels

• R. F. Service, Science, 329,

pp 784-785, 2010.

?

Page 11: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Challenges: Quantities • To replace 30% of

petroleum

consumption in the

US, it is estimated

that 1 billion OD

tons of biomass/yr

needed

• 368 million OD

tons/yr forest matl

out of 8.4 billion

tons standing, 1/20

• 998 million OD tons

agricultural out of

the 1.2 billion tons

available per yr, 1/1

• Figures are

optimistic: light

economics,

including assumed

yield increases, no

till, changing crops

and land uses

Biomass as a Feedstock for a Bioenergy Industry, USDA, 2005.

Page 12: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Challenges: Quantities

• International Energy Agency

estimates a 50% reduction of GHG by

2050 to require a factor of 4 increase

in bioenergy production, up to 20% of

the world primary energy

• If one type of material was used to

fulfill this, the corresponding volume

required is shown

• In contrast the global volumes

handled currently:

– Total of rice, wheat, soybeans, maize,

others is 2.75 bcm

– Coal 6.2 bcm/yr

– Oil 5.7 bcm/yr

• T. L. Richard, Science, 329, pp 793-

795, 2010. Assumptions: 15 billion mT, 60%

conversion efficiency, 17 MJ/kg dry matter, 150 and

225 kg/m3, baled grass and wood chip density.

Page 13: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Challenges: Low Energy Density

• R. C. Brown, Biorenewable Resources, Engineering New

Products from Agriculture, Blackwell Pub, 2003.

10x

Page 14: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Challenges: Land Mass Required

• A Cho, Science, 329, pp 786-787.

• San Jose population: ~1 million, California Dept of Finance. January, 2010.

Page 15: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Challenges: Solids Handling

• Transport, communition,

measurement, and dosing

problematic

• Storage conditions important

– Moisture and temperature sensitive

– Break down through the action of a

naturally occurring microorganisms,

such as bacteria, fungi, etc.

• Low bulk density

• D. L. Klass, Biomass for Renewable

Energy, Fuels and Chemicals,

Academic Press, 1998.

Page 16: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

How the current forest products industry

might fit in.

Biomass as a Feedstock for a Bioenergy Industry, USDA, 2005.

Page 17: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Chemical Components of Wood

LIGNIN

SW 25%

HW 21%

CELLULOSE

45%

HEMICELLULOSE

SW 25%

HW 30%

EXTRACTIVES

2-5%

WOOD

OH

OCH3

CarbohydrateO

OCH3

CH2OH

O

CH

HCOH

CHOCHOH2C

O

CH3O

OCH3

HOH2C

O

HC

HC

OCH3

O

CH3O

HC

CH

O

CHO

OH

CH2OH

O

CH

HC

HC

CH

O

H2COH

CH3O

HCOH

HC

O

CH2OH

OCH3

HOCH2

O

HC

HC

OCH3

C

HC

OH [O-C]

CH2OH

OH

CH

HCOH

CH3O H2COH

CH3O

HC

HC

O

H2C

CH2

OH

CH

CH

O

O

CH2OH

O

CH

HCOH

OCH3

HO

OCH3

HCOH

HC

O

H2COH

CH3O

CH2OH

OH

HC

CH

CH3O

O LigninCH3O

O

CH2OH

CH

HC

Ac

Ac

Ac

C H O REG

o o o o o o C H O REG

Hemicellulose: DP=150

“Sugar” Value

Cellulose:

DP=4000

“Polymer” Value

Lignin Crosslinked

“Heat” Value

Page 18: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Current: wood to paper process

Digester

Washers

Evaporators Recovery

Boiler

Caustic

Plant

Lime

Kiln

Pulp &

Black Liquor

Weak Black

Liquor

Strong Black

Liquor

Green

Liquor

White Liquor

Lime

Mud

CaCO3

Lime

Pulp

Wash

Water

Chips

Na2S, Na2CO3

Na2S, NaOH

CaO

Brown

Pulp

Storage

Screens &

Cleaners Bleach

Plant

Bleach

Pulp

Storage

To Paper Machine

Chipper &

Screens

Debarking

Drum Logs

Wash

Water

Steam Turbine

Generator

Power

Lignin and Hemicellulose Cellulose and Hemicellulose

Fatty Acids

Turpentine

Page 19: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Pulp and Paper

Manufacturing

Black Liquor

& Residuals

Source: Bioenergy Deployment

Wood used to

manufacture paper

Steam,

Power &

Chemicals

Purchased Fossil

Fuel & Power:

0.9 Quads

Power Boiler

Recovery Boiler

O2

90xE6 MT CO2

CO2

Current Wood Processing Industry

Page 20: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Black Liquor

& Residuals

Extracted

Hemicellulose and

other chemicals

Wood used to

manufacture paper

Steam,

Power &

Chemicals

Proposed: Biorefinery Industry

Biofuels/Chemicals

$17 billion

Biorefinery:

Gasifiers

Combined Heat/Power

Conversion to chemicals

and biofuels

O2

66xE6 MT CO2

CO2

Paper Products

$5.5 billion Source: Bioenergy Deployment

Page 21: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Bioenergy Program Department of Forest Biomaterials

Page 22: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Faculty in Bioenergy Science and Technology

Dimitris Argyropoulos

Professor

Wood Chemistry

Med Byrd

Associate Professor

Process Development

Hou-min Chang

Professor Emeritus

Wood Chemistry

Vincent Chiang

Professor

Forestry Biotechnology

Martin Hubbe

Professor

Surface Chemistry

Stephen Kelley

Dept Head & Professor

Polymer Chemistry

Adrianna Kirkman

Professor

Process Simulation

Lucian Lucia

Associate Professor

Wood Chemistry

Sunkyu Park

Assistant Professor

Bioenergy Process

Richard Phillips

Executive in Residence

Bioenergy Economics

Orlando Rojas

Associate Professor

Surface Chemistry

Daniel Saloni

Assistant Professor

Process Development

David Tilotta

Associate Professor

Wood Chemistry

Richard Venditti

Professor

Process Engineering

Hasan Jameel

Professor

Process Engineering

John Heitmann

Professor

Enzyme Biotechnology

Page 23: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Bioenergy Projects

• Bioethanol Pilot Plant

• Wood-to-Ethanol Research Consortium

• Value Prior to Pulping (VPP)

• Ethanol from Transgenic Hardwoods

• Ethanol from Coastal Bermuda Grass

• Enhancing Wood Penetration for More Efficient Hydrolysis and Optimized

Saccharification

• Opportunities with Dissolved Wood for the Forest Biorefinery

• Validation of Therminator Syngas Cleanup

• Advanced Technology for Low Cost Ethanol from Engineered Cellulosic Biomass

• Economics and Feasibility of North Carolina Biomass Conversion

• Producing Ethanol from Biomass by Extracting Value Prior to Extraction

• Low Cost Conversion of Industrial Sludges to Ethanol

• Integrated Torrefaction-Gasification for the Production of Biofuels

• Economic Analysis of Pine Biomass Varieties for Ethanol Production

• Life Cycle Analysis for the Production of Transportation Fuels

• Fast Pyrolysis of Forestry Biomass

Page 24: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Wood to Ethanol Research Consortium (1)

• Paper industry in US has idled about 25% of its production,

about 50 million tons/yr of wood processing (potential of 4

billion gallons of ethanol)

• Concept: Repurposing a kraft pulp mill into a ethanol mill

• Develop cost effectiveness by reusing existing asset: a pulp

mill is about $1 Billion in capital

Page 25: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Wood to Ethanol Research Consortium (2)

Kraft Mill

Repurposed Kraft Mill

To Produce Ethanol

Recovery

Boiler

Waste

Treatment Woodyard

Brownstock

Washers

Brownstock

Washers

Evaporators

Distillation Beer

Column

Fermentation Fiber

Hydrolysis

Biomass

Power Sales

Fiber

Hydrolysis

Fiber

Hydrolysis

Power

Generation

Continuous

Digester

Dehydration

Lignin

Filter

80% of sugars in wood can be

converted by enzymatic

hydrolysis when wood is

pretreated with green liquor.

Page 26: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Ethanol from Transgenic Hardwoods

• Challenge: bioconversion of wood to

ethanol, wood is recalcitrant to enzyme

hydrolysis, low sugar yields

• Must pretreat wood with alkali, acid…

• Evaluate potential for simplifying

pretreatments for low/modified lignin

hardwood (aspen)

Samples Lignin S/G Glucan

Wildtype 23 2.2 44

TG96 24 6.4 45

TG141 11 2.6 54

Figure 1. Effect of lignin content on glucose yield from

wildtype and transgenic woods

Page 27: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Low Cost Conversion of Industrial Sludges to Ethanol

• Biofuels Center of North Carolina

• Demonstrate an effective technology to convert industrial

papermaking sludge as a cost effective feedstock for the efficient

biochemical biomass conversion to ethanol

Papermaking Sludges

Negative feedstock

cost

Contains CaCO3 and

inorganics

Page 28: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

A closer look at three Biofuels projects:

1. Integrated biomass supply and financial

models

2. Extraction of hemicellulose for higher valued

products

3. Thermoconversion of Biomass to Liquid Fuel

Page 29: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

1: Integrated Biomass Feedstock

Supply and Financial Models

Ronalds Gonzalez, Hasan Jameel,

Richard Phillips

Page 30: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

30

Integrated Supply and

Financial Models

•Biometrics

•$/acre; $/BDT

•Ton

Carbohydrate/acre

•Land available to grow biomass?

•What are the strategies for conversion of land use?

•Whole tree chemical composition?

Harvesting

Storage

• $/BDT

•Sugar/Biomass loss

Freight Biorefinery

• Dilute acid

•Thermochem

•GL

•ZeaChem

• Plant location

•Complete financial

analysis

• $/BDT

•Bulk density

Page 31: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

SUPPLY CHAIN ASSESSMENT

31 0.2 0.2

0.4

0.5

1.01.1

1.8

2.2

2.4

3.0

3.8

3.9

0.0

0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

0.0

0.5

1.0

1.5

2.0

2.5

10 20 30 40 50 60 70 80 90 100 110 120

Mil

lio

ns

BD

T T

ota

l

Mil

lio

ns

BD

T

Corn Stalk Soybean stalk Wheat straw

Cotton stalk Sugar cane bagasse Sorghum G stalk

Total

Miles

• Integrated feedstock supply

• Biomass availability – curve supply

•Delivery costs, economic analysis

•Supply chain and logistic analysis

Page 32: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

Biomass to Cellulosic Ethanol in Southern

U.S.: Supply Chain and Delivered Cost

32

Page 33: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

BIOMASS PRODUCTIVITY AND REQUIRED LAND

2.45.6 5.1

28.9

22.527.0

101.2

26.622.5

202.3

17.1

20.2

2.2

15.7

20.2

16.8

4.5

0

5

10

15

20

25

0

50

100

150

200

Loblolly pine Eucalyptus Nat.

hardwood

Switchgrass Miscanthus Sweet

sorghum cane

Corn stover

Hectares per rotation Hectares total Productivity (dry ton per ha per year)

dry

ton

ha-1

yea

r-1

Th

ou

sand

hec

tare

s

Biomass productivity and hectares required for production to supply 453,597 dry ton yr-1

Page 34: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

20.2 20.217.1 16.8 15.7

4.52.2

37.8 37.841.1 41.4 42.9

80.3

113.6

0

20

40

60

80

100

120

Eucalyptus Miscanthus Loblolly pine Sweet

sorghum cane

Switchgrass Corn stover Nat. hardwood

Productivity (dry ton per ha per year) Sourcing distance (km)

So

urc

ing

dis

tan

ce (k

m) an

d P

rod

uct

ivit

y (d

ry to

n p

er a

cre

per

yea

r)

Sourcing distance (km) and productivity (dry ton ha-1 yr-1) for the different feedstocks

BIOMASS PRODUCTIVITY AND SOURCING DISTANCE

Page 35: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

24.6 25.2

14.0

43.2

36.4

52.3

22.0

35.6 35.6

35.6

13.3

13.3

13.3

26.2

9.2 8.7

21.3

14.2

12.9

21.2

23.5

13.1

13.1

13.1

13.1

2.1

1.9

2.6

2.2

0

20

40

60

80

100

120

Loblolly pine Eucalyptus Nat. hardwood Switchgrass Miscanthus Sweet

sorghum cane

Corn stover

Storage biomass loss cost Storage cost Freight cost Harvesting cost Biomass

$ p

er d

ry to

n

69.4 69.5 71.0

87.0

102.5

77.6

85.9

Biomass delivered cost for each of the feedstock, considering 5% covered area and annual supply of

453,597 dry ton year-1

BIOMASS DELIVERED COST

Page 36: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

PROCESS SIMULATION – CONVERSION ECONOMICS

36

Logs Debarking

Drum Chips

Chipper and

screens

Pulp & Black

LiquorWash

Water

Pulp

Weak Black

Liquor

Strong Black

LiquorSteam

Smelt

Green Liquor

Na2S, Na2CO3

Digester

Washers

Evaporators

Recovery

Boiler

Turbine

Generator

Pulp

storage

Enzyme

Lignin filter

Dis

tilla

tio

n

Fermentation

Ethanol

Enzym

atic h

ydro

lysis

Smelt

dissolvingClarifier

2.08

1.01

-0.62

-0.07

-0.05

-0.55

-0.17

-0.21

-0.09

-0.80 -0.30 0.20 0.70 1.20 1.70 2.20

Ethanol price

Ethanol subsidy

Biomass

Labor

Chemicals

Depreciation

Maintnance

Overhead

Other fixed costs

Costs and revenues (US$ per gallon ethanol)

Biomass

35.2%

Labor

4.0%

Chemicals

2.7%

Depreciation

31.3%

Maintnance

9.7%

Overhead

11.8%

Other fixed costs

5.3%

•Conversion simulation

• Lab demonstration, pretreatments

• Integrated analysis feedstock – final

product

• CAPEX & OPEX

• Industrial contacts – real financial

analysis

Page 37: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Forest Biomaterials NC State University

Cellulose to ethanol

EXAMPLE CASE: COSTS AND REVENUES:

37

-4 -3 -2 -1 0 1 2

Ethanol revenue

Ethanol subsidy

Wood

Chemicals

Yeast

Enzymes

Energy

Depreciation

Labor, overhead, others

Production cost

Cash cost

2.08

1.01

-1.00

-0.04

-0.07

-0.55

0.04

-0.31

-0.58

-2.51

-2.14

US$ per gallon ethanol

-1%

19%

39%

59%

79%

99%

Wood

39.8%

Chemicals

1.4%

Yeast

2.8%

Enzymes

21.8%

Energy

-1.4%

Depreciation

12.3%

Labor,

overhead, others,

23.2%

% T

ota

l co

sts

Production costs, cash cost and share cost for ethanol for natural mixed hardwood in the repurposing green liquor

scenario.

Page 38: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

2: Extraction of Hemicellulose from

Wood for Ethanol and Biopolymer Gels

Abdus Salam, Richard Venditti, Joel

Pawlak, Khaled El-tahlawy

Page 40: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Hot water extraction of hardwood:

Raw material: 100g Arabinan: 0.78g Rhabinan: 0.47g Galactan: 0.97g Glucan: 39.22g Xylan: 16.17g Mannan: 1.63g Klason Lignin: 22.36g ASL: 3.74g Acetic acid: N/A Furfural: 0.68g Others: 13.98g

Pretreated solids: 78.13g Arabinan: 0g Rhabinan: 0g Galactan: 0g Glucan: 38.40g Xylan: 7.43g Mannan: 1.06g Klason Lignin: 19.95g ASL: 1.72g Acetic acid: N/A Furfural: 0.75 Others: 8.71g Extract: 15.59g Arabinan: 0.55g Rhabinan: 0.14g Galactan: 0.21g Glucan: 0.05g Xylan: 1.10g Mannan: 0.05g Klason Lignin: N/A ASL: 2.36g Acetic acid: 2.44g Furfural:1.25g

Sugar in filtrate: 9.81g Arabinan: 0.54g Rhabinan: 0.28g Galactan: 0.61g Glucan: 0.25g Xylan: 7.56g Mannan: 0.57g

160 ˚C

1 hour

3%

H2SO4

Page 41: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Cross Linking of Hemicellulose Citrate with Chitosan to Make

High Value Foams

Ac

Ac

Ac

C H O REG

Hemicellulose: DP=150

“Sugar” Value

1.

2.

3.

Page 42: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Hemicellulose Citrate Chitosan based elastic foam

Page 43: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Absorption properties of

hemicellulose citrate-chitosan foam (vacuum filtration)

Results & Discussion

Water absorption percent with DI

water at 1hr

Water absorption percent with

0.9% NaCl at 1hr

Chitosan 640 550

Hemicellulose 120 160

Hemicellulosecitrate 350 380

Hemicellulose/

Chitosan foam

360 390

Hemicellulose citrate Chitosan

foam

1520 1780

Commercial

Cellulose foam

210 260

Acrylic Acid based

Super Absorbent Polymer

14880 1800

Page 44: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Desalination

Proposed technology to reduce brackish water from

3000 to 500 ppm salt content with two applications of

HCC gel at 1:40 ratio.

0

0.01

0.02

0.03

0.04

0.05

0.06

0.07

0 0.5 1 1.5 2 2.5 3 3.5

NaCl concentration g/L

Hy

dro

ge

l N

aC

l u

pta

ke

, g

/g

0

0.5

1

1.5

2

2.5

3

3.5

0 0.5 1 1.5 2 2.5 3 3.5

Initial NaCl, g/L

Na

Cl, g

/L

Page 45: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Water Remediation Material:

Arsenic Removal

• Arsenic uptake for various materials in a 5 PPM solution. (Absorbent

0.025g, 50ml, 6 minutes).

• TOF SIMS with a Bismuth(+3) primary ion beam.

Sample Metal Loading (mg/g)

Hemicellulose citrate-chitosan

1.28

Starch citrate-chitosan 1.84

Starch citrate 1.16

Starch 0.43

Chitosan 0.88

Sorba Tech 450 0.10

LaneRT 0.40

Alumina 0.48

Purolite FerrIX A33E 0.54

Absorbia GTO 0.04

Page 46: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

3: Process Model Based LCA of Biofuels

Production

Jesse Daystar, Richard Venditti, Hasan

Jameel

Page 47: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Thermal conversion of biomass to ethanol

Heat and Power

Feed Handling

& Preparation Gasification

Gas Cleanup &

Conditioning

Alcohol

Synthesis

Alcohol

Separation

Flue Gas

Ethanol

Higher

Alcohols

Page 48: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

LCA Approach

ASPEN Plus

Simulation

SimaPro

Inventory

Impact

Assessment

Informed

Biomass/Energy

Decision Making

Establish System

Boundaries

Page 49: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Gate-to-Gate Operating Parameters

• Facility size

– Matches production of the NREL biochemical process model

• 2,205 dry ton/day

• 772,000 dry ton/year

• 1,544,000 wet ton/year delivered

– Evaluate Various promising feedstocks

• No full scale plant exists currently

Page 50: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Product

Raw materials Intermediate Materials

Transportation Production

Transportation

Energy

Fuels Upstream fuel/energy

emissions

Emissions

Waste Landfill

Emissions

Cradle-to-gate boundary

System Boundary: Gate to Gate,

circled operations considered

Page 51: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Alcohol Yields Process Model Results

Forest

Resources

Energy Crops

Feedstock Hybrid poplar Mixed hwd Loblolly Eucalyptus

Units: (gal/OD ton) Δ % Δ % Δ %

Total gallons per OD ton 106 1.8% 5.6% -3.5%

Feedstock Hybrid poplar Corn stover Switch grass Miscanthus Units: (gal/OD ton) Δ % Δ % Δ %

Total gallons per OD ton 106 -13.0% -5.3% -5.4%

Page 52: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

GHG Emissions Hybrid poplar Mixed hardwood Loblolly pine Eucalyptus

Units - Δ % Δ % Δ %

lbs CO2 eq. /gal eth 23 -4.1% -5.4% 2.8%

GHG Emissions Hybrid poplar Corn stover Switchgrass Miscanthus

Units - Δ % Δ % Δ %

lbs CO2 eq. /gal eth 23 -0.3% -2.8% -2.5%

GHG Emissions Process Model Results

Forest

Resources

Energy Crops

Page 53: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Sensitivity to Moisture Content

-15%

-10%

-5%

0%

5%

10%

15%

-15%

-10%

-5%

0%

5%

10%

15%

30 35 40 45 50 55 60

Δ%

GH

G p

er

gallo

n

Yie

ld Δ

% g

allo

n/t

on

% Moisture Content

Yield gallon/OD ton

lb CO2 per gallon

Page 54: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Cradle-to-Grave Operating Parameters

• Facility size

– Matches the NREL biochemical process

• 2,205 dry ton/day

• 772,000 dry ton/year

– Moisture content @50%

• 1,544,000 wet ton/year delivered

– Feedstock:

• Softwood chips: SimaPro data for preliminary analysis

Page 55: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Product

Raw materials Intermediate Materials

Transportation Production

Transportation

Energy

Fuels Upstream fuel/energy

emissions

Emissions

Waste Landfill

Emissions

System Boundary

Cradle to Gate

System Boundary

Page 56: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

GHG Emissions GHG Emissions by process tons CO2 eq / yr lb CO2/OD ton wood Percentage

Hauling 4064 8 1.2%

Feller-buncher 51067 102 15.1%

Pick up truck 91 0 0.03%

Timber jack, Skidder 67664 135 20.1%

Prentice 37024 74 11.0%

450 hp 3-Knife Chipper 168704 337 50.0%

Reforesting emissions (no seedlings) 6227 12 1.8%

Seedlings emissions 1 0 0.0%

Fertilizer emisions 2465 5 0.7%

Total 337307 675 100.0%

Page 57: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Gas vs. Ethanol Single Score

Pt is the unit of environmental impact in eco-points

~40 mPt

Page 58: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Summary

• Enormous challenges exist for the Biofuels industry

• Impacts of a Biofuels industry are not known currently

• Selected biomass sources, technologies and products hold potential and may contribute to the world’s needs

• NCSU is active in developing new processes, products and analysis tools for biofuels

Page 59: Emerging Forest-based Products and Processes...Wood Chemistry Med Byrd Associate Professor Process Development Hou-min Chang Professor Emeritus Wood Chemistry Vincent Chiang Professor

Acknowledgements:

USDA, DOE, DOI, NSF, WRRI, NC Biofuels

Center, Consortium for Plant Biotechnology

Research, NCSU Forestry Foundation

Jesse Daystar, Ronalds Gonzalez, Abdus

Salam, Khaled El-tahlway, Yan Pu, Laura

Chen, James Lee,

Questions?