Download - 11IBBC - 22.2 - Zhu - TAPPI
2011 TAPPI IBBC
Atlanta, GA, March 14-16, 2011
J.Y. ZhuUS Forest Service, Forest Products Laboratory, Madison, WIUS Forest Service, Forest Products Laboratory, Madison, WI
Why is so unique about Why is so unique about woody biomass ?woody biomass ?
Strong structure and large physical sizeStrong structure and large physical sizeHigh energy for size reduction High energy for size reduction
Strong recalcitrance to deconstruction: Strong recalcitrance to deconstruction: Most pretreatment not efficient Most pretreatment not efficient Especially for softwoods Especially for softwoods
Supply of BiomassSupply of Biomass
~180 softwood~180 softwood
Forest BiorefineryForest BiorefineryEnergy for wood size reduction
Remove recalcitrance - Pretreatment
Enzyme adsorption to lignocellulosenonproductive adsorption by lignin washing
Feedstock ComparisonFeedstock Comparison
Cornstover
50 Wh/kg50 Wh/kg
500500‐‐1000 Wh/kg1000 Wh/kg
~50 Wh/kg~50 Wh/kg
1.3 cents/liter1.3 cents/liter
Energy Consumption for Energy Consumption for Size ReductionSize Reduction
Size reductionSize reductionNonwoody:Nonwoody: 50 Wh/kg = 50 Wh/kg = 0.180.18 GJ/tonGJ/tonWoody:Woody: 200200‐‐600 Wh/kg = 600 Wh/kg = 0.720.72‐‐2.162.16 GJ/ton GJ/ton
Biomass ethanol Biomass ethanol Energy Energy ~80 gallon/ton of ~80 gallon/ton of biomassbiomass (OD) (OD) Ethanol HHV = 90 MJ/gallonEthanol HHV = 90 MJ/gallonBiomass Biomass ethanol energyethanol energy = = 7.2 GJ/ton7.2 GJ/ton
Thermo to electric energy conversion: Thermo to electric energy conversion: 30%30%Nonwoody: Nonwoody: 8% 8% of total ethanol energyof total ethanol energyWoody: Woody: 3030‐‐90%90% of total ethanol energyof total ethanol energy
Sulfite, SPORL Technology
Lodgepole pine Wood chips
Steam
SPORLpretreatment
Spent Spent liquorliquor
Separation
Size reduction
WaterSubstrate
Press
HydrolysateHydrolysateFermentationFermentation EthanolEthanol
ChemicalsXAD columndetoxification
Filtration
Filtration water
Applied Microbiology Biotechnology (2010) 86:1355Applied Microbiology Biotechnology (2010) 86:1355
SPORL ChemistrySPORL Chemistry
Avoid excessive lignin condensation Avoid excessive lignin condensation
Sulfonated ligninSulfonated lignin
Hemicellulose degradationHemicellulose degradation
Cellulose depolymerizationCellulose depolymerization
Low delignificationLow degradation hemi.Low depolym. cellulose
Hemi. degradationCellulose depolym.Lignin condensation
Energy Savings byEnergy Savings byPostPost--Pretreatment SizePretreatment Size--ReductionReduction
Pretreatment @180oC for
30 mina
Initial liquor
pH
Disk milling energy
(kWh/ton wood)
Size-reduction energy savings
(%)
SED (%)
Untreated 699 12.7Hot-water 5.0 680 2.7 16.0Acid 1.1 412 41.0 41.6SPORL 4.2 594 15.0 75.1SPORL 1.9 153 78.1 91.6
Bioresource Technology (2010) 101:2782Bioresource Technology (2010) 101:2782
Effect of Milling DiskEffect of Milling Disk--Plate GapPlate Gap
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.08
16
32
64
128
256
512
Pretreatment pH(t=0) Hot water 5.0 Dilute acid 1.1 SPORL 4.2 SPORL 1.9
D
isk-
mill
ing
ener
gy(W
h/kg
od
untr
eate
d w
ood)
Disk-plate gap (mm)
Bioresource Technology (2010) 101:2782Bioresource Technology (2010) 101:2782
Effect of Milling DiskEffect of Milling Disk--Plate GapPlate Gap
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.030
40
50
60
70
80
90
100
Pretreatment pH(t=0) Dilute acid 1.1 y = 42.6 - 1.52x, r2 = 0.72SPORL 1.9 y = 97.2 - 1.68x, r2 = 0.61
SED
(wt%
of s
ubst
rate
glu
can)
Disk plate gap (mm)
Bioresource Technology (2010) 101:2782Bioresource Technology (2010) 101:2782
Woody Species StudiedWoody Species Studied
Softwood Softwood Lodgepole pineLodgepole pineRed pineRed pineSpruceSpruce
Hardwoods Hardwoods AspenAspenEucalyptus Eucalyptus Poplar: NE222, NM6, DN5Poplar: NE222, NM6, DN5
Decayed TreeDecayed Tree
High Solids Saccharification and Fermentation
0 20 40 60 80 100 120 140 160 1800
10
20
30
40
50
60
Fermentation Experiments I II-1 II-2 II-3 III
SPORL DA
E
than
ol c
once
ntra
tion
(g/L
)
Fermentation duration (h)
Solids @ 18%
High Solids Saccharification and Fermentation
Solids @ 18%
6 8 10 12 14 1620
30
40
50
60
70
80
90
SPORL DA
SSF
effic
ienc
y @
96
h (%
)
Cellulase dosage (FPU/g glucan)
Washing of SolublesWashing of Solubles
Enzyme adsorption to lignocellulosenonproductive adsorption by lignin washing
Unwashed SPORL Substrate: Unwashed SPORL Substrate: Comparing washing with MgSOComparing washing with MgSO44
5 10 15 20 25 3040
50
60
70
80
90
100
Unwashed Washed @ 25oC Unwashed + Mg(II)
Subs
trat
e en
zym
atic
dig
estib
ility
, SED
(%)
Cellulase loading (FPU/g cellulose)
Bioresource Technology (2010) 101:9120Bioresource Technology (2010) 101:9120
Material and Energy Analysis
0.18(50 wh/kg)
0.41(113 Wh/kg)
1.33
NA
NA
NANA
4.55GJ/ton wood
B
603
C397
Glucan: 32Mannan: 86Xylan: 27
D Lignin: 76
Ethanol: 67D Lignin: 76
AGlucan: 385Mannan: 4Xylan: 8
H Lignin: 195 Ethanol: 209H Lignin: 195
1000Glucan: 426Mannan: 110
Xylan: 69Lignin: 271
Ethanol
276 Liters
Dissolved (D) Ligninin spent liquor
Hydrolysis (H) lignin from solid substrate
Applied Microbiology Biotechnology (2010) 86:1355Applied Microbiology Biotechnology (2010) 86:1355
SPORL – Without detoxification
SPORLpretreatment
Steam
Che
mic
als
Separation
Size reduction
Water Press
CombinedCombinedFermentationFermentation
EthanolEthanol
Lignosulfonate
SpentLiquor
Filtration water
Bioresource Technology (2010) 101:8678Bioresource Technology (2010) 101:8678
Mass Energy BalanceMass Energy Balance
0.18(50 wh/kg)
0.76(212 Wh/kg)
1.33
NA
NA
NA
1000Glucan: 419Mannan: 117
Xylan: 55Lignin: 286
606
NA Ethanol
270 Liters
394Glucan: 27Mannan: 60Xylan: 22Lignin: 73
Ethanol: 213Lignin: 286
603Glucan: 367Mannan: 3Xylan: 3
Lignin: 213
4.05
Bioresource Technology (2010) 101:8678Bioresource Technology (2010) 101:8678
Pilot Scale StudyPilot Scale Study
CDCD‐‐300 Disk refiner with Impregnation 300 Disk refiner with Impregnation
SemiSemi‐‐continuouscontinuous
20 20 –– 40 kg per run40 kg per run
Future PlansFuture Plans
Partner with industry for Jet fuel Production Partner with industry for Jet fuel Production
Lignin coLignin co‐‐productsproducts
SPORL PublicationsSPORL PublicationsZhu, J.Y., Zhu, J.Y., Pan, X.J., Wang, G.S, Gleisner, R., Pan, X.J., Wang, G.S, Gleisner, R., (2009),(2009), ““Sulfite Pretreatment (SPORL) Sulfite Pretreatment (SPORL)
for Robust Enzymatic Saccharification of Spruce and Red Pinefor Robust Enzymatic Saccharification of Spruce and Red Pine““ Bioresource Technology, Bioresource Technology, 100(8):2411100(8):2411--2418.2418.
Wang, G.S., Pan, X.J., Wang, G.S., Pan, X.J., Zhu, J.Y., Zhu, J.Y., Gleisner, R., Rockwood, D.R., Gleisner, R., Rockwood, D.R., (2009), (2009), ““Sulfite Sulfite Pretreatment to Overcome Recalcitrance of Lignocellulose (SPORL)Pretreatment to Overcome Recalcitrance of Lignocellulose (SPORL) for Robust Enzymatic for Robust Enzymatic Saccharification of HardwoodsSaccharification of Hardwoods““ Biotechnology Progress, 25(4):1086Biotechnology Progress, 25(4):1086--1093 1093
Zhu, W., Zhu, W., Zhu, J.Y., Zhu, J.Y., Glesiner, R., Pan, X.J., Glesiner, R., Pan, X.J., (2010), (2010), ““On Energy Consumption for SizeOn Energy Consumption for Size--Reduction and Yield from Subsequent Enzymatic Hydrolysis of LodgReduction and Yield from Subsequent Enzymatic Hydrolysis of Lodgepole Pine,epole Pine,”” Bioresource Bioresource Technology ,101:2782Technology ,101:2782--27922792
Zhu, J.YZhu, J.Y., Zhu, W. OBryan, P., Dien, B.S.,Tian, S., Gleisner, R., Pan, X., Zhu, W. OBryan, P., Dien, B.S.,Tian, S., Gleisner, R., Pan, X.J., .J., (2010), (2010), ““Ethanol Production from SPORLEthanol Production from SPORL--Pretreated Lodgepole Pine: Preliminary Evaluation of Mass Pretreated Lodgepole Pine: Preliminary Evaluation of Mass Balance and Process Energy EfficiencyBalance and Process Energy Efficiency””. . Applied Microbiology and Biotechnology Applied Microbiology and Biotechnology 86:135586:1355--13651365
Tian, S., Luo, X., Yang, X.S., Tian, S., Luo, X., Yang, X.S., Zhu, J.Y., Zhu, J.Y., (2010) (2010) ““Robust Cellulosic Ethanol Production Robust Cellulosic Ethanol Production from SPORLfrom SPORL--Pretreated Lodgepole Pine using an Adapted s. cerevisiae withoutPretreated Lodgepole Pine using an Adapted s. cerevisiae without DetoxificationDetoxification””,,Bioresource Technology 101:8678Bioresource Technology 101:8678--86858685
Liu, H., Liu, H., Zhu, J.Y., Zhu, J.Y., Fu, S.Y., Fu, S.Y., (2010), (2010), ““Effects of LigninEffects of Lignin--Metal Complexation on Enzymatic Metal Complexation on Enzymatic Hydrolysis of CelluloseHydrolysis of Cellulose””. . J. Agricultural and Food Chemistry, 58:7233J. Agricultural and Food Chemistry, 58:7233--72387238
Liu, H., Liu, H., Zhu, J.Y., Zhu, J.Y., (2010)(2010) ““Eliminating Inhibition of Cellulase by Unbound Lignin in Eliminating Inhibition of Cellulase by Unbound Lignin in Unwashed SPORLUnwashed SPORL--Pretreated Lignocellulose Using LigninPretreated Lignocellulose Using Lignin--Metal ComplexationMetal Complexation““ Bioresource Bioresource Technology, 101:9120Technology, 101:9120--91279127
SPORL PublicationsSPORL PublicationsLuo, X.L., Gleisner, R., Tian, S., Zhu, W.Y., Negron, J., Horn, Luo, X.L., Gleisner, R., Tian, S., Zhu, W.Y., Negron, J., Horn, E., Pan, X.J, E., Pan, X.J, Zhu, J.Y., Zhu, J.Y., (2010), (2010),
““Evaluation of Mountain Beetle Killed Lodgepole Pine for CellulosEvaluation of Mountain Beetle Killed Lodgepole Pine for Cellulosic Ethanol Production by ic Ethanol Production by SPORLSPORL”” Ind. Eng. Chem. Res. Ind. Eng. Chem. Res. 49(17):8258‐8266Zhu, J.Y., Zhu, J.Y., Pan, X.J., Zalesny, R.S. Jr., Pan, X.J., Zalesny, R.S. Jr., (2010), (2010), ““Pretreatment of Woody Biomass for Biofuel Pretreatment of Woody Biomass for Biofuel
Production: Energy Efficiency, Technologies and RecalcitranceProduction: Energy Efficiency, Technologies and Recalcitrance”” Applied Microbiology and Applied Microbiology and Biotechnology, 87:847Biotechnology, 87:847‐‐857857Tian, S. , Zhu, W., Gleisner, R., Pan, X.J., Tian, S. , Zhu, W., Gleisner, R., Pan, X.J., Zhu, J.Y., Zhu, J.Y., (2010) (2010) ””Comparisons of SPORL and Comparisons of SPORL and
Dilute Acid Pretreatments for Sugar and Ethanol Productions fromDilute Acid Pretreatments for Sugar and Ethanol Productions from AspenAspen”” Biotechnology Biotechnology Progress (accepted)Progress (accepted)Zhu, J.Y., Zhu, J.Y., Wang, G.S., Gleisner, R., Pan, X., Wang, G.S., Gleisner, R., Pan, X., (2009), (2009), ““Specific Surface for Evaluating Wood Specific Surface for Evaluating Wood
Size Reduction and Pretreatment EfficienciesSize Reduction and Pretreatment Efficiencies”” Chemical Engineering ScienceChemical Engineering Science, , 64(3):47464(3):474‐‐485. 485. Zhu, J.Y. Zhu, J.Y. and Pan, X.J., and Pan, X.J., (2010), (2010), ““Woody Biomass Pretreatment for Cellulosic Ethanol Woody Biomass Pretreatment for Cellulosic Ethanol
Production: Technology and Energy Consumption EvaluationProduction: Technology and Energy Consumption Evaluation”” Bioresource Technology Bioresource Technology 101:4992101:4992‐‐50025002
EthanolFL: 206 L/ton
FDD: 222 L/ton
NA
FL: 2.62FDD: 3.21
0.18
FDD1000
Glucan: 420Mannan: 95Xylan: 46
K. Lignin: 282
1.33
FL: 0.68
FDD: 0.46
FL:634
Glucan: 351Mannan: 9Xylan: 9
Lignin: 241
FDD:630
Glucan: 380Mannan: 7Xylan: 7
Lignin: 207
FL:Ethanol: 162Lignin: 241
FDD:Ethanol: 175Lignin: 207
FL1000
Glucan: 391Mannan: 100
Xylan: 60K. Lignin: 286
FDD: 370Glucan: 21 Acetic acid: 8Mannan: 45 HMF as hexsan: 4Xylan: 20 Furfural as pentosan: 5Lignin: 75
FL: 366Glucan: 20 Acetic acid: 9Mannan: 46 HMF as hexsan: 4Xylan: 26 Furfural as pentosan: 6Lignin: 51
NA
FL:
Gluc
ose:
264
FDD:
Gluc
ose:
277
SPORL SPORL -- Dilute Acid ComparisonsDilute Acid Comparisons
EthanolSPORL: 238 L/ton
DA: 214 L/ton
NA
SPORL: 4.09DA: 3.40
0.18
1000Glucan: 438Mannan: 16Xylan: 164K. Lignin: 208
NA
SPORL/DA:1.25
SPORL: 0.07
DA: 0.17
SPORL:627
Glucan: 432Mannan: 0Xylan: 12Lignin: 161
DA:664
Glucan: 418Mannan: 1Xylan: 13Lignin: 194
DA:336
Glucan: 13 Acetic acid: 50Mannan: 12 HMF as hexsan: 2Xylan: 97 Furfural as pentosan: 16Lignin: 14
SPORL:373
Glucan: 11 Acetic acid: 68Mannan: 12 HMF as hexsan: 2Xylan: 108 Furfural as pentosan: 13Lignin: 47
SPORL:627
Ethanol: 188Lignin: 161
DA:664
Ethanol: 169Lignin: 194
SPORL:H2S04: 11NaHS03: 30
DA:H2S04: 11