Post on 01-Sep-2018
transcript
NREL is a national laboratory of the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, operated by the Alliance for Sustainable Energy, LLC.
Realizing the Potential of Advanced BioFuels
Thomas D. Foust, Ph.D., P.E. Director, National Advanced Fuels Consortium June 14, 2012
2
Project Objective – Develop cost-effective technologies that supplement petroleum-derived fuels with advanced “drop-in” biofuels that are compatible with today’s transportation infrastructure and are produced in a sustainable manner.
3 year effort - $50M/year
Consortium Partners Albemarle Corporation Amyris Biotechnologies Argonne National Laboratory BP Products North America Inc. Catchlight Energy, LLC Chevron Colorado School of Mines General Motors Honda Iowa State University
Los Alamos National Laboratory National Renewable Energy Laboratory Oakridge National Laboratory Pall Corporation RTI International Tesoro Companies Inc. University of California, Davis UOP, LLC Virent Energy Systems Washington State University 2
National Advanced Fuels Consortium
4
Conventional (Starch) Ethanol Biodiesel Cellulosic Ethanol Other Advanced Biofuels
0
5
10
15
20
25
30
35
40
2000 2002 2004 2006 2008 2010 2012 2014 2016 2018 2020 2022
Billion Gallons
Actual Production Renewable Fuels Standard (RFS) Targets
~ Equivalent to National E10
~ Equivalent to National E15
~ Equivalent to National E20
~ Equivalent to National E25
Marketplace for Renewable Fuels
Need to Create Market Demand for Cellulosic Ethanol
Conventional Gasoline
• E10 - saturated with corn ethanol
• E15 - EPA approved for 2001 and newer cars but not implemented in the field
• E85 – flex fuel vehicles grew but fuel at the stations never materialized ICBR investors asked to take on market risk as well as new technology risks Chicken-n-Egg problem between high ethanol fuel blends and vehicles in the market
6
Ethanol Can Enable More Efficient Engines
• Higher compression ratio yields higher efficiency
• Above CR of 14 piston ring friction dominates
• CR=14 is optimal
• Current engine CR about 10
• Higher CR would be enabled by HIGHER Octane Number
• Ethanol has a much higher blending Octane Number than hydrocarbon blendstocks
• Another advantage of ethanol is cooling effect of vaporization – much greater than hydrocarbon
7
Ethanol market
• EPA has approved E15 as substantially similar to gasoline for 2001 and newer models
– Currently be rolled out state by state
– Car manufacturers need higher octane specially high RON low MON to meet new café standards
• mid level ethanol blends are a cost effective manner to achieve this
• High RON low MON benefits to E25
• Butanol also good for high RON low MON
• Likely to start approving models in model year 2012 with more to follow in 2013 and 2014
– Small engines, pumps and dispensers remain an unresolved issue
– RFA aggressively working these issues and is strongly committed to E15
• E85 volumes gaining slightly but still very small as overall percentage of ethanol volumes
• VETC (ethanol tax credit) phased out on January 1, 2012
• Effect on EtOH production difficult to ascertain
•
Ethanol
8
U.S. Transportation Fuel Demand – gasoline use dropping rapidly
Gasoline* (Finished Motor Gasoline – E10) (cars & trucks)
Diesel (on-road, rail)
Aviation (jet fuel)
23 bgy
126 bgy
43 bgy
2010 2035 Gasoline 126 116 Diesel 43 52
Jet fuel 23 27
Source: Energy Information Agency
Products in a Barrel of Crude (gal)
* Peaked in 2004 at 136 bgy
11
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
100%
USA Europe Asia Pacific
Pro
du
ct D
em
and
- 2
00
4
Other
Heavy Fuel Oil
Middle Distillate
Gasoline
US Refining System Is Built To
Meet Gasoline Demand
BP Statistical Review of World Energy June 2005
12
With all of the technological
improvements to gasoline and
diesel engines in the past 20
years and what will be
required to meet CAFÉ
standards, is our current fuels
menu optimum for maximizing
fuel economy ?
13
US GASOLINE POOL - RON
Year Pool RON Avg.
EtOH % HC Pool
RON
1990 93.2 1 92.1
2000 92.8 1.5 91.0
2010 92.9 8.6 82.6
14
US GASOLINE SALES BY GRADE –
% OF TOTAL
Year Regular Mid Grade Premium
1990 69 9 22
2000 79 7 14
2010 88 3 9
US EIA/Petroleum Marketing Monthly, Feb. 2012
15
Ethanol Prices – April 2012
Prices NL E85 E10 E15 E30
Gasoline $3.3500 $3.3500 $1.0050 $3.0150 $2.8475 $2.3450
Ethanol $2.1300 $1.4910 $0.2130 $0.3195 $0.6390
Product Cost $3.3500 $2.4960 $3.2280 $3.1670 $2.9840
Fed Tax - Gas $0.1840 $0.1840 $0.1840 $0.1840 $0.1840 $0.1840
VEETC - Ethanol $0.0000 $0.0000 $0.0000 $0.0000 $0.0000
State Tax $0.2800 $0.2800 $0.2800 $0.2800 $0.2800 $0.2800
TOTAL COST $3.8140 $2.9600 $3.6920 $3.6310 $3.4480
Copyright ©2012 Blend Your Own Ethanol Campaign. All Rights Reserved.
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Partial Hybrids, Hybrids and Plug-in Hybrids Electrics Extended Range Electrics Fuel Cell Vehicles Biofuels Alternative Fuels Low Temperature Combustion Diesel Engines Improved SI Engines/Transmissions
TECHNOLOGIES FOR IMPROVING FUEL ECONOMY
and REDUCING PETROLEUM IMPORTS
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Advanced Biofuel Conversion Routes
Biomass Algae growth & oil harvest
Hydrotreating & Upgrading
Refinery
Pyrolysis/ Liquefaction
Gasoline Diesel
Jet
Sugar Catalytic-
Conversion
Fermentation with engineered microbes
Gasoline Diesel
Jet
Syngas gasification
Fischer-Tropsch Synthesis
Methanol Synthesis
19
Gasification
Technology fairly well developed
Classes of gasifiers
Air Blown Gasification (updraft or downdraft) – low cost and thermally efficient, product gas not well suited for fuel synthesis – high N2
content
Indirect Gasification – good thermal efficiency, syngas not diluted with N2 – product gas relatively high in tars
Direct Gasification – Good product gas, lower in tars, - high cost of O2,, lower thermal efficiency, syngas high in CO2
Entrained Flow Gasification – Excellent product gas, essentially no tars – high cost of O2, low thermal efficiency, higher capital cost because of increased complexity
20
Thermodynamics and kinetics of biomass conversion
Intermediates
• Gasification is inherently a lower efficiency process based on thermodynamic analysis
21
SyngasMethanol Synthesis
DME Reactor
Multiple MTG
Reactors
Product Separation Gasoline
LPG
Fuel Gas
Water
Combined Synthesis Reactors
Product Separation Gasoline
LPG
Fuel Gas
Water
Syngas
BASE CASE
IMPROVED CASE
Challenge - Fuel Synthesis is Process/Capital Intensive
Need to simplify the process to achieve economics
22
Pros/Cons and challenges of gasification routes
Pros
• Good experience base
• Only significant technical challenge is cost and complexity
• Capable of producing high quality diesel and jet fuels
• Chemistry works and is relatively proven
Cons
• Cost is a significant challenge
• Previous attempts to reduce costs have met with limited success
Challenges
• Reducing capital costs
• High process complexity
23
Sugar or Soluble Carbon Intermediate Pathway
Pretreatment & Conditioning
HC Fuels
Enzyme Production
Enzymatic Hydrolysis
Fermentative Cell
ANTI-MALARIAL DRUG
ISOPRENE
Aqueous Phase Reforming
Acid Condensation
Condensation & HDO
Dehydration & Oligomerization
Gasoline
Jet Fuel
Diesel Heat and Power
Lignin
Diesel
Value Add
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Fermentation Pathway
Mevalonate Pathway
YEAST CELL
hydrolysate
Diesel & Chemical Precursor
Farnesene Synthase
-Farnesene
[1] [2] [3] [4]
[1] Cane juice [2] Fermentation broth [3] Separations [4] Purification
25
Catalytic Pathway
Soluble Sugars
Lignin
PolysaccharidesC5&C6 SugarsFuransPhenolicsAcids
DehydrationAlkene
Oligomerization
Base Catalyzed Condensation
AlkeneSaturation
HDO
ZSM-5
Hydrogenolysis
HydrogenationSugar Alcohols
C2-C6
Oxygenates
Bio
ma
ss F
ract
ion
atio
n
and
Pre
tre
amen
t
H2
H2
Aqueous Phase Reforming
Process Heat
LignocellulosicMaterials
Starches
Gasoline
KeroseneJet Fuel
Diesel
Aromatics, Alkanes
Alkanes
Alkanes
C1-C4
Alkanes
26
Extracting from lignin via low energy approaches
Fractionation/ Catalytic Deconstruction
Dis
tilla
tio
n
C6-C9 stream
C number
Pro
du
ct d
istr
ibu
tio
n
C6 C9 C20
Lignin is a heterogeneous alkyl-aromatic polymer with labile C-O bonds
C9-C20 stream
>C20 stream
Catalytic Upgrading
Catalytic Upgrading
Heat/Power
Research needs: - Fractionation process development - Catalyst and process development for lignin deconstruction - Catalyst and process development for lignin upgrading to fuels
C9-C20 hydrocarbons/ Diesel & Jet Fuel Range
Potential strategies - Fractionation: lignin post Prt/EH, upstream fractionation of carbs/lignin - Deconstruction: base-catalyzed depolymerization, acid hydrolysis,
transition metal catalysts - Upgrading: Retro-Diels Alder, partial ring saturation, selective ring
opening, acid oligomerization
27
Pros/Cons and challenges of sugar routes
Pros
• Produces high quality components for diesel and jet – both fermentative and catalytic routes
• Initial higher value applications
• Builds upon OBP cellulosic ethanol technologies so good building base
Cons
• High capital cost approaches
• Overall yields and efficiencies lower than thermal routes
• Lignin component only used for heat and power at high capital cost
Challenges
• Better organisms –fermentative
• Better catalysts – catalytic
• Lower costs
• Better utilization of lignin
28
TAGs
Lipid (Autotrophic/Heterotrophic) Intermediate
HC Fuels
Fatty Acids TAGs
Reduction/Decarbonylation
n-Alkanes Olefins
Algae Cyanobacteria
Photosynthetic Bacteria
Commodity Chemicals (Ethylene)
Specialty Chemicals
(Carotenoids)
Pretreatment & Conditioning
Enzyme Production
Enzymatic Hydrolysis
Algae Yeast or Bacteria Fungi
29
Conversion and End-use
• Process optimization • Thermochemical
• Biochemical
• Fuels characteristics
• Co-Products
• Energy efficient harvesting
and dewatering systems
• Biomass extraction and
fractionation
• Product purification
• Algal Strains - Growth,
productivity, stability, and
resilience
• Cultivation system design
• Temperature control
• Invasion and fouling
• Input requirements
• CO2, H2O sources, energy
• Nitrogen and phosphorous
• Siting and resources A nano-membrane filter being developed by a NAABB partner.
A gasifier being used by a NAABB partner to convert algal biomass to fuels
Algal routes to advanced biofuels
Biomass Harvesting and
Recovery
Biology and Cultivation
30
Pros/Cons and challenges of algal routes
Pros
• Capable of producing high quality fuels
• High yields
• Negates food versus fuel debate
• Does not need fresh water
Cons
• Significant technical risk
• Cost barriers significant and numerous
Challenges
• Cell biology
• Cultivation
• Harvesting and extracting
• Economic uses of cell mass
31
Bio-Oil Intermediate
Initial Results (NABC data) Good • Feasibility tests very positive • Economics show the potential to be very attractive (< $2.00 gge for refinery
integration case) • Refiners are very interested Bad • Products are almost exclusively aromatics mostly in the gasoline range • Chemistry is very complex and poorly understood making process design
dubious
32
Fast pyrolysis oil is converted to fuels in a 2-step process
The product carbon recovery based on biomass was about 35% Process is capital intensive Logistics issue since pyrolysis oil is highly corrosive and unstable Process may not be scalable or replicable for large volume fuel production without new infrastructure
Holmgren, J. et al. NPRA national meeting, San Diego, March 2008.
HC
light products
medium products
heavy products
H2
HT
H2O aqueous byproduct
Hydroprocessed Bio-oil (from Mixed Wood)
Petroleum Gasoline
Min Max Typical
Paraffin, wt% 5.2 9.5 44.2
Iso-Paraffin, wt% 16.7 24.9
Olefin, wt% 0.6 0.9 4.1
Naphthene, wt% 39.6 55.0 6.9
Aromatic, wt% 9.9 34.6 37.7
Oxygenate, wt% 0.8
33
Catalytic Fast Pyrolysis (CFP) Hydropyrolysis (HYP)
Based on Fluidized Catalytic Cracking (FCC) Technology
Pervasive in Petroleum Refining
34
CFP/HYP Catalyst Impact
min0 2.5 5 7.5 10 12.5 15 17.5 20 22.5
pA
0
10
20
30
40
50
60
70
80
90
FID1 A, (PY_081010-24\NB3425221R108IPA_2-1.D)
Area
: 20.5
488
0.5
49
1.2
72
2.5
94 2
.644
2.6
85 2
.827
- A
ceta
dehy
de 3
.250
3.4
17 3
.470
- A
ceto
ne 3
.779
- IP
A 4
.034
4.3
27 4
.385
4.5
61 4
.648
4.8
53 4.9
04 4
.959 5.2
29 -
2-B
utan
one
5.5
90 -
Ace
tic a
cid
+ 5
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5.8
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.683
- m
ethy
l-pro
pano
l 7
.052
7.2
73 -
Ben
zene
7.4
24 7
.581
7.6
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7.8
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.873
7.9
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8.1
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8.2
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9.0
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- To
luen
e 1
0.73
2 1
0.82
1 1
0.94
4 1
1.22
2 1
1.31
6 1
1.54
8 1
1.60
6 1
1.68
7 1
1.76
5 1
1.80
8 -
Furfu
ral
11.
897
- O
ctan
e 1
2.08
7 1
2.20
5 1
2.29
3 1
2.38
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2.49
6 1
2.66
2 1
2.69
6 1
2.76
1 1
2.85
0 -
dim
ethl
ycyc
lohe
xane
12.
936
13.
013
13.
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13.
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13.
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- Et
hylb
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3 1
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p-Xy
lene
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14.
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Xyle
ne 1
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3 1
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4.55
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8 1
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6 1
4.86
0 1
4.93
7 1
5.03
9 1
5.10
6 1
5.21
2 1
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6 1
5.31
8 -
Fura
ncar
boxa
ldeh
yde
15.
378
15.
432
15.
472
15.
604
15.
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15.
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- Ph
enol
15.
952
16.
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16.
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16.
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- C
9H20
O2
ethe
r 1
6.23
3 1
6.30
1 1
6.37
6 1
6.51
7 1
6.60
0 1
6.70
5 1
6.74
1 1
6.81
4 1
6.86
0 -
C10
H22
O2
ethe
r 1
6.91
0 -
Dec
ane
17.
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17.
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17.
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17.
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17.
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- C
reso
l iso
mer
-1 1
7.57
0 1
7.61
3 1
7.68
3 1
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1 1
7.82
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8 -
Cre
sol i
som
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18.
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396 2
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8
Standard Fast Pyrolysis
min0 5 10 15 20 25 30
pA
0
10
20
30
40
50
60
70
80
90
FID1 A, (PY_100410-32\NB3425253R134IPA_2-5.D)
2.559
2.643 3.7
62 - IP
A 4.5
72
7.252
- Benz
ene
10.52
1 - To
luene
13.24
0 - Et
hylben
zene
13.46
2 - p-X
ylene
14.07
1 - o-X
ylene
16.86
3 - De
cane
20.52
4 - Na
phthal
ene
22.61
4 - me
thyl-N
aphtha
lene
22.91
0 - dim
ethoxy
Pheno
l
30.17
7
Catalytic Fast Pyrolysis/Hydropyrolysis
Quality Yields
35
Hydrothermal Liquefaction
Hydrothermal Liquefaction
Liquid hydrocarbons
H2
Catalytic upgrading
solids
Wet biomass
~350ºC, 200 atm, biomass slurry in water Long residence times
Slow pyrolysis in pH-moderated, pressurized water
36
Bio-Oil Intermediate Research Needs
Pyrolysis Vapor 4” FBR
Research Needs • Determine chemistry mechanisms
• Minimize BTX (aromatics) • Form C-C bonds towards diesel
and jet fuels (straight and branched chain alkanes)
• Develop and test deoxygenation catalysts
• Test catalyst deactivation and regeneration
• Produce sufficient quantities of oil for refinery integration testing
• Investigate effects of catalytic pyrolysis (effects of alkali metals, etc)
• Test in reactor representative of petroleum refinery FCC reactor
This area has very big promise but significant research needs to be done
37
Potential Co-Processing Points
Source: Wikipedia
• Typically designed to remove sulfur • Potentially suitable to deoxygenate triglycerides or other bio-oils
Hydroprocessing Units
Conversion Units
• Designed to break down larger molecules into smaller ones • Potentially suitable for upgrading of pyrolysis oils into fuels
Refineries contain many potential insertion points for co-processing of a variety of biomass-derived feedstocks
38
Conclusions
• Ethanol future still uncertain – Café standards driving to higher compression engines – Significant activity in commercialization – Butanol also a possibility
• Future is advanced biofuels “drop- in”. Although preliminary results are promising many challenges remain:
Biomass
• Yields and costs • Lignin utilization • Must integrate into future fuel mix need
Algae
• Significant technical challenges – Cell biology – Cultivation – Harvesting – Cell mass utilization
39
Biomass for Transportation Deployment
Near Term Impact (< 5 yrs) Mid Term Impact ( 5-10 yrs) Long Term Impact (> 10 yrs)
Bio
fuel
s D
eplo
ymen
t B
iop
ow
er
An
alys
is
Battery Electric Vehicles
Biochem/Thermochem Cellulosic Ethanol
Advanced Biofuels From Simple Sugar
Feedstocks
Algal Biofuels R&D - Gasoline
-Diesel -Jet
Advanced Biofuels Market Analysis
- 3rd generation - 4th generation
Sustainability Analysis - Cellulosic ethanol - Advanced biofuels
Advanced Biofuels Lignocellulosic
Feedstocks - Gasoline
- Diesel - Jet Fuel
Breakthrough Technology Anal. - direct PS -Genetically modified plants
Pathway Technoeconomic Analyses
4th Gen Biofuels - direct photosynthesis
-GMO plants
IGCC Cofiring
41
Pros/Cons and challenges of catalytic pyrolysis routes
Pros
• Based on proven technology – FCC technology in petroleum industry
• Low cost – both operating and capital
• Integrates well with petroleum refining
Cons
• Produces only gasoline and only aromatics which are least desirable from a refinery perspective
• Produces a less desirable co-product steam that must be utilized to achieve economics and GHG benefits
Challenges
• Better catalysts
• Shift product ratio to higher percentage of fuel fraction versus co-product portion
• Better understanding of underlying chemistry
42
16.76
15
8
5
6
5
3
27
32
14
8
8
11
5
5
0 10 20 30 40
North America
Non-OECD Asia
OECD Europe
OECD Asia
Central and South America
Middle East
Non-OECD Europe and Eurasia
Africa
2007
2035
Figure 27. World liquids consumption by region and country group, 2007 and 2035 million barrels per day Figure 27. World liquids consumption by region and country group, 2007 and 2035 million barrels per day
U.S. demand is leveling off but world wide demand is rapidly increasing
25
44
But…. Nobody likes
• CNG vehicles – short range, safety issues in a crash and trunk taken up by large tanks •Ethanol – lower mileage, higher food prices plus specialty engine issues • Small underpowered cars and hybrids
45
Need • Better fuel efficient vehicle options • Better natural gas vehicles and/or better fuels from natural gas – gas to liquids • Better biofuels
47
Corn Ethanol
• 97% of gasoline used in U.S. is E10 • 14 Billion gallons produced in 2011 • 40% of US corn crop is used for
ethanol production • Ethanol production is the biggest
use of corn has now overtaken animal feeding
• Much debate on the impact on food prices but corn prices have doubled over the past decade from historic levels
• No detrimental impact on modern cars (2000 and newer) however can have negative impacts on lean burn, marine or small engines
48
Cellulosic Ethanol
• Made from plant material not corn and hence does not compete with food
• Environmentalists like it better – lower CO2 emissions and environmental impacts in general
• Higher cost near-term, lower-cost long-term
• Still ethanol
49
Ethanol Can Enable More Efficient Engines
• Higher compression ratio yields higher efficiency
• Above CR of 14 piston ring friction dominates
• CR=14 is optimal
• Current engine CR about 10
• Higher CR would be enabled by HIGHER Octane Number
• Ethanol has a much higher blending Octane Number than hydrocarbon blendstocks
• Another advantage of ethanol is cooling effect of vaporization – much greater than hydrocarbon
50
Why not just make gasoline, diesel and jet from biomass
Gasoline (cars & trucks)
Diesel (on-road, rail)
Aviation (jet fuel)
25 bgy
140 bgy
43 bgy
51
Make biomass a liquid
Initial Results Good • Feasibility tests very positive • Economics are superb (< $2.00 gge for refinery integration case) • Refiners are very interested Bad • Products are almost exclusively in the gasoline range • Chemistry is very complex and poorly understood making process design
dubious
52
TAGs
Fuels from Algae
HC Fuels
Fatty Acids TAGs
Reduction/Decarbonylation
n-Alkanes Olefins
Algae Cyanobacteria
Photosynthetic Bacteria
Commodity Chemicals (Ethylene)
Specialty Chemicals
(Carotenoids)
Pretreatment & Conditioning
Enzyme Production
Enzymatic Hydrolysis
Algae Yeast or Bacteria Fungi
54
Evolution of Cars
1970s Car
• 15.8 mpg
• 136 hp
• 0-60 in 14.2 seconds
• carbureted
• 3 spd transmission
• Minimal emission controls
2012 Car
• 32.7 mpg
• 192 hp
• 0-60 in 9.5 seconds
• Direct injection
• 6 -8 spd transmission
• Emit 95% less pollutants – sophisticated electronic engine management systems
55
Evolution of Fuels 1970s Refinery
• Distillation only
• Sulfur 1000 ppm
• Minimal specs
• No specs on N levels
• Leaded to bypass octane ratings
2012 Refinery
• Multiple processes
• Sulfur < 15 ppm
• Must blend ethanol, RFS, CAA
• Extensive specifications that vary by region and season
56
Bio-fuels are actually beneficial to making better fuels
Source: Wikipedia
• Typically designed to remove sulfur • Potentially suitable to deoxygenate triglycerides or other bio-oils
Hydroprocessing Units
Conversion Units
• Designed to break down larger molecules into smaller ones • Potentially suitable for upgrading of pyrolysis oils into fuels
Refineries contain many potential insertion points for co-processing of a variety of biomass-derived feedstocks
57
Take away points
• The days of cheap fuels from petroleum are over
• The Middle East controls oil prices o Not the President
o Not Congress
o Not the oil companies
• US situation is improving o Reduce demand
– More and better fuel efficient cars and trucks
o Increase supply – Offshore drilling in the near term
– Canadian tar sands
– Natural gas to liquid fuels
– Biofuels (gasoline, diesel and jet fuels)
• Ethanol may reach 15- 25% of gasoline but E85 is essentially dead