Post on 20-May-2022
Forest BioRefineriesTransforming the Forest
Products Industry
Arthur J. RagauskasInstitute of Paper Science and Technology
Georgia Institute of TechnologyChalmers University of Technology
Global ChallengesEnergy Needs
Terawatts Challenge-1940 2 TW-2004 15 TW
Biomass 1.6 TW
2050 ~30 – 60 TWBiomass 30 TW
2003 6.3 Billion People2050 8-10 Billion People
world population
0
2
4
6
8
10
1750 1800 1850 1900 1950 1998 2050
0
2,000
4,000
6,000
8,000
10,000
12,000
14,000
16,000
18,000
1971 1990 2004 2015 2030
OECD Transition Economies Developing Countries
Ener
gy D
eman
d (M
toe)
Stabilization of CO2 concentrations means fundamental change to the global energy system
Oil Oil + CCSNatural Gas Natural Gas + CCSCoal Coal + CCSBiomass Energy Nuclear EnergyNon-Biomass Renewable Energy End-use Energy
History and Reference Case
0
200
400
600
800
1000
1200
1400
1600
1850 1900 1950 2000 2050 2100
Glo
bal P
rimar
y E
nerg
y 18
50-2
100
(Exa
joul
es)
FutureHistory
Stabilization of CO2 at 550 ppm
0
200
400
600
800
1000
1200
1400
1600
1850 1900 1950 2000 2050 2100
Glo
bal P
rimar
y E
nerg
y 18
50-2
100
(Exa
joul
es)
.
FutureHistory
Preindustrial280ppm
Preindustrial280ppm
Source: Jae Edmonds
Decreasing U.S. Petroleum ConsumptionCongress:The “30 by 30” goal
World Ethanol and Biodiesel Annual Production
(Petroleum use @ 1150 B g/yr)
0
1
2
3
4
5
6
7
8
9
10
975
980
985
990
995
000
005
Fuel
(bill
ion
annu
al g
allo
ns)
EthanolBiodiesel
Energy Bill H.R.6:
• Replace 30% of gas and diesel consumption with biofuelsby 2030
• Requires approximately 1B dry tons of biomass for 60B gal using current technology
• “Billion Ton Study” – there is enough biomass in the US
• Decrease consumption by 18%in 14 years
• Grow production of renewable fuels to 31B gal/year by 2017
4359 4288
528251 79 79 40 32
0
500
1000
1500
2000
2500
3000
3500
4000
4500
Mill
ion
Ann
ual G
al
Braz
il
US
China EU Ind
iaCa
nada
Columbia
Others
Annual Ethanol Production by Country in 2005
Upper limit of corn ethanol is set to 15 billion gal per year (National Corn Growers Association)
With capacity being built we will reach this limit within two years
We must add cellulosic biofuels in order to meet our national goals
State of the Union Address
Potential Biomass Resource and Refinery Capacity in 2012: Logging
Residues, Crop Residues, Switchgrass
Source: Perlack et al., ORNL
Data do not include pulp & paper assets in the Southeast
Potential Biomass Resource and Refinery Capacity in 2030: Forest Residues (all),
Crop Residues, Switchgrass
Source: Perlack et al., ORNL
Data do not include pulp & paper assets in the SoutheastThe Southeast and Midwest will be the sources for US biomass
Cellulosic BioRefineries
Today- Tomorrow’s Forest Products BioRefiner
Current Products: Pulp, Tall Oil, TurpentineFuture Select Hemicellulose, Wood Extractives, Lignin
Material
Syngas Syngas Power Export 116 million BOE
or Liquid
Fuels/Chemicals109 million barrels
O2
PulpSW 55 million tons
Steam, Power& ChemicalsBL Gasifier
Wood Residual GasifierCombined Cycle SystemProcess to manufactureLiquid Fuels and Chemicals
Manufacturing
CO2
Extract Hemicellulosesnew productschemicals & polymers1.9 billion gallons Ethanol
600 million gallons Acetic Acid
Black Liquor& Residuals
The Forest Biorefinery – Production
•Add Fischer-Tropsch unit; convert BLG •Syngas to Renewable Fischer-Tropsch Fuel
BioRefinery: Hemicellulose Extraction
Experimental Pre-Extraction ConditionsLoblolly Pine Experimental Parameter
Alkaline Pre-extraction
Acidic Pre-extraction
Steam Pre-extraction
Temperature/ oC 100 - 170 130 - 150 130 - 170 Time/h 0.5, 1.0, 1.5 0.5, 1.0 0.5, 1.0, 1.5, 2.0 Chemicals/% 1.0, 1.5% NaOH 0.0, 0.2, 0.5% H2SO4 53 psi Ratio of Liquor to Wood
5.0 : 1.0 5.0 : 1.0 4.0 : 1.0
Post Extraction Washing
No Yes & No No
Acidic Pre-Extractions – Kraft Pulping
BioRefinery: Hemicellulose ExtractionAcidic Pre-Extracted Woodchips: Monosaccharide Analysis
Mass Terminal pH % Recovery
0.5h Pre-Extraction
0.0% H2SO4: 5 3.20.2% H2SO4: 5 2.70.5% H2SO4: 8 2.3
1.0h Pre-Extraction
0.0% H2SO4: 8 3.70.2% H2SO4: 10 2.40.5% H2SO4: 12 2.2
0
5
10
15
20
25
30
35
40
45
50% Hydrolyzed
Sugars
0 %H2SO4
0.2%H2SO4
0.5%H2SO4
0 %H2SO4
0.2%H2SO4
0.5%H2SO4
Arabinose
Galactose
Glucose
Xylose
Mannose
0.5 h 1.0 h
0 5.0 10.0 15.0 20.0 25.0 30.0 35.0Minutes
0
25
50
75
100
125
150
175
200
nC
1-2
Fuc os e
Arabinose
Galac tos e
Gluc ose
Xy los e
Mannose
Yields 10 – 18%
BioRefinery: Hemicellulose Extraction
0
5
10
15
20
25
30
Kap
pa #
Control(
no pre-
extra
ction)
0.5hr
pre-extr
acted
/With
was
hing
0.0 %
H2SO4
0.2% H
2SO4
0.5% H
2SO4
1.0hr
pre-extr
acted
/With
was
hing
0.0 %
H2SO4
0.2% H
2SO4
0.5% H
2SO4
1.0hr
pre-extr
acted
/With
out w
ashin
g
0.0 %
H2SO4
0.2% H
2SO4
0.5% H
2SO4
Kraft Pulping Acidic Pre-Extracted Woodchips: Kappa #(Lignin Content
BioRefinery: Hemicellulose ExtractionKraft Pulping Acidic Pre-Extracted Woodchips: Viscosity
0.0
5.0
10.0
15.0
20.0
25.0
30.0
35.0
Visc
osity
/cP
Contro
l(no p
re-ex
tracti
on)
0.5hr
pre-ex
tracte
d/With
was
hing
0.0 %
H2S
O40.2
% H2S
O40.5
% H2S
O4
1.0hr
pre-ex
tracte
d/With
was
hing
0.0 %
H2S
O40.2
% H2S
O40.5
% H2S
O4
1.0hr
pre-ex
tracte
d/With
out w
ashin
g0.0
% H
2SO4
0.2% H
2SO4
0.5% H
2SO4
BioRefinery: Hemicellulose ExtractionKraft Pulping Acidic Pre-Extracted Woodchips: Burst
0.0
0.5
1.0
1.5
2.0
2.5Orig
inal
0.5hr
pre-ex
tracte
d(with
was
hing)
0 % H
2SO4
0.2% H
2SO4
0.5% H
2SO4
1.0hr
pre-ex
tracte
d(with
was
hing)
0 % H
2SO4
0.2% H
2SO4
0.5% H
2SO4
1.0hr
pre-ex
tracte
d(with
out w
ashin
g)0 %
H2S
O40.2
% H2S
O40.5
% H2S
O4
Burst Index
BioRefinery: Hemicellulose ExtractionAcidic Pre-Extracted Woodchips: Pretreatment Modification
Prior StudiesDirect H2SO4/H2O
t=0
H2SO4/H2Ot= 48 hSpray Chips 1 h, 150 oC
AlternativeApproachDelayed
BioRefinery: Hemicellulose ExtractionAcidic Pre-Extracted Woodchips: Pretreatment Modification
H2SO4/H2O
Direct & Delayed
1 h, 150 oC
Reducing Sugars (mg/ml) % Hemicellulose0.5% H2SO4 Direct (t:0) 36.3 12Delayed (t: 48 h) 57.8 19
0.75% H2SO4 Direct (t:0) 67.9 22Delayed (t: 48 h) 72.2 23
Basic Pre-Extractions – Kraft Pulping
BioRefinery: Hemicellulose ExtractionAcidic Pre-Extracted Woodchips: Pretreatment Modification
NaOH/H2O
1 h, 150 oCExp. Terminal pH %Sugar Recovery Reducing Sugar (mg/ml)150 oC 4.5% NaOH1.0 h: 10.6 8 1.9
160 oC 4.5%% NaOH1.0 h: 10.0 11 2.0
170 oC 4.5% NaOH, 2 h 8.9 11 2.36.0% NaOH, 1 h 11.3 14 2.59.0% NaOH, 1 h 12.7 16 3.312.0% NaOH, 1h 12.7 18 4.0
BioRefinery: Hemicellulose ExtractionKraft Pulping Alkali Pre-Extracted Woodchips: Kappa #
Experimental Conditions: NaOH: 4.5 – 12.0% t: 1.0 – 3.0 hrTemp.: 150 - 170 oC
0
10
20
30
40
50
60% Monosaccharide
150 C
NaOH 4.
5%, 1
hr
160 C
NaOH 4.
5%, 1
hr
170 C
NaOH 4.
5%, 1
hr
NaOH 4.
5%, 2
hr
NaOH 4.
5%, 3
hr
NaOH 6.
0%, 1
hr
NaOH 9.
0%, 1
hr
NaOH 12
.0%, 1
hr
ArabinoseGalactoseGlucoseXyloseMannose
Exp. Terminal pH150 oC 4.5% NaOH1.0 h: 10.6
160 oC 4.5%% NaOH1.0 h: 10.0
170 oC 4.5% NaOH, 1 h 9.14.5% NaOH, 2 h 8.94.5% NaOH, 3 h 8.06.0% NaOH, 1 h 11.39.0% NaOH, 1 h 12.712.0% NaOH, 1h 12.7
BioRefinery: Hemicellulose Extraction
Benefits of Pre-extraction• Significant reliable source of Hemicelluloses• Improves pulpability• Benefits some bleaching operations
Concerns of Pre-extraction• Capital Costs - Partnership• Impact on strength properties
- Grade - Technology• Yield
- Technology - Data
OO
O OAcO
O
HOOAc
O
HOO
OO
AcOOH
O-XylanO
O
HOOAc
OO
AcOOAc
O
O
H3CO HO
OHHO2C O
HO
HOOH
Today- Tomorrow’s Forest Products TMP BioRefiner
Wood Debarking Collection Wood Chipping
Pulp Bleaching
Papermaking
Bark Energy
Wood
Chips
Pulping
WoodExtractives Sulfur Free
BiochemicalBioLube
Value-AddedChemicals
Glucomannans
- Strength Aid/Yield for Kraft- Clean Polysaccharide Resource
Current Products: PulpFuture Select Hemicellulose, Wood Extractives
Biorefinery: Mechanical PulpingCO2H
H
H
Abietic Acid
0.0%
0.5%
1.0%
1.5%
2.0%
2.5%
3.0%
0 7 14 21Day
Ace
tone
Ext
ract
ab
Ambient60oC, 80% RH45oC 73% RH
Filtrate Extractives
0.00
0.05
0.10
0.15
0.20
0.25
0.30
0.35
Chip wash Plug screwpressate
Reject screwpressate
Cloudy WW Central WW
mg/
ml
Fatty AcidsResin AcidsMonoglycerolSterolUnknown
Challenge: • Wood extractives cause process –
quality problemsPulp Extractives
0.00
0.20
0.40
0.60
0.80
1.00
1.20
1.40
1.60
1.80
Chips
1o R
efine
r2o
Refi
ner
Quenc
h Tan
k
1o Scr
een a
ccep
ts
1o S
creen
rejec
ts
Rej. Scr
een f
eed
Rej. Scr
een a
ccep
ts
TMP po
st re
finer
Y Blea
ched
pulp
PY Blea
ched
pulpGWD si
loPM H
eadb
ox
mg/
od g
Fatty AcidsResin AcidsAlkanolMonoglycerolSterolUnknown
Starting Chips 2.8%Pressure WashAcetone 70 oC 1.2%Ethyl alcohol 90 oC 1.2%0.2% Ethoxylates surfactant 90 oC 1.4%
TMP Woodchips Extractives
Biorefinery: Mechanical Pulping
OrginalAcetone Extracted
Ethanol Extracted
Aqueous Surfactant
Hexadecanoic acid
9,12-Octadecadienoic acid
Linolenic acid
Octadecanoic acid
11-Eicosaenoic acid
0
0.2
0.4
0.6
0.8
1
1.2
1.4
Hexadecanoic acid9,12-Octadecadienoic acidLinolenic acidOctadecanoic acid11-Eicosaenoic acid
mgr/gr od pulp
Fatty Acids
Biorefinery: Mechanical Pulping
Resin Acids
0
1
2
3
4
5
6
7
8
9
Control TMP Acetoneextracted
TMP Ethyl alcoholextracted
TMP Surfactantpretreated
Tensile Index
Original
Biorefinery: Mechanical Pulping
Resin Acids
50.5
51
51.5
52
52.5
53
53.5
54
54.5
55
55.5
Control TMP Acetoneextracted
TMP Ethylalcohol extracted
TMP Surfactantpretreated
ISO Brightness
Original
Biorefinery: Mechanical Pulping
BiolubeCurrent Products
Markets for nonsulfurplant extractives
Biorefinery: Mechanical Pulping
Related BioMass-BioFuels ActivitiesRagauskas Team
Lignocellulosicbiomass
Sugar/starchcrops
Oil plants>>Extractives<<
Gasification
Anaerobicdigestion
Flash pyrolysis
Hydrothermalliquefaction
Hydrolysis
Milling andhydrolysisPressing orextraction
Syngas
Biogas
Bio oil
Sugar
Plant Oil
Water gas shift+ separation
Catalyzedsynthesis
Purification
Hydro treatingand refining
Fermentation
Esterification
Hydrogen(H2)
Methanol(CH3OH)
DME(CH3OCH3)
FT Diesel(CxHy)
SNG(CH4)
Biodiesel(CxHy)
Ethanol(CH3CH2OH)
Biodiesel(alkyl esters)
Bio oil
Early Adoption/Paper Mill Sludge-Municipal Waste
OO
HOOH
OO
HOOH
OH
OH
O
HOOH
OO
HOOH
O-Cellulose
OH
OH
O
Ethanol from Cellulosic Waste
Glucose
Ethanol
Bark for Biofuels/Biochemicals`
Conversion Chemistry• Cat. Pyrolysis Chemistry
OH
OCH3
R
OH
OHOH
OHOH
OCH3
OH
Phenolics Feedstocks
Green Diesel/Gasoline
Bark for Biofuels/Biochemicals`
Pyrolysis of Black Liquor
Hydrogen Carbon Oxygen Sulfur Ash Sample name [wt%] [wt%] [wt%] [wt%] [wt%] Black Liquor 3.63 35.14 33.80 4.13 23.30 BL Solid 2.36 36.06 30.24 1.53 29.81 BL Pyr. Oil 8.88 67.69 17.18 2.19 4.06
UnaccountedUnaccounted(Gas)(Gas)
Solid yieldSolid yield(Char)(Char)
Pyrolysis oil Pyrolysis oil yieldyield
14.7814.7842.2542.2542.9842.98P 9.5 (extracted)P 9.5 (extracted)0.920.9267.5567.5531.5331.53P 9.5 (crude)P 9.5 (crude)2.712.7164.1464.1433.1633.16Black liquor (crude)Black liquor (crude)
[wt%][wt%][wt%][wt%][wt%][wt%]SampleSample
UnaccountedUnaccounted(Gas)(Gas)
Solid yieldSolid yield(Char)(Char)
Pyrolysis oil Pyrolysis oil yieldyield
14.7814.7842.2542.2542.9842.98P 9.5 (extracted)P 9.5 (extracted)0.920.9267.5567.5531.5331.53P 9.5 (crude)P 9.5 (crude)2.712.7164.1464.1433.1633.16Black liquor (crude)Black liquor (crude)
[wt%][wt%][wt%][wt%][wt%][wt%]SampleSample
Profiling Biomass Resources Kraft Lignin Isolation
Assorted Possibilities
Ultra-filtration
Low MW Lignin
High MW LigninEvaporators
To recovery boiler
Black liquor
Dewatering
Washed lignin
Precipitation vessel
Wash liquor
“Re-slurry” tank
Weak black liquor tank
Acid Precipitation
Profiling Biomass Resources Kraft Lignin Application: Carbon Fibers
10% of U.S. kraft lignin is sufficient to produce enough carbon fiber to replace half of the steel in all domestic passenger transport vehicles
153-172189-19895/5
120-157150-18275/25
138-172191-20087.5/12.5
138-165195-228100/0
Alcell (°C)HWKL (°C)Lignin/PEO
153-172189-19895/5
120-157150-18275/25
138-172191-20087.5/12.5
138-165195-228100/0
Alcell (°C)HWKL (°C)Lignin/PEO
Alcell and Hard Wood Kraft Lignin (HWKL) were spun continuously into satisfactory fibersAlcell/PEO blends: inter-fiber fusing SWKL: formed chars instead of fibers
Profiling Biomass Resources Kraft Lignin Application: Pellet Binder
District Heating
Drivers for Wood Pellets • Investment Tax Credit• Capital Grants• Consumer Rebates• Excise Tax Exemptions• Tax Credits• Targets/Quotas with Penalties• Subsidies
• Production of Green Electricity• Consumption
Lignin: Binder for Wood Pellets
Profiling Biomass Resources Kraft Lignin Application: Resin/Adhesive
Strength Properties of OSB-Panels Produced with Combination of Phenolic Resin and Lignin
Binder Property 100% Phenolic 80% Phenolic/20% Lignin Powder Resin MOR/psi 3456 3654 IB/psi 59.4 60.1 D-4/lbs 144 143 D-5/lbs 115 141 Liquid Resin MOR/psi 5204 4866 IB/psi 83 295 D-4/lbs 276 97
Novel Oxidative/Reductive Chemistryfor Lignin
OH
OH
OCH3HO
OCH3
O
HO
HO
H3COO
HO
HO OCH3
O
HOOCH3
OHO OH
OOH3CO
HO
HO
O
OH
OH
OCH3
OCH3
OH
OH
OOCH3
OO
OCH3
O
OCH3
HO
HO
OCH3
O
O
OCH3
HOO
HO
HO
OCH3
C8 – C22
OH
HO
O OCH3
O
OCH3
O
HO
O OCH3
O
OCH3
Oxid.
∼ C800 – C900
OH
HO
O OCH3
O
OCH3
OH
HO
HO OCH3
O
OCH3
H2/Cat
Catalytic Conversion of Biomass to Biofuels
Biofuel precursor:Biofuel precursor:
OH
OH
OCH3HO
OCH3
O
HO
HO
H3COO
HO
HO OCH3
O
HOOCH3
OHO OH
OOH3CO
HO
HO
O
OH
OH
OCH3
OCH3
OH
OH
OOCH3
OO
OCH3
O
OCH3
HO
HO
OCH3
O
O
OCH3
HOO
HO
HO
OCH3
CC99 –– CC1818
∼∼ CC800800 –– CC900900
Cracking BiopolymerCracking Biopolymer Viable BiodieselViable Biodieselor Biogasolineor BiogasolineComponentComponentCurrent Research Activities:Current Research Activities:
-- Utilization of conventional Utilization of conventional heterogeneous hydrogenationheterogeneous hydrogenationcatalystscatalysts
-- Development of homogenousDevelopment of homogenousaqueous phase catalysis aqueous phase catalysis chemistry for hydrogenationchemistry for hydrogenationcleavage of: cleavage of:
ArylAryl--OO--Aryl Aryl ArylAryl--OO--Aliphatic EthersAliphatic Ethers
BioChemical: Novel Reductive Catalytic Chemistry
BioMaterial PrecursorsOH
OH
OCH3HO
OCH3
O
HO
HO
H3COO
HO
HO OCH3
O
HOOCH3
OHO OH
OOH3CO
HO
HO
O
OH
OH
OCH3
OCH3
OH
OH
OOCH3
OO
OCH3
O
OCH3
HO
HO
OCH3
O
O
OCH3
HOO
HO
HO
OCH3
C6 – C24
∼ C800 – C900
Cracking Biopolymer
Current Research ActivitiesDevelop heterogeneous/homogenous aqueous
phase catalysis chemistryhydrogenation cleavage
Non-water-soluble hydrogenation complexes
Water-soluble hydrogenation complexes
Ruthenium [Ru(Cl)2( PPh3)3] [Ru(Cl)2( TPPTS)3] [Ru(H)(Cl)( PPh3)3] [Ru(H)(Cl)(TPPTS)3] [Ru(H)2(PPh3)4] [Ru(H)2(TPPTS)4] Rhodium [RhCl(PPh3)3] [RhCl(TPPTS)3]
Reductive
Experimental Setup
• 4560 Mini Parr reactor equipped with a 4842 temperature controller.
• Pressurized with UHP Hydrogen gas.
• Under on-line controlled time and pressure.
Lignin Hydrogenation
TgTg = 148 = 148 ±± 1 1 °°CC
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
Schlenk 50 C Parr 200 CParr
50 C 100 C 150 C 175 C 200 C
Reaction conditions
Mass Balance lignin Hydrogenolysis RuCl2(PPh3)3
CharredUnsolluble PhaseSolluble Phase
Lignin HydrogenationReaction conditions Solubility in
ethanol (% dry wt.)
Mn
(g mol-1) EOL * 52.1 1191 Blank * 65.0 1026 Heterogeneous catalysts Co/Mo 54.3 1075 Raney-Ni * 71.8 1148 Pd/C 69.8 995 Pt/C 76.5 953 Homogeneous catalysts NaBH4/I2 * 72.4 404 RhCl(PPh3)3 76.3 787 Ru(Cl)2( PPh3)3 * 96.4 893 Ru(H)(Cl)( PPh3)3 77.2 837 Ru-(PVP) 58.1 902
Profiling Biomass Resources Kraft Lignin Application
Phenols, Cresols Phenol, Acetic Acid Acetylene Substituted Phenols Substituted Phenols, CO, CH4 Ethylene HYDROGENATION PYROLYSIS FAST PYROLYSIS Phenol HYDROLYSIS ALKALI Phenolic Acids Substituted Phenols Catechols OXIDATION MICROBIAL OXOREDUCTASE Vanillin, MeS2 Lignin with Increased Vanillic, Ferulic Oxidized Lignin MeSH, DMSO Polymerization Coumaric/other Coating/Paint Acids Additive
Thank You!
W.J. BryanDestiny is not a matter of chance, it is a matter of choice, it
is not a thing to be waited for, it is a thing to be achieved