Agro-energy feedstock: Miscanthusg gy Miscanthus x giganteus

Sterile hybrid propagated though rhizomes Sterile hybrid propagated though rhizomes Bulk sample harvested in Germany Air dried and

stored in freezerstored in freezer Composite sample being used for all analyses

Biomass to Bioethanol1

Agro-energy feedstock: Miscanthusg gy

Perennial crop Perennial cropGrows to 11-14 ft in height/year

High biomass yields High biomass yieldsC4 grass with high rate of carbon fixation14 17 t / ( t 27 t / i t i l )14 – 17 tons/acre (up to 27 tons/acre in trials)Crop stands survive 25-30 years without

significant loss in biomass yieldssignificant loss in biomass yields

Presently used in Europe for power and heat tigeneration

Biomass to Bioethanol2

Moisture and Ash content

Moisture content of air dried Moisture content of air dried Miscanthus sawdust (6 mm)4 6%4.6%

Ash contentMe ed b mped he ting to 525Measured by ramped heating to 525 °C in a muffle furnace

2 2%2.2%Higher than Loblolly pine (0.2 %) &

sweetgum (0 8 %)sweetgum (0.8 %)

Biomass to Bioethanol3

Elemental analysisyMeasured on 0.05 mm ground samples using elemental micro analyzer

60.0

50.0

40.0 MiscanthusSweetgumLoblolly Pine

30.0

Wt.%

10 0

20.0

0.0

10.0

Biomass to Bioethanol4

0.0C H O N

Inorganic elementsg

Analyzed in 6 mm ground samples Analyzed in 6 mm ground samples Acid digestion followed by ICP-emission

spectroscopyspectroscopy Coulometric method for total halogen (Cl+Br+I)

Biomass to Bioethanol5

Inorganic elementsg

340 0

360.0

380.0

280.0

300.0

320.0

340.0

MiscanthusSweetgumL.Pine

200 0

220.0

240.0

260.0

) o.d

. wei

ght

L.Pine

140.0

160.0

180.0

200.0

onte

nt (m

g/K

g)

60 0

80.0

100.0

120.0Co

0.0

20.0

40.0

60.0

Biomass to Bioethanol6Ba Cu Fe Na P Si

Inorganic elementsg

2000.0

1750.0

ght)

Miscanthus

1250.0

1500.0

en d

ried

wei

g MiscanthusSweetgumL.Pine

750 0

1000.0

ent (

mg/

Kg

ove

500.0

750.0

Con

te

0.0

250.0

Biomass to Bioethanol7Ca K Mg S Mn Cl+Br+I

Extractives Solvent-soluble, non-volatile

material Condensermaterial Extracted with dichloromethane

Condenser

Characterized using GC-MS Extractives content: Sample

1.0 % 2.9 % for Loblolly pine Solvent

0.4 % for Sweetgum

Water soluble extractives (important for grassy biomass)3.6 %

Biomass to Bioethanol8

Dichloromethane extractives composition

350.0

400.0

250 0

300.0

wei

ght

Miscanthus

200.0

250.0

ams/

g o.

d. Miscanthus

SweetgumL.Pine

100.0

150.0

mic

rogr

a

0.0

50.0

rboxy

lic ac

ids

Resin ac

ids

Alkanols

Sterols

gnin/Aro

matic

Biomass to Bioethanol9

Carb Lign

Dichloromethane Extractives : Miscanthus120.0 O OH

80.0

100.0

scan

thus

60.0

/gra

m o

.d. m

is

C2H5

20 0

40.0

mic

rogr

ams/

COOH

HO

0.0

20.0

cid cid cid cid cid ol cid rol rol rol

Tetrad

ecan

oic ac

idPen

tadec

anoic

acid

Hexad

ecan

oic ac

idOcta

deca

dieno

ic ac

idOcta

deca

noic

acid

Octaco

sano

Dehyd

roabie

etic a

cid

Ergoste

roStig

master

o

Sitoste

ro

Biomass to Bioethanol109,1

2-O

D

Water soluble extractives: MiscanthusCompound Amount (µg/g Miscanthus)

Alpha-L-Galactopyranose 40.24p py

Alpha-D-Arabinopyranose 52.81

Xylitol 512.22

D Gl 30 12

MannitolD-Glucose 30.12

p-hydroxyl cinnamic acid 1145.21

D-Mannitol 1358.42

Mannose 105.84

O OHCH2OH OH

XylitolOHO

O

OH

OH OHOH

M

O

OH

OHHOOH

Gl

OH

OH

HO

A biMannose Glucose Arabinopyranose

P-hydroxyl cinnamic acid

Biomass to Bioethanol11

Acid soluble and insoluble ligning Klason lignin

Acid insoluble lignin isolated using NREL methods Acid insoluble lignin isolated using NREL methods Extractive free (40 mesh) sample hydrolyzed using 72 % H2SO4

Acid soluble lignin Acid soluble lignin Measured using UV-vis spectrophotometer Calculated from absorption at 205 nm

Pretreatment effluents pH adjusted by the addition of 72 % H2SO4 and autoclaved at 121

°C f 1 h°C for 1 hour Solution filtered and lignin content measured as the sum of solid

residue (Klason lignin) and soluble lignin measured with UV.( g ) g

Biomass to Bioethanol12

Lignin content and compositiong

CH

CH2OH

CH

CH2OH

CH

CH2OH

Klason lignin

26

CH

CH

1CH

CH

126

CH

CH

126

Klason lignin Miscanthus: 25 %Loblolly pine: 29 %Sweetgum: 26 %

CH3OOH

3

4 OCH35

OH

3

45

OH

3

4 OCH35

Sweetgum: 26 %

A id l bl li i

SW x xGuaiacyl Syringyl p-Coumaryl

OHAcid soluble ligninMiscanthus: 1.1 %Loblolly pine: 0.5 %Sweetgum: 2 6 %

HW x x xGrass x x x

Sweetgum: 2.6 %

Biomass to Bioethanol13

Carbohydrate analysisy y

40 mesh extractive free wood Hydrolyzed with 72 % H2SO4

Diluted to 3% H2SO4 and autoclaved at 121°C for 1 hour121 C for 1 hour

For pretreatment effluentspH adjusted by the addition of 72 %H2SO4p j y 2 4

Autoclaved at 121 °C for 1 hourFiltered and filtrate used for sugar analysis

S ga s meas ed sing HPLC ith Sugars measured using HPLC with pulsed amperometric detector

Biomass to Bioethanol14

Carbohydrate profile

0 0

55.0

60.0y

OOH

OH

HOOH

40 0

45.0

50.0

drat

es

OH

30 0

35.0

40.0

of c

arbo

hyd

MiscanthusSweetgumL.Pine

O

20.0

25.0

30.0

dry

wei

ght o

OOHOH

OHCH2OH

O

OH

OH

OHOH

CH2OH

10.0

15.0

% d

OOH

HO

HOOH

O

OH

OH OHOH

CH2OH

0.0

5.0

A bi G l t Gl X l M

OH

HO

Arabinose Galactose Glucose Xylose Mannose

Biomass to Bioethanol15

Summary: Miscanthus compositiony Higher ash content than sweetgum or pineHi h t t f P K Si d h lidHigher contents of P, K, Si and halides

Dichloromethane extractives mostly carboxylic d lk l d lacids, alkanols and sterols

Water extractives mostly derived from carbohydrates

26 % total lignin content 26 % total lignin contentLower than woody biomass feedstocks

Carbohydrates are mostly glucose and xylose Carbohydrates are mostly glucose and xyloseXylose content highest among the three feedstocks

Biomass to Bioethanol16