The potential and challenges of “drop in” biofuels€¦ · · 2015-09-03The potential and...
Transcript of The potential and challenges of “drop in” biofuels€¦ · · 2015-09-03The potential and...
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
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Commissioned Task 39 ‘drop in’ biofuel report
§ OVERVIEW § Definition § Role of Hydrogen in drop in biofuels § Role of Hydrogen in petroleum industry
§ TECHNOLOGIES
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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)
§ Examples:
§ Hydrotreated Vegetable Oils (HVO) § Hydrotreated Pyrolysis Oils (HPO) § Fischer Tropsch Liquids (FT liquids)
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Properties of transportation fuels
Drop-in biofuels need to have similar properties to petroleum fuels:
• Fit the carbon number range
• Low to No oxygen
0
50
100
150
200
250
300
350
400
0 2 4 6 8
10 12 14 16 18 20 22 24
Ethanol Gasoline Jet A Diesel Biodiesel
carbon number
boiling point
? Jet
E10
B10
Unlike conventional biofuels, “drop-in” biofuels should be indistinguishable from petroleum fuels for end uses!
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Oxygen Challenge
§ Oxygen is present in biomass in the form of hydroxyls, esters, and ethers
§ Can oxidize fuel components, reactors and pipeline metallurgy to cause corrosion
§ Oxygen content reduces energy density
Ethanol Biodiesel (fatty acid methyl ester)
CH3
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Oxygen content vs. energy density
Ethanol
Butanol
Biodiesel
Crude oil
R² = 0.99438
0 5
10 15 20 25 30 35 40 45
0 0.1 0.2 0.3 0.4 0.5 0.6
Ener
gy d
ensi
ty (
MJ/
L)
O/C molar ratio Increasing Oxygen content reduces fuel energy density
Drop in biofuel
(35% O2)
(21.5% O2)
(11% O2)
(No O2)
Biomass/ Sugar (50% O2)
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A Carbohydrate e.g. Glucose C6H12O6
A Hydrocarbon e.g. Butane C4H10
-H2O
-CO2
Deoxygenating biomass dilemma …add H2 or lose yield?
- O2
Insert Hydrogen
Oxidize Carbon
“sacrificing” feedstock
High H/C ≈ 2
7
Objective is to deoxygenate and enrich H2 content of biomass
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O
OH
HH
H
OH
OH
H OH
H
OH
H C C C C
H
H
H
H
H
H H
H
H
Effective hydrogen to carbon ratio (Heff/C)
§ A high Effective Hydrogen to Carbon ratio is desired for drop-in biofuels
§ Heff/C = 𝑛(𝐻)−2𝑛(𝑂)/𝑛(𝐶)
Carbohydrate Hydrocarbon (e.g. Butane, Diesel)
Heff/C = 0 Heff/C ≈ 2
O
OH
HH
H
OH
OH
H OH
H
OH
H C C C C
H
H
H
H
H
H H
H
H
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The Effective H/C ratio staircase…
Sugar 0
0.2 Wood
Ethanol 0.4
Diesel 2.0
1.8 Lipids Oleochemical
Thermochemical
Biochemical
‘Drop-in’ biofuel
1.0
0.6
0.8
1.2
1.4
1.6
Lignin
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High O2 or low H/C feedstocks require more processing and H2 inputs
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The Hydrogen-Oxygen dilemma
§ “Drop-in biofuels” is a loose term referring to liquid biofuels containing low or no oxygen content
§ Deoxygenation requires hydrogen inputs or “oxidizing/burning” of feedstock carbon
§ High Heff/C ratio feedstocks such as lipids are well suited for drop-in biofuel production
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What will determine the success of “drop in biofuels”?
§ Drop-in biofuel technologies complexity/selectivity and hydrogen demand
§ Commercialization challenges such as capital, yield and refinery insertion
§ Crude oil is becoming increasingly hydrogen deficient (‘heavier’ and ‘sourer’)
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Purvin & Gertz forecast for world crude oil quality (Source: data from EIA)
Crude oil quality declining…
0
10
20
30
40
50
60
70
80
90
1990 2000 2010 2020
Mill
ion
barr
els
per
day
Heavy Sour
Light Sour
Light Sweet
“Heavy” and “Sour” oil increasing
“Sour” = High Sulfur
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The H/C ratio staircase for petroleum…
0.4
Diesel 2.0
1.8 Light crude
1.0
0.6
0.8
1.2
1.4
1.6
Coal
Oil sands
Heavy crude
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Lower quality fossil feedstocks = lower H/C ratio = higher H2 inputs
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Hydrotreating and Hydrocracking
§ Hydrotreating (Removes sulfur impurities as H2S) § Hydrocracking (breaks heavy oil to lighter molecules)
Heavy crude molecule
Diesel range molecule Gasoline range molecule
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US Hydrotreating capacity 1990-2030
0
5
10
15
20
25
30
1990 1995 2000 2004 2010 2015 2020 2025 2030
mill
ion
barr
els
per
day
Rapid increase in H2 consumption in US refineries
Source EIA, Annual Energy Outlook 2006 15
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Natural gas: Where H2 comes from
§ 90 % of commercial H2 comes from steam reforming natural gas
Steam reforming CO
2
CH4 H2
ENERGY INTENSIVE PROCESS!!
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Role of H2 in upgrading petroleum and drop-in biofuels
Petroleum Drop-in Biofuels
§ No Sulfur
§ High Oxygen content of feedstock needs hydrogenation
! Increasing Sulfur content
! Increasing heavy oil needs cracking
Both require Hydrogen for upgrading to finished fuels
Hydrogen will likely come from Natural Gas
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Commissioned Task 39 ‘drop in’ biofuel report
§ OVERVIEW § Definition § Role of Hydrogen in drop in biofuels § Role of Hydrogen in petroleum industry
§ TECHNOLOGIES
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The commercialization potential of Drop in Biofuel platforms and their H2 dependence
§ Oleochemical (HVO, algae)
§ Thermochemical (Pyrolysis - HPO, Gasification FT-liquids)
§ Biochemical (Advanced Fermentation)
§ Hybrid platforms (e.g. Virent, Zeachem, Lanzatech)
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drop-in fuel
Technology pathways to “drop-in”
sugars
syngas
biooil
lipids
fermentation
catalytic conversion
upgrading
hydrolysis
gasification
pyrolysis
oilseed crop
Autotrophic algae
sugar crop
Sun
phot
ons,
wat
er, C
O2
and
nut
rient
s
Bio
mas
s fib
er
Hyd
ropr
oces
sing
animal digestion
Higher alcohols (e.g. Gevo)
Isoprenoids (e.g. Amyris)
Blending
FT liquids (e.g. CHOREN)
HPO (e.g. ENSYN)
materials
processes
LEGEND
CONVENTIONAL INTERMEDIATES
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Bio
Ther
mo
Ole
o
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Oleochemical Platform Hydrotreated Vegetable Oils or HEFAs Major advantages § “Simple” technology, low risk (processes already commercial)
§ Bio SPK ASTM certification § High Hydrogen to carbon ratio (low Oxygen) of Feedstock
§ Palm oil § Tallow (rendered animal fat)
Challenges § Costly feedstock (approx. $500-1000/t) § Sustainability?
Fatty acid feedstock
H
ydro
proc
essi
ng
Gasoline
Diesel
Jet
Gases
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Commercial drop-in biofuel companies
§ 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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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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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
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Example of pyrolysis drop in facility: KiOR § 50,000,000 L per year in Mississippi (in operation)
H2
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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
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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
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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
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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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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
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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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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
broth and intracellular expression § Sugar feedstock highly oxidized (H/C = 0)
SUGAR FERMENTATION Target molecule Modified algae, bacteria or yeast
Long alcohols Aliphatic chains
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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
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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
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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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ACKNOWLEDGEMENTS
International Energy Agency Bioenergy Task 39 colleagues
www.Task39.org