USDA, Agricultural Research Service

Teleseminar Series on Chemical Conversion Technologies

December 13, 2011

Hydrocarbons
H d b via
i Th
Thermall Deoxygenation
D ti
of Biomass Hydrolyzates

M. Clayton Wheeler
M
University of Maine, Forest Bioproducts Research Institute (FBRI)
 UMaine Forest Bioproducts Research Institute
http://www.forestbioproducts.umaine.edu/

FBRI Technology 
Research Center

FBRI Chem. Bio. Eng.
Chemistry

Advanced 
Composites

Biology

Forestry

Margaret Chase Smith 
Policy Center

USDA/ARS    December 13, 2011 2
 FBRI Technology Research Center

USDA/ARS    December 13, 2011 3
 Energy Comparison
> Barrel of Oil Equivalent (BOE) = 6.1GJ (5.8 MMBTU or 1.7 kW-hr)

Fuel Energy Density BOE/MT

(GJ/MT)
Oven Dry Wood
Oven Dry Wood 20 33
3.3
Cellulose, Hemicellulose 17.5 2.9
Lignin 25 4.1
Ethanol 29 4.7
Butanol 33 5.4
Crude Oil
Crude Oil 44 73
7.3
Diesel 45 7.4
Gasoline 47 7.7

USDA/ARS    December 13, 2011 4
 Oxygen and Hydrogen Affect
Energy Density

crude
42-45 MJ/kg
heavy oil 20 MJ/kg
(oven dry)
25 MJ/kg

hard coal 17-20 MJ/kg

anthracite 31 MJ/kg

van Krevelen diagram adapted from M. Kleinert and T. Barth, Energy and
F l 2008 (22)
Fuels, (22), 1371.
1371

USDA/ARS    December 13, 2011 5
 Theoretical Removal of Oxygen from Biomass
(Example: Cellulose to Hydrocarbon)
> Hydrodeoxygenation
6 H 2 + C6 H 10O5 → 6CH 2 + 5 H 2O
─ ~81% theoretical energy yield
─ 100% carbon efficiency
─ 48% mass efficiency
Hydrocarbon (HC)
> Theoretical Decomposition
C6 H 10O5 → 4CH 2 + H 2O + 2CO2
─ ~87% theoretical energy yield
─ 67% carbon efficiency
Oxygen removal as CO2
─ 35% mass efficiency
is more energy efficient

USDA/ARS    December 13, 2011 6
 Ketonization of Organic Acids
O

O
O
Δ
Ca + CaCO3

> Net removal of 1 CO2 and 1 H2O or 1.5 O atoms/acid:

─ Slaking CaO + H 2O → Ca (OH )2
─ Ketonization R1COOH + R2COOH + Ca (OH )2 → R1COR2 + 2 H 2O + CaCO3
─ Calcination CaCO3 → CaO + CO2
> Increases carbon chain length to R1+R2 +1
> Ketones can be hydrogenated and dehydrated to olefins which
can then be oligomerized to hydrocarbon mixtures

USDA/ARS    December 13, 2011 7
 Hybrid Biological/Thermal Process
> Mixed
Mi d alcohol
l h l biofuels
bi f l from
f industrial
i d i l bi
biomass streams
─ van Walsum and Wheeler, US DOE DE-FG36-08GO18165
Pulp 
P l
Wood Pulp
mill Ketonization
Extract  H2
Hemicellulose
Anaerobic  Calcium
Calcium  Thermal 
Thermal Ketones Hydrogenation
Fermentation Drying
Fermentation  Mixed
Fermentation       Carboxylates conversion
Broth Alcohols
(Mixed Culture)
CaCO3

Fermentation 
Broth

Calcium
Calcium 
Carboxylates
Mixed Ketones Hydrogenation

USDA/ARS    December 13, 2011 8
 Hydrolysis and Carboxylate
Ketonization Removes Oxygen as CO2
> Hydrolysis (Fitzpatrick, S.W., U.S. Patents 4,897,497 and 5,608,105 [Biofine])
Cellulosic H2SO4 Recycle
y Hydrolysis and Dehydration Products
Feed

PFR
CSTR Char

> Hypothetical Ketonization of Levulinic Acid

O

O O O

O
Ca + CaO + CO2
O

O O

USDA/ARS    December 13, 2011 9
 Thermal Deoxygenation (TDO) of
Calcium Levulinate
O 450 C

OH

20

Intensity
O
O
OH

10

0
20 40 60

Retention Time (min)

T. Schwartz, et al., Green Chem., 2010, 12, 1353–1356.

> Ramp to 450°C with N2 purge

> Water
W t soluble
l bl products
d t
> No predicted ketone observed
> 35 MJ/kg (calorimetry of extracts)

USDA/ARS    December 13, 2011 10
 TDO Reactions
O
O
O
O
O

O
Ca
O
CaCO3 + Base Base
O
O
O O H+ O H+ OH
O

Base

Base
O O

H2O OH
H2O
+ +

O O

Products can be explained by

─ initial Ketonization
─ followed by Pyrolysis
• Aldol condensation + dehydration
• High-temperature free radical reactions
USDA/ARS    December 13, 2011 11
 TDO of Unpurified Hydrolyzate Produces HC Oil

Trash H2SO4 Recycle Hydrolysis Products

PFR
CSTR Char

Δ
+ Ca(OH)2

Levulinic Acid + Impurities

USDA/ARS    December 13, 2011 12
 Formic Acid is the Key
+ + Ca(OH)2 + Δ

Aqueous +
A
arbon Conttribution

Gas

Oil
% Ca

Char

Carbonate

Formic/Levulinic Acid Ratio

> 82% of optimal carbon (to 44MJ/kg) and 78% of optimal mass
P.A. Case et al., Green Chem. 18 Nov. 2011, DOI:10.1039/C1GC15914C

USDA/ARS    December 13, 2011 13
 Thermogravimetric Analysis of Reagent
Formate and Levulinate Salts
> Cellulose hydrolyzates contain equimolar levulinate and formate
)2 → CO + H2 + CaCO3
> Ca(HCOO)
(

Virtually no carbon in residue of levulinate/formate mixture!

USDA/ARS    December 13, 2011 14
 Efficiencies of Carbohydrate Conversion
Cellulose: C6 H10O5 → 4CH 2 + H 2O + 2CO2
Xylan: .
C5 H 8O4 → 3 33CH 2 + 0.67 H 2O + 1.67CO2
Mass Efficiency (%) Energy Efficiency (%) §
Basis Theoretical Actual/Calculated Theoretical Actual/Calculated
Levulinate/Formate
35 27† 87 63
1/1
Cellulose 35 19† 87 44
Xylan 35 13‡ 89 32
Wood* 26 13 59 27
§ HHV(MJ/kg)
HHV(MJ/k ) = carb(17.5),
b(17 5) lilignin(25),
i (25) perfect
f t oil(44),
il(44) and
d actual
t l oil(41)
il(41)
† 70% levulinic acid yield, 78% oil yield
‡70% furfural yield, 70% conversion to levulinic acid, 78% oil yield
* Ash-free, 50% C6, 25% C5, 25% Lignin

USDA/ARS    December 13, 2011 15
 Summary of Product Yields
((Barrel of Oil Equivalent
q ((BOE)) = 6.1 GJ))
(% energy yield)
(70%) 95 kg
g (63%)
*
500 kg
g 350 kg
H d
Hydrocarbon
b Oil
Cellulose Organic Acids
(0.64 BOE)
(1.4 BOE)

(60%) 42 kg
1 DMT Wood 250 kg 154 kg (63%)*
Hydrocarbon Oil
(3.1 BOE) Xylan Organic Acids (0.32 BOE)
(0.7 BOE)
*Theoreticalmass yield to 44 MJ/kg = 0.35×87%
0 35×87%
Actual mass yield to 41 MJ/kg oil = 0.35×78%
250 kg Energy yield = 41/44×0.78×87% = 63%
Lignin
(1 BOE)
2 BOE available for:
• process energy
• improvements in mass or energy yields
• co-products
co products

USDA/ARS    December 13, 2011 16
 Drop-in Fuels via TDO of Biomass
Hydrolyzate
High yields of carbohydrate conversion to oil
HHV>41MJ/kg
<1% Oxygen
TAN = 1 mgKOH/g

Hydrolysis 
and 
Dehydration
Pyrolysis

Neutralize 
with Ca(OH)
with Ca(OH)2

USDA/ARS    December 13, 2011 17
 Independent Testing of Washed Crude TDO Oil
Produced from Biomass Hydrolyzate
Total Acid Number 1.02 mg KOH/g
Ramsbottom Carbon Residue 0 48 wt%
0.48
Boiling Point Distribution 
(ASTM D7169)
TRACE ICP 100
OXYGENATES (0.86%) METALS (ppm) 90
80

%Recoveered
GC Low Ox method (ppm) Aluminum <0.1 70
Acetaldehyde 43 A
Arsenici <0 1
<0.1 60
Methanol 18 Barium <0.1 50
Ethanol 53 Beryllium <0.1 40
30
Propanols 44 Bismuth <0.1 20
n-Butanol 14 Boron <0.1 10
Butyraldehyde 16 Cadmium <0 1
<0.1 0
Methyl T-Butyl Ether 24 Calcium 4.5 100 300 500
Ally Alcohol 4 Chromium <0.1 Boiling Point, °C
tert-Amyl Alcohol 15 Cobalt <0.1
Vinyl Acetate 8338 Copper 0.4
Iron 88
8.8
Lead 0.3
Magnesium <0.1
Potassium 0.2
Sodium 0.2

USDA/ARS    December 13, 2011 18
 Comparison of Boiling Point Distributions
Crude TDO Oil
Retorted Oil Shale
Oil Sands HGO
Light Arabian Crude
ure (°F)

#2 Diesel
Temperatu
T

Recovery (mass%)
> ~80%
80% Overlap with #2 diesel

USDA/ARS    December 13, 2011 19
 PONA Analysis (ASTM D6730)
35
Sub-400°F “Green Gasoline" Cut
30
Calculated Properties
O t
Octane, (R+M)/2 = 81.9
81 9 Paraffins
P ffi (2.7%)
(2 7%)
Volumee % Reccovered

25
Specific Gravity = 0.793 I-Paraffins (30.0%)
H/C ratio = 1.75 Olefins (16.8%)
20
Benzene = 0.8
0 8 vol% Cyclo-Paraffins
Cyclo Paraffins (19.0%)
(19 0%)
Aromatics (31.5%)
15

10

0
3 4 5 6 7 8 9 10 11 12 13 14 15
Carbon Number

USDA/ARS    December 13, 2011 20
 Conclusions/Implications
> Two-step pathway to fungible hydrocarbon oil (>41 MJ/kg)!
> 0.9 BOE / ODMT Wood demonstrated (1.9 BOE potential)
> Atmospheric pressure TDO
> No hydrogen
> No precious metal or other solid catalysts
> Cation may be regenerated in pulp mill based biorefinery
> Pyrolytic
y y “deoxyhydrogenation”
y y g tolerant to impurities
p
> Future improvements likely from lignin (1 BOE potential)
and improved carbohydrate yields

USDA/ARS    December 13, 2011 21
 Acknowledgements
> Prof. Adriaan van Heiningen
> Thomas Schwartz
> Paige Case
> Scott Eaton
> Nick Hill
> Dr.
Dr Sedat Beis
> Prof. Hemant Pendse
> Prof. Peter van Walsum

> Funding
─ U.S.
U S Dept
Dept. of Energy DE-FG02-07ER46373
DE FG02 07ER46373 and DE DE-FG36-08GO18165
FG36 08GO18165
─ U.S. Dept. of Defense, Defense Logistics Agency SP4701-11-C-0010
─ UMaine Forest Bioproducts Research Institute

USDA/ARS    December 13, 2011 22