comparative data from application of leading pretreatment technologies to corn stover
DESCRIPTION
Comparative Data from Application of Leading Pretreatment Technologies to Corn Stover. Charles E. Wyman, Dartmouth College Y. Y. Lee, Auburn University Bruce E. Dale, Michigan State University Tim Eggeman, Neoterics International Richard T. Elander, National Renewable Energy Laboratory - PowerPoint PPT PresentationTRANSCRIPT
Comparative Data from Application of Leading Pretreatment Technologies
to Corn Stover Charles E. Wyman, Dartmouth College
Y. Y. Lee, Auburn UniversityBruce E. Dale, Michigan State University
Tim Eggeman, Neoterics International Richard T. Elander, National Renewable Energy Laboratory
Michael R. Ladisch, Purdue UniversityMark T. Holtzapple, Texas A&M University
25th Symposium on Biotechnology for Fuels and ChemicalsBreckenridge, Colorado
May 7, 2003
Outline of Talk
• Overview of Consortium
• USDA IFAFS project overview
• Participants and Advisory Board
• Pretreatment technologies
• Selected results and preliminary material balances to date
• Preliminary economic comparisons
• Future work
Brief History of Biomass Refining Consortium for Applied Fundamentals
and Innovation (CAFI)• Pretreatment researchers working together in a
coordinated, disciplined way to understand the fundamentals underlying lignocellulosic biomass pretreatment and hydrolysis
• Organized in late 1999, early 2000• CAFI recognizes that pretreatment operates as
part of a system that includes hydrolysis and fermentation—pretreatment effects on downstream processes must be better understood
• IFAFS opportunity arose in March 2000, and a subset of CAFI pursued and won an award
USDA IFAFS Project Overview• Multi-institutional effort funded by USDA Initiative for Future
Agriculture and Food Systems Program for $1.2 million to develop comparative information on cellulosic biomass pretreatment by leading pretreatment options with common source of cellulosic biomass (corn stover) and identical analytical methods– Aqueous ammonia recycle pretreatment - YY Lee, Auburn University– Water only and dilute acid hydrolysis by co-current and flowthrough
systems - Charles Wyman, Dartmouth College– Ammonia fiber explosion (AFEX) - Bruce Dale, Michigan State University– Controlled pH pretreatment - Mike Ladisch, Purdue University– Lime pretreatment - Mark Holtzapple, Texas A&M University– Logistical support and economic analysis - Rick Elander/Tim Eggeman,
NREL through DOE Biomass Program funding• Emphasis on quality not quantity
USDA IFAFS Project Tasks1. Apply leading pretreatment technologies to prepare
biomass for conversion to products
2. Characterize resulting fluid and solid streams
3. Close material and energy balances for each pretreatment process
4. Determine cellulose digestibility and liquid fraction fermentability/toxicity
5. Compare performance of pretreatment technologies on corn stover on a consistent basis
Project period: 2000-2003
USDA IFAFS Project Advisory BoardServe as extension agents for technology transfer
Provide feedback on approach and resultsMeet with team every 6 months
Mat Peabody, Applied CarboChemicals
Greg Luli, BC InternationalParis Tsobanakis, CargillRobert Wooley, Cargill DowJames Hettenhaus, CEAKevin Gray, DiversaPaul Roessler, DowSusan Hennessey, DuPont
Michael Knauf, Genencor
Don Johnson, GPC (Retired)
Dale Monceaux, Katzen Engineers
John Nghiem, MBI
Rene Shunk, National Corn Growers Association
Joel Cherry, Novozymes
Leo Petrus, Shell
Corn Stover Composition• NREL supplied corn stover to all project participants
(source: BioMass AgriProducts, Harlan IA)• Stover washed and dried in small commercial operation,
knife milled to pass ¼ inch round screen
Glucan 36.1 %
Xylan 21.4 %
Arabinan 3.5 %
Mannan 1.8 %
Galactan 2.5 %
Lignin 17.2 %
Protein 4.0 %
Acetyl 3.2 %
Ash 7.1 %
Uronic Acid 3.6 %
Non-structural Sugars 1.2 %
Dilute Acid Pretreatment
• Mineral acid gives good hemicellulose sugar yields and high cellulose digestability
• Sulfuric acid usual choice because of low cost• Requires downstream neutralization and conditioning
• Typical conditions: 100-200oC, 50 to 85% moisture, 0-1%
H2SO4
• Some degradation of liberated hemicellulose sugars
Mineral acid
Hemicellulose sugarssolid cellulose and lignin
BiomassReactor
Solubilized Xylan Partition vs. LogMo– Dilute Sulfuric Acid
0%
20%
40%
60%
80%
100%
2.5 3 3.5 4 4.5 5 5.5Log Mo
Max
Po
ten
tial
Xyl
ose
Yie
ld,
X/X0
140C, 0.5% H2SO4
160C, 0.5% H2SO4
180C, 0.5% H2SO4
140C, 1% H2SO4
160C, 1% H2SO4
180C, 1% H2SO4
Mo = t An exp{( T - 100)/14.75} – for acid
Fate of Xylan for Dilute Acid Hydrolysis
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 20 40 60 80 100 120 140 160 180 200Reaction Time, min
Max
Po
ten
tial
Xyl
ose
, X
/X0
Residual Xylan
Soluble Xylooligomers
Soluble Xylose + Xylooligomers
140 oC
0.5% H2SO4
Kh=.044 min-1
Ka=.232
Ko=.116 min-1
Kd=.0016 min-1
n:mj for
a1)C(jkaC2kdt
dCjh
n
1jiih
j :sEq.' Model
n
miia a1)C-(jk
dt
da
Schematic Diagram of Flowthrough Pretreatment
Back Regulator
Sand Bath
Valve-1
P
Cold WaterR
eact
or
T1
HPLC
Pump
Wateror
DiluteAcid
TC
Valve-2
Sample
Effect of Flow Rate and Acid on Residual Xylose at 180oC
1
10
100
0 4 8 12 16Time, minutes
% o
f p
ote
nti
al x
ylo
se
hot water only,0mL/min
hot water only,1mL/min
hot water only,10mL/min
0.05wt% acid,0mL/min
0.05wt% acid,1mL/min
0.05wt%acid,10mL/min
0.1wt% acid,0mL/min
0.1wt% acid,1mL/min
0.1wt% acid,10mL/min
0.00250 0.00252 0.00259
0.003640.00390
0.00579265
0.0106
0.000
0.002
0.004
0.006
0.008
0.010
0.012
20% solids 10% solids 5% solids Batch 25%sol0.1%acid
1ml/min 1000 rpm 10ml/min
Batch Batch Batch FT Parr FT
Kd
(m
m^2
/min
)Initial Mass Transfer Coefficient kd for Water Only Hydrolysis Changes
with Reactor Type (180oC)
k1 = 0.1272 min-1
without acid
Solubilization of Xylan and Lignin for Water Only Hydrolysis
0102030405060708090
100
0 10 20 30 40 50 60 70 80
Lignin removal (% of the original Klason lignin)
So
lub
iliza
tio
n o
f x
yla
n (
% o
f p
ote
nti
al x
ylo
se
)
180C, 0mL/min
180C, 1mL/min
180C, 10mL/min
200C, 0mL/min
200C, 1mL/min
200C, 10mL/min
220C, 0mL/min
220C, 1mL/min
220C, 10mL/min
Controlled pH Pretreatment
• pH control through buffer capacity of liquid• No fermentation inhibitors, no wash stream• Minimize hydrolysis to monosaccharides thereby
minimizing degradation
Water
Steam Stover Heat Recovery
Saccharification
Trim Heat Plug Flow
Reactor Coil
0%
5%
10%
15%
20%
25%
30%
35%
40%
45%
50%
0 5 10 15 20 25Pretreatment Time (min.)
So
lub
iliza
tio
n (
%)
200°C190°C180°C170°C
Solubilization of Corn Stover by Controlled pH Pretreatment
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25
Pretreatment Time (min.)
Glu
cose
Yie
ld (
%)
200 °C
190 °C
180 °C
170 °C
Cellulose Digestibility vs Hemicellulose Solubilization
0
10
20
30
40
50
60
70
80
90
100
0 5 10 15 20 25
Pretreatment Time (min.)
Xyl
ose
/Gal
acto
se Y
ield
(%
)
200 °C
190 °C
180 °C
170 °C
Controlled pH Hot Water Pretreatment (non flow-through) improves digestibility primarily by removal of hemicellulose without degrading the monosaccharides improved porosity / enzyme accessibility
Glucose Yields Xylose Yields
Fermentation of Pretreated, Saccharified Corn Stover
0
5
10
15
20
25
30
35
0 10 20 30 40 50 60
Time (hrs.)
Co
nce
ntr
atio
n (
g/L
)
GlucoseXyloseGlycerolEthanol
Xylose Fermenting Recombinant Yeast 426A (LNH-87). Data provided by Dr. Nancy Ho.
What is AFEX/FIBEX?
• Liquid “anhydrous” ammonia treats and explodes biomass
• Ammonia is recovered and reused• Ammonia can serve as N source downstream• Batch process is AFEX; FIBEX is continuous version• Conditions: 60-110oC, moisture 20-80%, ammonia:biomass ratio 0.5-1.3 to 1.0 (dry basis)
• No fermentation inhibitors, no wash stream required, no overliming
• Only sugar oligomers formed, no detectable sugar monomers• Few visible physical effects
Reactor Explosion
AmmoniaRecovery
BiomassTreatedBiomass
LiquidAmmonia
GaseousAmmonia
Reactor Explosion
AmmoniaRecovery
BiomassTreatedBiomass
LiquidAmmonia
GaseousAmmonia
• Moderate temperatures, pH prevent/minimize sugar & protein loss
0
10
20
30
40
50
60
70
80
90
100
0 24 48 72 96 120 144 168 192
Time (hrs)
% G
luca
n C
onve
rsio
n
110ºC
100ºC
90ºC
Untreated
Kinetics of G lucan Hydrolysis
Conditions:5 m in A FEX treatm ent168 hrs hydrolysis60 % m oisture1:1 A m m onia: B iom ass@ 15 FPU /g of glucan
Conversion of G lucan and Xylan vs.
AFEX Treatment Temperature
0
10
20
30
40
50
60
70
80
90
100 6
0ºC
70ºC
80º
C
90º
C
100
ºC
110
ºC
% G
luca
n or
Xyl
an C
onve
rsio
n
Glucose yield
Xylose yield
Conditions:5 min AFEX treatm ent168 hrs hydrolysis1:1 Ammonia: Biomass,60% moisture60 FPU/g glucan
Features of Ammonia Recycle Pretreatment (ARP)
• Aqueous ammonia is used as the pretreatment reagent: Efficient delignification Volatile nature of ammonia makes it easy to recover
• Flowthrough column reactor is used
• Value-added byproducts are obtained Low-lignin cellulose (“filler fiber” grade) Uncontaminated lignin
Composition and Digestibility for ARP Pretreatment
[mL/min]
Lignin Glucan XylanLiquid1Solid1Flow rate Digestibility2
60FPU 15FPU
Note.; 1. All data based on original feed. 2. Enzymatic hydrolysis conditions; 60 or 15 FPU/g of glucan, pH 4.8, 50C, 150 rpm, at 72h
Glucan Xylan
2.5
5.15.1 35.635.6 10.310.3
6.4 35.9 10.7
5.05.07.5 5.6 35.7 10.1
0.50.5 10.110.1
0.5 10.6
0.8 10.591.391.3 86.986.9
91.5 83.2
93.4 86.9
Untreated 17.2 36.1 21.4 - - 21.2 15.7
• Pretreatment conditions Liquid throughput: 3.3 mL of 15 wt% NH3 per g of corn
stover at 170 C Air dried corn stover is used without presoaking.
Enzymatic Hydrolysis of a Representative ARP Sample (15 wt% NH3, 170ºC)
60 FPU/g of glucan
0
20
40
60
80
100
0 24 48 72
Time [h]
Dig
es
tib
ilit
y [
%]
ARP-treatedα-CelluloseUntreated
Pretreatment conditions: 170C, 3.3 mL of 15 wt% of ammonia per g of corn stover, 2.3 MPa; Enzymatic hydrolysis conditions : 60 or 15 FPU/g cellulose, pH 4.8, 50C, 150 rpm ; α
93.4%@60FPU
15 FPU/g of glucan
0
20
40
60
80
100
0 24 48 72
Time [h]D
ige
sti
bil
ity
[%
]ARP-treatedα-CelluloseUntreated
86.9%@15FPU
Lime Pretreatment
Biomass + Lime
Gravel
Air
Typical Conditions: Temperature = 25 – 55oC Time = 1 – 2 months Lime Loading = 0.1 – 0.2 g Ca(OH)2/g biomass
Pretreatment Time (weeks)
Kla
son
Lig
nin
Con
tent
(w
t %)
0
5
10
15
20
25
0 5 10 15 20
untreated
Pretreatment Time (weeks)
Kla
son
Lig
nin
Con
tent
(w
t %)
25oC35oC45oC55oC
0
5
10
15
20
25
0 5 10 15 20
untreated
No Air Air
Effect of Air/Temperature on Lignin
Enzymatic Digestibility for Lime Treated Biomass
Cellulase Loading (FPU/g dry biomass)
3-d
Sug
ar Y
ield
(mg
equi
v. g
luco
se/g
dry
bio
mas
s)
25oC 55oC
0
100
200
300
400
500
600
700
1 10 100
0
100
200
300
400
500
600
700
1 10 100
Air
No Air
untreated
Cellulase Loading (FPU/g dry biomass)
0
100
200
300
400
500
600
700
1 10 100
0
100
200
300
400
500
600
700
1 10 100
Air
No Air
3-d
Sug
ar Y
ield
(mg
equi
v. g
luco
se/g
dry
bio
mas
s)
Hydrolysis
Enzyme
ResidualSolids
HydrolyzateLiquidAFEX
SystemTreatedStover
Ammonia
Stover
100.5 lb100 lb(dry basis)
21.4 lb xylan 3.5 lb arabinan 1.8 lb mannan
38.3 lb glucose (G)16.6 lb xylose (X)1.11 lb arabinose(A)1.92 lb mannose (M)38.7 lb
95% glucan to glucose, 68% xylan to xylose(93% overall glucan + xylan solubilization)97% overall mass balance closure (All solids + G + X + A + M)3.76 gallons ethanol (90% yield of glucose plus xylose)
Wash
2 lb
98.5 lb
Removed Solids
36.1 lb glucan
Preliminary Mass Balances: Example for AFEX Pretreatment
15 IU/g glucan
Preliminary Yield ComparisonsProcess Xylose yields Glucose yields
Dilute acid ~85% increasing to ~95% w cellulase @ 60 FPU/g glucan
~90 @ 15 FPU/g SSF1 to 95% w cellulase @ 60 FPU/g glucan
Flowthrough ~97-98% in pretreatment ~93-98% @ 15 FPU/g glucan cellulase
Controlled pH ~62% after pretreatment and enzyme
~73% @ ~30 FPU/g glucan
AFEX ~68% after both steps ~95% @ 7.5 FPU/g glucan
ARP ~70% from both steps at 15 FPU/g glucan
~87% at 15 FPU/g glucan
~95% at 60 FPU/g glucan
Lime ~77-93% overall as cellulase raised from ~2 to 20 FPU/g glucan
Increasing pH
1 – NREL data on Sunds
NREL CAFI Project Contributions
• Properly store and provide feedstock • Provide/monitor cellulase preparation• Train students on analytical procedures, etc.• Perform process engineering evaluations• Conduct periodic comparative SSF evaluations• Supported by US DOE Office of the Biomass Program
Economic Modeling MethodologyCapital Costs
Fixed - Direct Purchased Equipment Installation - Indirect - Contingency - Start-up
Working
Revenues
Ethanol SalesElectricity Sales
Operating Costs
Variable - Stover Enzymes Other
Fixed - Labor Maintenance Insurance Depreciation
Discounted Cash Flow
2.5 yr Construction, 0.5 yr Start-up 20 yr Operation100% Equity, No Subsidy
Rational EtOH Pricing Rather Than Market Pricing10% Real After Tax Discount Rate
Performance Measures
Total Fixed Capital Per Annual Gallon of CapacityMinimum Ethanol Selling Price (MESP)—$/gallon
Plant Level Cash Costs
Based on NRELeconomic modelfor ethanol from cellulosics
-Pricing per 2001NREL design-2,000 dry mtons/day stover
MESP and Cash Cost
0.00
0.25
0.50
0.75
1.00
1.25
1.50
1.75
2001 NRELDesign
AcidCocurrent
AutoCocurrent
Neutral pHHot Water
ARP AFEX Lime Corn DryMill
Net Stover Other Variable Fixed w/o Depreciation Depreciation Income Tax Return on Capital
CashCostPlantLevel
MESP
Proof Year: 4th Year of Operation$/gal EtOH
Caveats About Economic Projections
• Current economic models…Not final!– Pretreatment assumptions: Modeling currently based on
many assumptions—will be updated with more data at conclusion of project
– Assumptions in other areas: All cases have similar assumptions….thus similar performance—will be updated with additional data
• No distinctions for level of development
Some Conclusions to Date• Dilute acid and neutral pH pretreatments solubilize
mostly hemicellulose while ammonia and lime remove mostly lignin. AFEX removes neither.– Hemicellulose hydrolysis to monomers can reduce post
processing– Lignin removal can reduce cellulase use although AFEX
reduces cellulase without lignin removal• Greater hemicellulase activity would improve yields
from higher and controlled pH approaches• All are capital intensive for differing reasons
– Costly reactor materials and waste treatment, in some cases– Pretreatment catalyst recovery, in others
• Some advantages in operating costs– e.g., low waste generation with AFEX
Future Work• Complete pretreatments with each technology• Complete data on enzymatic digestibility
– Gather max yield data at 15 and 60 FPU/g glucan– Determine yields in SSF configuration
• Characterize hydrolyzate toxicity to organisms• Characterize pretreated materials to improve
picture of key differences and similarities, e.g., acetyl content, crystallinity
• Update process economic models with more developed pretreatment and enzymatic digestibility performance data
Acknowledgments The United States Department of Agriculture
Initiative for Future Agricultural and Food Systems Program through Contract 00-52104-9663 for funding this CAFI research
The United States Department of Energy Office of the Biomass Program and the National Renewable Energy Laboratory for NREL’s participation
Our team from Dartmouth College; Auburn, Michigan State, Purdue, and Texas A&M Universities; and the National Renewable Energy Laboratory