BiofueI

Promised Land or Mirage?(*)

And other musings on bio-fuel, sustainable transportation
and energy
Luca Zullo, Ph.D.
luca.zullo@verdenerollc.com
www.verdenerollc.com
(*) both involve a lengthy walk in the desert
-out me..
and my work
Education
Ch Degree Padova, taly
PhD Ch mperial College, London UK
ProfessionaI
Shell Research
Cray Research
Cargill
The wilderness of start-ups.
emicaI engineering in a nutseII
nlet Outlet + Production Consumption = Accumulation
Corollary 1: The above applies to mass AND money
Corollary 2: f Accumulation of money is <= 0 investors are unhappy
Corollary 3: (recently stated) Uncle Sam will not correct 2 forever
Regardless of what many think, thermodynamics are NOT an opinion
Corollary: ventually applies also to people on Sandy Hill and Foggy Bottoms
Mass balances in moles were not just an invention to drive student crazy
Corollary: They work pretty well though on that too.
The world is a complex system: non-linear, dynamic and full of lags and
feedback loops. deal with it
All models are wrong, some are
convenient
Prof George Box
%aIking a-out energy is fraugt wit inteIIectuaI and semantic risks.
013 mpg @ 500 mph 40 mpg @ 60 mph
What is energy efficiency?
Which one is more energy efficient?
I% DEPENDS! *
( * typical weasel answers given by engineers to fudge tough issues or escape admitting ignorance)
%e answer is: it depends.
013 mpg @ 500 mph 40 mph @ 60 mph
Gallons per passenger mile
400 passengers in a 747 -> 0019
Lone commuter in a Prius -> 0025
We do not care about energy We do care about energy services
We do not purchase fuel
We purcase mo-iIity
nergy Transportation Residential Commercial
source 1973 2010 1973 2010 1973 2010
Petroleum
a
95 932 19 55 165 39
Natural gas
b
40 25 333 22 279 10
Coal 00 00 06 00 17 03
Renewable 00 40 24 25 01 07
Nuclear 00 00 00 00 00 00
lectricity
c
02 03 447 691 539 771
Total 1000 1000 1000 1000 1000 1000
nergy ndustrial lectric utilities
source 1973 2010 1973 2010
Petroleum
a
279 266 17 10
Natural gas
b
31 269 190 190
Coal 124 54 43 40
Renewable 37 72 145 106
Nuclear 00 00 46 213
lectricity
c
242 33 02 02
Total 1000 1000 1000 1000
Distri-ution of energy use -y source (source US Dept of Energy).
Source: US DO Transportation nergy Data Book
EvoIution of car registrations.
EvoIution of air transportation.
et Fuel consumption in
Mtoe
Revenue Passenger Kilometer
Source ATA-CAO
No foreseeable alternative to liquid fuel for aviation
Sustaina-Ie transportation is not optionaI
Personal mobility one of the most distinctive conquests of the modern society s one of
the most coveted goals of people worldwide as they gain increased affluence
Access to inexpensive and widespread mobility for goods and people essential to the
unprecedented economic growth of the XX century and its continued expansion in the XX
We cant deny to so much of humankind the benefits the western world had for so long
worId witout afforda-Ie transportation is going to -e a sociaIIy and
economicaIIy grim one
worId witout sustaina-Ie transportation is going to -e an environmentaIIy grim
one
Delivering access to sustainable and
affordable mobility is one
the defining challenges of the XX
century
BiofueIs to te rescue?
BiofueIs, an emotionaI topic -etween rigteous -ut often misinformed
outrage..
.. and triumpant -ut often incompIete and misIeading marketing or
pandering
BiofueIs: some definition from te we-
iofuels are a wide range of fuels which are in some way derived from biomass. The term covers solid biomass, liquid fuels and
various biogases. iofuels are gaining increased public and scientific attention, driven by factors such as oil price spikes and the
need for increased energy security.
enwikipediaorg/wiki/Biofuel
Any fuel that is obtained from a renewable biological resource, especially from biomass
enwiktionaryorg/wiki/biofuel
A form of renewable fuel that's derived from biomass, which includes organic materials produced by plants, animals or
microorganisms.
joulebiocom/why-solar-fuel/glossary
Gas, such as methane, or liquid fuel, such as ethanol (ethyl alcohol) made from organic waste material, usually by microbial action.
wwwtravelmattersorg/about/glossary
Fuels devised from biological materials including crops (especially trees) and animal wastes
wwwecifmrdgacuk/glossaryhtm
Gas or liquid fuel made from plant material (biomass). Includes wood, wood waste, wood liquors, peat, railroad ties, wood sludge,
spent sulfite liquors, agricultural waste, straw, tires, fish oils, tall oil, sludge waste, waste alcohol, municipal solid waste, landfill
gases, other waste, and ...
wwwnatsourcecom/markets/indexasp
fuels that are generated by solar energy and photosynthesis, either on an annual basis (crops, grasses, etc.) or over a period of a
number of years (trees). iofuels do work, but the scale of use is the main issue with them, since our overconsumption cannot be
met with biofuels. ...
wwwpermatopiacom/dictionaryhtml
A biofuel is liquid or gaseous product that can be used in the internal combustion engine of a transportation vehicle. It is notable in
that it contains a percentage of renewable products produced from plant or animal sources. ...
wwwveoliacom/en/glossary/Bhtm
A fuel produced from dry organic matter or combustible oils produced by plants. Examples of biofuel include alcohol (from fermented
sugar), black liquor from the paper manufacturing process, wood, and soybean oil
wwwwwforghk/eng/conservation/climate/glossaryphp
Any fuel that is derived from biomass recently living organisms or their metabolic byproducts from sources such as farming,
forestry, and biodegradable industrial and municipal waste. See renewables.
wwwchevronaustraliacom/glossaryaspx
is any liquid, solid or gas fuel refined in whole or in part from sustainable biological materials, usually plants. Some biofuels, like
ethanol, are refined from food plants such as corn, but technologies are being developed to use nonfood plants and crop residue
from food plants.
wwwamericagov/st/energy-english/2009/une/2000725134616mlenuhret2274722e-02html&distid=ucs
Fuels such as ethanol and diesel produced from sugars, vegetable oils, or other organic matter using biotechnology methods
biotech-ucom/courses/mod/glossary/viewphp
%rigIyceride (%) structure
% structure and fueIs.
FOG = biogenic fats, oils and greases
17
ydrotreating of Iipids over Ni/Mo cataIysts
CH
2
CH
CH
2
O C
O
O C
O
O C
O
Rx
Rx
Rx
Rx: saturated or mono/polyunsaturated aliphatic chain (typically C14-C1)
+1 H
2
Backbone cleavage
CH
2
CH
2
CH
3
+ O C
O
Rx
Rx H + CO
2
Rx CH
3
+ 2H
2
O
+ H2 according to un saturation level
Cn/Cn+1
3
somerization and Hydrocracking
to control cold flow properties
and carbon chain distribution
#enewa-Ie paraffins
#enewa-Ie fueIs cost structure. It is a feedstock game!
Feedstocks
1%
Hydrogen
2%
Utilities
2%
Production
Overhead
2%
nterest &
Depreciation
6%
Licensing Fee
2%
Target RO
on Plant
5%
Production osts per aIIon of
renewa-Ie jet fueI
0
50
100
150
200
250
300
350
400
02 03 04 05 06 07 0 09 1 11
$
/
-
-
I
$/I-
Current crop oil price
Igae promise : Large Iipids (veg. OiI) production
OiI yieIds
Source unknown, -ut wideIy used ta-Ie. It is on te Internet so must -e true.
OiI yieIds
Source unknown, -ut wideIy used ta-Ie. It is on te Internet so must -e true.
%e pitfaIIs of aIgae
Algae are deceptive because they are very good at
pigment production
ven in best conditions (much) less than 1 gram (db)
biomass per liter!
Physical and biological processes prevents higher
concentrations
Key differences with conventional crops:
Dilution
Fast growth requires continuous harvesting
Storage is not viable
Nutrient delivery
Wat are te reaIistic -iomass yieIds?
22
t starts with solar radiation
Only 45% of solar radiation is photosynthetically active (PAR)
The maximum teoreticaI and termodynamicaIIy Iimited conversion of PAR into biomass is 27%
ence te maximum teoreticaI yieId of soIar irradiation into -iomass energy is 12%
n real life most common <1%
highly productive corn hybrids are ~1% aiming to 3 to 4%
5 to 10% may be possible in future but not without extensive use of genetic engineering
Under these conditions it becomes difficult to reconcile some of the large yield numbers that are
proposed.
For comparison PV efficiency are:
PV cells ~ 10-15%
ExampIe of -iomass production potentiaI - we get -ack to tis Iater.
23
. and remember 10% efficiency is RALLY good.
Best US potentiaI - US Soutwest
141 t/ac
74 t/ac of C - > 271 t/ac of CO2
112 t/ac of N -> 24 t/ac of Urea (CH4N2O2)
30 kg/ac of P -> 1 ton/ac of Ammonium Phosphate (H12N3O4P)
Slightly reduces stoichiometric need of ammonia
Algae biomass composition example Source: Phyllis Database
Productivity in controIIed Ia- conditions of some non-gmo aIage strains
Source: Prof Mario Tredici
University of Florence, taly
<<1% ds
Note the tradeoff
between total biomass
and lipid yields
<<1% ds
Note the tradeoff
between total biomass
and lipid yields
ow tat transIates in oiI productivity per acre?
26
Say: 86 mg/It/day productivity of oiI
Igae grow in te smaII Iayer were Iigt can penetrate,
around 10 cm dept
ence 8.6 gr/m2/day of oiI
Biomass is 28 gr/m2/day
Over a year tat transIates into tis oiI production:
28,260 It/a/yr
3026 gaI/ac/yr
This under the best laboratory conditions!
Challenging to be easily and consistently reproduced in large scale.
This under the best laboratory conditions!
Challenging to be easily and consistently reproduced in large scale.
#eaIity ceck! %ermodynamics are not an opinion!
500 to 3500 - 5000 500 to 3500 - 5000
Still good, but where, at which cost and what are the
challenges
Basic fIow diagram of micro-aIgae processing
Primary harvesting step
Concentration, may include more than one step
More than 20% ds unlikely without physical disruption
of cell wall structure and drying
May require drying to get to oil concentration high
enough for oil extraction
May require additional treatment step to disrupt cell
wall structure and facilitate separation
Current oil extraction approaches (eg solvent extraction)
work fine but not optimal for relatively low fat content
We need to reduce the need for drying
IittIe exercise to visuaIize and quantify diIution impact on cost
A regulation Olympic pool
50 m x 25 m x 2 m
2,500,000 liters
661,375 gallons
Now tat we know ow muc water we ave..
Let's assume:
That the same amount of water in an Olympic pool is used in a raceway
pond 50 cm (16 ft) deep
That is a growing area of 5000 m2 or 127 ac
Very good but not impossible - productivity values
20 g/m2/day
30% lipids
That means:
100 kg (220 lb) of biomass per day
33 l (7 gal) of oil per day
2,500 gal/ac of oil yield
In order to produce 8.7 gaI of oiI we need to process 661,000 gaIIons of water
EVE# D
Some -ack of a smaII enveIope caIcuIation
Pumping cost for 661,000 gpd
Pumping cost ($/hr) = 0746 * F_gpm * H_ft * P_cost/(3960 * _p*_m)
Assuming:
$007/kWh
10 ft head
$10/day or $0.20/gaI of oiI
Net of capital cost
Primary concentration
661,000 gpd to 1322 gpd
gnore costs and energy demand
Secondary concentration
1322 gpd to 500 gpd
Centrifugation of 1322 gpd
500 gpd product (20% ds)
1/3 to 2/3 hp centrifuge
$0.07/gaI of oiI
Net of capital cost
Dewatering
500 gpd @ 20% ds
6% oil content
Remove enough water to be at 10% oil, 72 gpd
72 gpd -> 52 lb of water @ 1000 BTU/lb -> 52,000 BTU/day
Assuming gas at $4/MMBTU
$232/day or $0.26/gaI of oiI
Net of capital cost and efficiency factors
n this extremely simplified circumstances
already the processing cost is > $0.50/gaI
nergy inputs:
256 kWh/day
nergy yield of oil
307 kWh/day
2/3 of oiI energy aIready Iost!
DetaiIed num-ers indicate tat a <$1.00/gaI faciIity is nowere insigt
Economic
Parameters
Desired rate of return 1000%
Depreciation years 10
Analysis Period (years) 20
Tax Rate 4000%
Capital Recovery Factor 0117
Present Value
Depreciation 0614
Fixed Charge Rate 014
Igae Pond
OperationaI
Data
Pond Depth cm 20
Single Pond Area ha 10
vaporation Rate cm/day 0591366243
Area Productivity g/sq m-d 10.93990123
Pond Algae Concentration
g/l 0.38934736
% Lipid Content 15%
Total Pond Area (incr 10
ha) 1,000
Single Pond Flow lpd 2,09,05
Total Pond Flow lpd 20,90,491
Pond volume liters 20,000,000
Retention Time days 7
Oter Inputs
lectricity Cost $007
Power Plant Recov CO2
Cost oper mt $5046
Natural Gas Price per
MMBtu $651
Soy meal price per mt $2033
Land Price per acre $3,00000
Total to Pond Acres 150
Water Price per acre-ft $2196
Water Price per cu m $001
Kadam (1997) cost $4000
nflation adjusted $4946

Total Biomass Production 1,504,236

Total Oil Production 1,45,42
Total Capital $7,164,222
Total Operating Cost $13,706,21
Capital per Annual Gallon $5262
Oil (gal)Algae ( mt) Pond (ha)
Annualized Capital $777 $320 $11,541
Operating Cost $923 $30 $13,707
Total Cost $1700 $699 $25,24
Credit Algae Coprod $277 $114 $4,110
Credit lec $000 $0 $0
Net Cost $1423 $5549 $21,137
CO2 from flue gas
Dedicated algae ponds
Primary dewater: belt filter
Secondary dewater: centrifuge
Drying natural gas
Hexane solvent extraction
Basic economics of a faciIity for 1.5 MgaI/yr
(sources: Jon Seean - U of MN and Ben Wu - Sandia NationaI La-s)
%e -iomass diIemma
Power
Liquid fuel
eg cellulosic ethanol
%e -iomass diIemma
Biomass
(Bio)Chemical
Conversion
Liquid Fuel
Oil
Combustion Power
Coal
Cars (LDV)
Grid Users
%e -iomass diIemma
Biomass
Chemical
Conversion
Liquid Fuel
Oil
Combustion Power
Coal
Cars (LDV)
Grid Users
1 dry ton
$0
16,00 M
70 gal tOH
9,960 M
$210 @
$3/gal/60% eff
~ 50 gge
66 kg of CO2
~ 0 tce
2,040 kg of CO2
gge=gallons of gasoline equivalent
tce=tons of coal equivalent
1,400 kWh
5,100 M
$9 @ $007/kWh - 30% eff
ueI is onIy a component of a transportation system
BOMASS POWRD!
%e -iomass diIemma
Cost of CO2
-$20/tonne
-1 gal of gasoline (~30 $/gal) -> kg of CO2 ->$017/gal (+5%)
-1 ton of coal (~55 $/ton) -> 2,547 kg of CO2 -> $501/ton (+100%)
Biomass
(Bio) Chemical
Conversion
Liquid Fuel
Oil
Combustion Power
Coal
Cars (LDV)
Grid Users
1 dry ton
16,00 M
~ 50 gge
440 kg of CO2
~ 0 tce
2,040 kg of CO2
1990 M
20% dte
11% ese
$010/M
4335 M
5% dte
25% ese
$002/M
70 gal tOH
9,960 M
$210 @
$3/gal/60% eff
1,400 kWh
5,100 M
$9 @ $007/kWh - 30% eff
dte = drive train efficiency
ese=energy service efficiency
%ings may not -e -etter wit "advanced" -iofueIs..
thanol
C6H12O6 -> 2 CH2H2OH + 2 CO2 (051/049) 1472 M, 064 lt
Butanol
C6H12O6 -> C4H9OH + 2CO2 + H2O (042/04/01) 134 M, 051 lt
n-Octane
C6H12O6 -> 04 CH1+217 CO2+163 H2O (030/053/017) 1333 M, 042 lt
thylbenzene
C6H12O6 -> 057 CH10 + 142 CO2 + 314 H20 (033/034/031) 1350 M, 03 lt
One kg of glucose of glucose can give us:
#etink te assumptions..
Production and transformation
systems can be very distant in
high energy density systems
.. %ey need to -e cIoser wen te energy density is Iower
Energy in a -arreI of oiI..
1 -arreI of oiI equivaIent (-oe)
6.1 J
IdeaI -iomass production potentiaI wit aIgae
42
500 boe
150 boe
1 ha = 247 ac
. cIoser to ome: corn stover
About 10 tons db per year per acre
Based on average 150 bu/ac of corn
(56 lb/bu @ 15% moisture)
Theoretical energy availability
Heating value ~ 000 lbu/lb, dry basis
16 MMBTU/ac or 177 G (30 boe)
Typical constraints
Biomass 15% to 30% moisture at
harvest More if left on the ground
longer
Max 50% of biomass available to
preserve soil health
High bulk density (3 lb/cft)
Wic pat to foIIow?
Sustainable transportation should be addressed from a
comprehensive point of view that includes the whole supply chain
including the demand side
Technology advances, need to be evaluated across the whole
supply chain
New feedstock, new molecules, new drive trains, new transportation
options
By reducing liquid consumption we can meet blending level with lower
volumes
Societal factors are important
SocietaI factors?..
Land usage and global resources
Food vs fuel
Water and land disposition
Fossil fuels dependency of global agricultural system
Phosphorus and nitrogen supply
Actual carbon footprint
De-carbonization of the economy
LCA approaches
nergy independence diversification and energy policy goals
Transportation policy
Public vs Private
Societal and human issues
Urban development
Personal freedom
Work attitudes
.. possi-Ie pat forward for -iofueIs
Biofuel R&D should focus in the area where the need of a high density liquid fuel
remains critical and electrons cannot be a replacement
We cannot win on the supply side alone
The need of gasoline blending stock remains, but is moderated by the reduction in
consumption and the trend towards electrification
As the overall volume is nonetheless increasing we need to have better integration
with the existing energy infrastructure
Biofuels needs to be valued by their energy value and not by the volume
Key sectors: Aviation Fuels and HDV (aka large trucks)
et Fuel (Kerosine) and Diesel
Middle distillates (C10-C22 range)
Strong and growing demand especially in BRC economies
No clear replacement of drive trains to reduce dependency on liquid fuels
ey areas of deveIopment
BOMASS
SPARATON
AND
PRTRATMNT
Simple Sugars
Polysaccharides
Starch
Cellulose
Hemicellulose
Lignin
Lipids
THRMAL
PROCSSNG
Alcohols
thanol
Butanol
Cyclic hydrocarbons
Fatty acid methyl esters
Bio-SPK
Pyrolysis oil
Syngas
Hydrocarbons
MeOH, DM, MTG, FT fuels
HARVSTNG
thanol
Hydrocarbons
ALGAE
New land crops
Virent
LS9
Amerys
Coskata
Range Fuels
UOP
NESTE
COP
COP/ISU
UOP
GTI
Evergent
Gevo
Mascoma
Other
Solazyme
Saffire
Aurora
and many more
Choren
Rentech
noter -iofueI diIemma. for te investors
Product
Differentiation
Operational
fficiency
Technology
driven
Commodity
driven
High
Margin
High
Volume
noter -iofueI diIemma: wat is te -usiness modeI?
Product
Differentiation
Operational
fficiency
Technology
driven
Commodity
driven
Second
Generation
Biofuel
Companies
We are just -eginning...
" Voyages of discovery are made not
-y seeing new pIaces -ut -y aving
new eyes"
MarceI Proust