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NREL Update—CAFI 2 Teleconference

Rick ElanderNational Renewable Energy Laboratory

National Bioenergy CenterGolden, CO

February 18, 2004

Biomass Refining CAFI

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Outline

• Dilute Acid Pretreated Corn Stover Data

• Dilute Acid Pretreated Hybrid Poplar Data (Bench Scale-Steam Gun)

• Description of Dilute Acid Pretreated Hybrid Poplar (Pilot Scale-Sunds Reactor)– Data not yet available

Biomass Refining CAFI

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Dilute Acid Pretreated Corn Stover• Feedstock: 2nd pass corn stover from Kramer farm (Wray, CO)

– Collected using high rake setting to avoid soil pick-up– Milled to pass 0.25 inch screen (Mitts and Merril knife mill)

– Pretreated in Sunds vertical reactor, with and without hot washing

Biomass Refining CAFI

Component Composition (wt %)

Sucrose 2.2Glucan 34.4Xylan 22.8

Arabinan 4.2Mannan 0.6Galactan 1.4

Lignin 11.0Protein 2.3Acetyl 5.6Ash 6.1

Uronic Acids 3.8Extractives 8.5

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Biomass Refining CAFI

Pilot Scale Sunds Vertical Reactor

Steam, Hot Water, Hot Acid, Alkali, or Solvent, Hot Air

Pneumapress Filter

Pressurized Solids Tank (Jaygo Reactor)

Steam, Hot Water, Hot Acid or Alkali

High Solids Discflo Pump and Heated Transfer Line

Optional “Hot-Washing” in Pneumapress Filter

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Dilute Acid Pretreated Corn StoverPretreatment Conditions:1. Typical “mid severity” condition in the Sunds vertical pretreatment reactor (190 C, ~ 1.5 minute

residence time in “flowthrough mode”, 0.045 g sulfuric acid/g dry feedstock, 30% insoluble solids) 2. “Low severity” condition in the Sunds vertical pretreatment reactor (180 C, ~ 1.5 minute residence

time in “flowthrough mode”, 0.03 g sulfuric acid/g dry feedstock, 25% insoluble solids) 3. “Low severity” condition in the Sunds vertical pretreatment reactor (180 C, ~ 1.5 minute residence

time in “flowthrough mode”, 0.03 g sulfuric acid/g dry feedstock, 25% insoluble solids) and hot washed in Pneumapress pressure belt filter with hot water.

Biomass Refining CAFI

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Dilute Acid Pretreated Corn Stover—Pretreated Solids Composition and

Component Solubilization

Biomass Refining CAFI

Pretreated Solids Composition (wt %)

Amount of Original Component Remaining After Pretreatment

(%)Pretreated Solids

Composition (wt %)

Amount of Original Component Remaining After

Pretreatment (%)Pretreated Solids

Composition (wt %)

Amount of Original Component Remaining After Pretreatment

(%)Glucan 59.5 78.2 57.7 84.7 59.3 93.4Xylan 4.9 13.0 10.5 24.9 9.3 27.2

Arabinan 1.4 22.2 1.3 24.8 0.8 20.1Mannan 0.9 20.2 0.8 29.1 0.8 57.4Galactan 0.9 27.8 0.8 25.1 0.5 22.8

Lignin 29.5 82.4 22.7 81.2 22.5 n/aProtein 2.2 n/a 2.5 n/a 1.9 n/aAcetyl 0.0 n/a nd n/a 1.4 n/a

Ash 4.3 n/a 3.7 n/a 4.6 n/a

Mass % of feedstock remaining insoluble after pretreatment: 46.5

Mass % of feedstock remaining insoluble after pretreatment: 55.9

Mass % of feedstock remaining insoluble after pretreatment: 54.5

Sample 3

Low Severity Sunds Hot Wash, CS040427-J

Sample 2

Low Severity Sunds, 031209CS #7DALW-CSR-180C-1.5m-0.030H2SO4:Dry wt-25% solids-4/27/04-J

Sample 1

Mid Severity Sunds, 031209CS Mix 2-5 DALW-CSR-190C-1.5m-0.045H2SO4:Dry wt-30% solids-12/9/03-Mix 2:5 DALW-CSR-180C-1.5m-0.030H2SO4:Dry wt-25% solids-12/9/03-#7

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Dilute Acid Pretreated Hybrid Poplar (Bench Scale-Steam Gun)

• Feedstock: USDA-supplied hybrid poplar (Alexandria, MN)– Debarked, chipped, and milled to pass 0.25 inch screen (Mitts and Merril knife mill)

– Pre-impregnated with H2SO4 and pretreated in 4 L NREL steam gun

Biomass Refining CAFI

Component Composition (wt %)Glucan 43.8Xylan 14.9

Arabinan 0.6Mannan 3.9Galactan 1.0

Lignin 29.1Protein ndAcetyl 3.6Ash 1.1

Uronic Acids ndExtractives 3.6

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Dilute Acid Pretreated Poplar in Steam Gun

Biomass Refining CAFI

190 C

70 s

Acid Loading: 0.02 g H2SO4/g bone dry feedstock

190 C

120 s

200 C

70 s

200 C

120 s

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Composition of Pretreated Solids from Dilute Acid Pretreated Hybrid Poplar (Bench

Scale-Steam Gun)

Biomass Refining CAFI

Pretreatment Conditionw

t % A

sh

wt %

Pro

tein

wt %

Lig

nin

wt %

Glu

can

wt %

Xyl

an

wt %

Gal

acta

n

wt %

Ara

bina

n

wt %

Man

nan

wt %

Uro

nic

acid

wt %

Ace

tate

Tota

l %

MP041004 A-G (190 C/70 s) 0.1 0.0 46.1 57.3 2.1 0.0 0.0 0.0 0.0 0.0 105.5MP041005 A-G (190 C/120 s) 0.0 0.0 42.5 60.3 1.8 1.0 0.0 0.0 0.0 0.0 105.6MP041005 H-N (200 C/70 s) 0.0 0.0 49.1 54.6 1.5 0.9 0.0 0.0 0.0 0.0 106.1MP041006 A-G (200 C/120 s) 0.0 0.0 59.3 44.3 0.7 0.3 0.0 0.0 0.0 0.0 104.6

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Composition of Pretreated Liquids from Dilute Acid Pretreated Hybrid Poplar (Bench

Scale-Steam Gun)

Biomass Refining CAFI

Hydrolyzate pH 1.48 1.48 1.48 1.50Glucose Concentration as Cellobiose (g/L) 1.5 1.5 1.9 3.1 as Glucose Monomer (g/L) 43.4 42.5 47.2 66.2 as Total Monomer + Oligomer (g/L) 50.1 49.7 54.5 75.5Xylose Concentration as Monomer (g/L) 44.3 44.0 42.3 22.5 as Total Monomer + Oligomer (g/L) 44.7 45.2 43.7 21.1Galactose Concentration as Monomer (g/L) 4.1 4.0 3.9 2.6 as Total Monomer + Oligomer (g/L) 4.7 4.7 3.7 2.5Arabinose Concentration as Monomer (g/L) 2.3 2.3 2.2 1.1 as Total Monomer + Oligomer (g/L) 1.5 1.7 1.7 0.9Mannose Concentration as Monomer (g/L) 9.7 9.8 8.2 6.0 as Total Monomer + Oligomer (g/L) 10.5 10.2 9.4 5.7Soluble Lignin Concentration (g/L) 22.8 20.4 24.1 29.5Acetic Acid Concentration (g/L) 22.1 20.9 21.5 20.2Furfural Concentration (g/L) 8.7 7.7 8.7 12.2HMF Concentration (g/L) 1.8 1.6 1.9 3.8

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Glucose and Xylose Component Balance from Dilute Acid Pretreated Hybrid Poplar

(Bench Scale-Steam Gun)

Biomass Refining CAFI

Glucose Component Balance as Glucan (% of original) 87.9 88.0 75.7 67.0 as Glucose Monomer (% of original) 20.7 19.6 24.4 29.4 as Glucose Oligomer (% of original) 3.2 3.4 4.3 4.5 as HMF (% of original) 0.4 0.4 0.5 0.8 Total (% of original) 112.2 111.4 104.9 101.7Xylose Component Balance as Xylan (% of original) 8.3 7.9 5.4 2.9 as Xylose Monomer (% of original) 61.8 56.5 62.4 28.9 as Xylose Oligomer (% of original) 0.6 1.5 2.9 -1.4 as Furfural (% of original) 19.5 18.0 22.0 28.3 Total (% of original) 90.2 83.9 92.7 58.7

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Example of Detailed Component Balance from Dilute Acid Pretreated Hybrid Poplar

(Bench Scale-Steam Gun)

Biomass Refining CAFI

Pretreatment ConditionsPretreatment Temperature (deg C) 190Pretreatment Time (sec) 70Sulfuric Acid Loading 0.02 g acid/g B.D. feedstock

Sample Label (NREL nomenclature) MP-041004 a-gSample Label (CAFI nomenclature) DASE-POP1-190C-70s-0.02H2SO4:Dry wt-30% solids-10/4/04-N-A:G

Total pretreated mass output including rinsate (O.D. wt) (g) 2529.8Total charge of preimpregnated feedstock--wet wt. (g) 5950.0 Total wet wt of pretreated feedstock (g)--including steam condensate 8143.0Total feedstock input (O.D. wt) (g) 2664.4 Measured total dry solids of pretreated feedstock (wt%) 30.1

Feedstock mass solubilized in pretreatment (% of original feedstock) 29.5

Total SolublesRecovery Recovery

(wt%) Total (wt%) Total (g/L) (g/L) Total (g/L) (g/L) Total (% in feed) (% in feed)wt (g) wt (g) Monomeric Total sugar wt (g) Monomeric Total sugar wt (g)

43.80 1295.4 57.32 1138.4 43.41 50.10 305.0 0.85 0.98 4.0 112.6 23.93.94 116.5 0.00 0.0 9.74 10.50 63.9 0.44 0.47 2.0 66.1 56.51.02 30.2 0.00 0.0 4.07 4.69 28.6 0.19 0.22 0.9 97.6 97.6

14.85 447.1 2.07 37.0 44.28 44.69 272.1 1.64 1.66 6.8 83.1 62.40.61 18.4 0.00 0.0 2.30 1.53 9.3 0.00 0.00 0.0 50.7 50.7

Crude protein 0.00 0.0 0.00 0.029.12 775.9 46.06 824.1 22.82 22.82 138.9 124.1 17.9

3.56 94.9 0.00 0.0 0.0 0.03.62 96.5 0.00 0.0 22.12 134.7 0.97 4.0 143.81.07 28.5 0.06 1.1 3.8

8.71 53.0 0.67 2.81.78 10.8 0.20 0.8

Furfural included in xylan component balanceHMF included in glucan component balance

GalactanXylan

AshFurfural*HMF*

Component

Arabinan

Total LigninExtractivesAcetic acid*

GlucanMannan

Water-solubles (in pressate by HPLC) RinsateFeedstock

input Water-insolublesPretreated Solids Pretreated Liquids

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Dilute Acid Pretreated Hybrid Poplar (Pilot Scale-Sunds Reactor)• Feedstock: USDA-supplied hybrid poplar (Alexandria, MN)

– Debarked, chipped, and milled to pass 0.25 inch screen (Mitts and Merril knife mill)• Utilized Sunds reactor, with and without Pneumapress hot washing• Pretreatment conducted at less severe conditions than steam gun runs, due to apparent “over-pretreatment”

– 175 C, ~ 1.5 minute residence time in “flowthrough mode”, 0.025 g sulfuric acid/g dry feedstock, 25% insoluble solids

• Five samples sent– Separation only (no washing)– Hot water washed– Hot dilute ethanol (0.5 wt%) washed– Hot dilute NaOH (0.2 wt%) washed– Hot dilute ethanol (0.5 wt%) and NaOH (0.2 wt%) washed

• Compositional analysis and mass balance data not yet available

Biomass Refining CAFI

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CAFI Labeling Nomenclature for Previously Sent Samples

Biomass Refining CAFI

Date Shipped Sample ID as sent Sample ID--CAFI Nomenclature Sample Description031209 CS-Mix 2-5 DALW-CSR-190C-1.5m-0.045H2SO4:Dry wt-30% solids-12/9/03-Mix 2:5 Pretreated corn stover solids -mid severity031209 CS #7 DALW-CSR-180C-1.5m-0.030H2SO4:Dry wt-25% solids-12/9/03-#7 Pretreated corn stover solids-low severityCS-040427-J DALW-CSR-180C-1.5m-0.030H2SO4:Dry wt-25% solids-4/27/04-J Pretreated and hot washed corn stover solids

MP-041004a-g DASE-POP1-190C-70s-0.02H2SO4:Dry wt-30% solids-10/4/04-N-A:G Steam Gun Pretreated Minn. Poplar solids (190 C, 70 sec)MP-041005a-g DASE-POP1-190C-120s-0.02H2SO4:Dry wt-30% solids-10/5/04-N-A:G Steam Gun Pretreated Minn. Poplar solids (190 C, 120 sec)MP-041005 h-n DASE-POP1-200C-70s-0.02H2SO4:Dry wt-30% solids-10/5/04-N-H:N Steam Gun Pretreated Minn. Poplar solids (200 C, 70 sec)MP-041006 a-g DASE-POP1-200C-120s-0.02H2SO4:Dry wt-30% solids-10/6/04-N-A:G Steam Gun Pretreated Minn. Poplar solids (200 C, 120 sec)

MP-041214 b-c DALW-CSR-175C-1.5m-0.025H2SO4:Dry wt-25% solids-12/14/04-B:C Sunds Pretreated Minn. Poplar solids -air blow-downMP-041214 e-f DALW-CSR-175C-1.5m-0.025H2SO4:Dry wt-25% solids-12/14/04-E:F Sunds Pretreated Minn. Poplar solids - hot water washMP-041214 g-i DALW-CSR-175C-1.5m-0.025H2SO4:Dry wt-25% solids-12/14/04-G:I Sunds Pretreated Minn. Poplar solids- hot washed w/ 0.5% EthanolMP-041214 k-m DALW-CSR-175C-1.5m-0.025H2SO4:Dry wt-25% solids-12/14/04-K:M Sunds Pretreated Minn. Poplar solids- hot washed w/ 0.2% NaOHMP-041214 n-p DALW-CSR-175C-1.5m-0.025H2SO4:Dry wt-25% solids-12/14/04-N:P Sunds Pretreated Minn. Poplar solids- hot washed w/ 0.5% Ethanol and

0.2% NaOH

9/20/2004

11/2/2004

12/22/2004