Forest Products Biotechnology/Bioenergy (FPB/B) The potential and challenges of “drop in” biofuels Sergios Karatzos, Jim McMillan and Jack Saddler International Energy Agency Bioenergy Task 39 (liquid biofuels) Carbohydrate Hydrocarbon “Petroleum-like” biofuel - O 2 H C C C C H H H H H H H H H O OH H H H O H OH H OH H OH
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Forest Products Biotechnology/Bioenergy (FPB/B)
The potential and challenges of “drop in” biofuels
Sergios Karatzos, Jim McMillan and Jack Saddler International Energy Agency Bioenergy Task 39 (liquid biofuels)
Carbohydrate Hydrocarbon “Petroleum-like” biofuel
- O2 O
OH
HH
H
OH
OH
H OH
H
OH
H C C C C
H
H
H
H
H
H H
H
H
O
OH
HH
H
OH
OH
H OH
H
OH
H C C C C
H
H
H
H
H
H H
H
H
Forest Products Biotechnology/Bioenergy at UBC
Commissioned Task 39 ‘drop in’ biofuel report
§ OVERVIEW § Definition § Role of Hydrogen in drop in biofuels § Role of Hydrogen in petroleum industry
§ TECHNOLOGIES
Forest Products Biotechnology/Bioenergy at UBC
Definition of a “drop-in” biofuel
§ Bioethanol: Biogenic ethyl alcohol
§ Biodiesel: Fatty acid methyl esters (FAME)
§ Drop-in biofuels are liquid hydrocarbons that are functionally equivalent and as oxygen-free as petroleum-derived transportation blendstocks (fuels)
§ All based on oleochemical § Neste Oil: 2,400,000,000 L diesel
from palm oil
§ Dynamic Fuels: 280,000,000 L diesel from animal fat
Neste Oil facility, Rotterdam
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Forest Products Biotechnology/Bioenergy at UBC
Many examples of commercial biofuel flights
§ Virtually all based on oleochemical § US Navy: Sept 2011 Solazyme algae oil and palm oil § Continental Airlines: Nov 2011 Solazyme algae oil § Alaska Airlines: Jan 2012 tallow and algae § Lufthansa: July 2011 Jatropha, Camelina § Finnair: July 2011 Used Cooking Oils § Many more
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Forest Products Biotechnology/Bioenergy (FPB/B)
CATALYTIC UPGRADING
INTER- MEDIATES
Hyd
ro
trea
tmen
t 1
Thermochemical drop-in biofuel platforms
Pyrolysis oil
Fisc
her
Trop
sch Gasification
Syngas
Biomass
H
ydro
crac
king
HPO
FT liquids
Gasoline
Diesel
Jet
Gases
500°C No O2
900°C some O2
Hyd
ro
trea
tmen
t 2
24
Forest Products Biotechnology/Bioenergy at UBC
Example of pyrolysis drop in facility: KiOR § 50,000,000 L per year in Mississippi (in operation)
H2
25
Forest Products Biotechnology/Bioenergy at UBC
Forest BtL Oy and Choren’s Carbo-V
§ 130,000,000 L per year of Gasification FT liquids by 2016 (Finland)
Gasification conditioning FT Hydrocracking
H2
H2
CO2
Pretreat.
26 Sundrop biofuels 190 MLPY
Forest Products Biotechnology/Bioenergy at UBC
0 2 4 6 8
10 12 14 16 18
HVO Pyrolysis Gasifica6on
USD
/ Gallon Gasoilin
e Eq
uivalent
Feedstock cost
Capital (installed capacity)
Feedstock and Capital cost of drop-in Biofuels
Feedstock intensive vs Capital intensive platforms Source: Kazi et al. 2010, Pearlson et al. 2011, Jones et al. 2009
Oleochemical
Forest Products Biotechnology/Bioenergy at UBC
0 2 4 6 8
10 12 14 16 18
HVO Pyrolysis Gasifica6on
USD
/ Gallon Gasoilin
e Eq
uivalent
Feedstock cost
Capital (installed capacity)
“Over the fence” Hydrogen inputs can reduce capital and feedstock costs
3% H2 7% H2
H2
Pyrolysis is highly dependent on access to cheap Hydrogen
Oleochemical
Source: Kazi et al. 2010, Pearlson et al. 2011, Jones et al. 2009
Forest Products Biotechnology/Bioenergy (FPB/B)
OIL REFINERY
over the fence H2
Hyd
ro
trea
tmen
t 1
Pyrolysis oil
Fisc
her
Trop
sch Gasification
Syngas
Biomass
H
ydro
crac
king
HPO
FT liquids
Lipids
Gasoline
Diesel
Jet
Gases
OLEOCHEMICAL
THERMOCHEMICAL
Hyd
ro
trea
tmen
t 2
Drop in biofuels leveraging on Oil refineries
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Crude oil
Drop in biofuels leveraging on Oil refineries
Distillation
tower
Vacuum unit
Light ends
Heavy ends
Reformer Gasoline
Jet
Hydrotreatment Diesel, Jet
Hydrocracker Diesel, Jet Gasoline
Fluid catalytic cracking
Coker
Coke
Hydrotreatment Gasoline Diesel, Jet
Lipids
Product blending
FT liquids HPO
DISTILLATION (CATALYTIC) UPGRADING BLENDING
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Forest Products Biotechnology/Bioenergy at UBC
Challenges of hydroprocessing biofeed: The Haldor Topsoe experience
§ Higher Hydrogen consumption § requirements more than doubled when just 5% of feed
was replaced with biofeed!
§ Presence of oxygenated gases such as CO and H2O
§ Heterogeneity of feedstock (Catalyst design challenges)
Source: Haldor Topsoe, 2009 31
Forest Products Biotechnology/Bioenergy at UBC
Major scale up challenges for each platform
§ Pyrolysis § Hydrogen § Hydrotreating catalyst
§ Gasification § Capital / scale § Feedstock /yields
§ HVO oleochemical § Feedstock
§ Refinery insertion challenges Sources: Jones et al. 2009; Swanson et al. 2010; Pearlson et al. 2011
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Forest Products Biotechnology/Bioenergy at UBC
Biochemical: Sugar fermentation to drop-in
§ Major advantages § Pure and “functionalized” product streams suitable for
value added markets
§ Major challenges § Volumetric productivity about 10x lower than ethanol § Recovery challenges: e.g. recovery from fermentation
SUGAR FERMENTATION Target molecule Modified algae, bacteria or yeast
Long alcohols Aliphatic chains
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Forest Products Biotechnology/Bioenergy at UBC
Fermentation pathways for deoxygenating Carbohydrates
Compared to ethanologenic yeast: • Energy intensive
• High requirement for reducing power (derived from NADPH or Hydrogen)
Example: Fatty acid biosynthesis
CO2
Repe
at 7
x
PPP cycle
Acetoacetyl-ACP
HCO3-
Glucose (C6)
Pyruvate (C3)
Acetyl-ACP (C2)
Malonyl-ACP (C3)
ACP + HCO3
-
2 x NADPH
Palmitate (C18)
Butyryl-ACP (C4)
ACP
Elon
gati
on
cycl
es:
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Lanzatech CO2 + H2 example
Forest Products Biotechnology/Bioenergy at UBC
Climbing fewer steps on the Heff /C staircase …
Sugar 0
0.2 Wood
Diesel 2.0
1.8 Lipids
Biochemical feedstock
‘Drop-in’ biofuels
1.0
Value-added biorenewables 0.6
0.4
0.8
1.2
1.4
1.6
35 Value added chemicals have lower Heff /C ratios than fuels
Forest Products Biotechnology/Bioenergy at UBC
Summary § Oleochemical: commercial now and less H2-dependent with considerable potential for growth (feedstock challenges?)
§ Thermochemical well suited for long term drop-in biofuels § H2 and catalyst challenges (Pyrolysis), Scale challenges (Gasification) § Leveraging on oil refineries: more challenging than expected
§ Biochemical “drop-in” products more valuable in rapidly growing chemicals markets
§ Accessing cheap/renewable Hydrogen will be a key challenge for both drop-in biofuels and crude oil of decreasing quality
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Forest Products Biotechnology/Bioenergy (FPB/B)
ACKNOWLEDGEMENTS
International Energy Agency Bioenergy Task 39 colleagues