SAFTechSAFTech

Non-food Sources for Biodiesel

Dr. Richard S. Sapienza

METSS Corporation

Westerville, OH. and

Thomas Sapienza

Strategic AgFuel Technologies

Phoenix, AZ

SAFTechSAFTechObservations of Climate Change

Evaporation & rainfall are increasing;

• More of the rainfall is occurring in downpours

• Corals are bleaching

• Glaciers are retreating

• Sea ice is shrinking

• Sea level is rising

• Wildfires are increasing

• Storm & flood damages are much larger

"I think the environment should be put in the category of our national security. Defense of our resources is just as important as defense abroad. Otherwise what is there to defend?“ — Robert Redford

SAFTechSAFTechRecycling Carbon Dioxide

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Biodiesel Feedstocks

Traditional The most common form of Biodiesel is that made by the transesterification of vegetable oils

• In the US, soybeans provide the most common feedstock• In Europe, rapeseed [canola] provides the most common

feedstock

Other Common Feedstocks• Sunflower oil is commonly used in France and Eastern Europe• Palm Oil is common in Malaysia• Used cooking oil is quickly becoming a common feedstock• Tallow is also becoming common and contains highly Saturated

Fatty Acid Triglycerides.

SAFTechSAFTechGreenwashing

• Environment, Perils, Promises and Perplexities of Green Propaganda - analyzing our perceptions and actions

• The diverse practices proclaim a 'correct' ethical or green choice, but make more tangible the contradictions and responsibilities that we encounter personally and as a society.

• Biofuels policy has increased biofuel production

• However, at a high cost– Feed prices up 60-100%, or more– Total cost increases $25-33

billion/year– True retail cost of gasoline

replaced over $5/gallon– Regressive effects on food and fuel

prices

• For little real gain– Energy security is lower– International scorn increased– Little net gain in energy supply

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the other oil shock

• shortages and soaring prices for vegetable oils are the latest, most striking example of a developing global problem: costly food.

• foodstuffs, climbed 37 percent last year

• protests have erupted • And all this is happening even as

global climate change may be starting to make it harder to grow food in some of the places best equipped to do so, like Australia.

• in Chongqing, China, announced a limited-time cooking oil promotion in November, a stampede of would-be buyers left 3 people dead and 31 injured.

• in the developing world, cooking oil is an important source of calories and represents one of the biggest cash outlays for poor families

Biofuels accounted for almost half the increase in worldwide demand for vegetable oils last year

"An Agricultural Crime Against Humanity"

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Biofuel Policy Effect

0¢

10¢

20¢

30¢

40¢

50¢

60¢

70¢

2004/2005 2005/2006 2006/2007 2007/2008 2008/2009 2009/2010

Ce

nts

/Lb

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Average Price, With Biofuels Tax Credit Average Price, No Biofuels Tax Credit

Soyoil Price

$0

$50

$100

$150

$200

$250

$300

$350

$400

$450

2004/2005 2005/2006 2006/2007 2007/2008 2008/2009 2009/2010

$/T

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Average Price, With Biofuels Tax Credit Average Price, No Biofuels Tax Credit

Soymeal Price

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5

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15

20

25

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35

2004/2005 2005/2006 2006/2007 2007/2008 2008/2009 2009/2010

$B

illio

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costs to domestic soybean users

Item 2004 Jan. 2008 % ChangeMeat and Bone Meal/Ton $191.68 $347.75 81%Meat Meal/Ton $190.63 $335.39 76%Sunflower Meal/Ton $107.42 $215.17 100%Feather Meal/Ton $246.86 $400.87 62%Yellow Grease/Ton $335.70 $528.40 57%Rice Millfeed/Ton $27.05 $50.00 85%

costs of other feed ingredients68.5% of these increases attributed to biofuels policy

SAFTechSAFTechEmerging Feedstocks• Plants that can thrive under adverse conditions:

Jatropha curcas

• Hydroxylated Fatty Acid Triglycerides: Castor Oil and Lesquerella Oil

• Short-chain Fatty Acid Triglycerides: Cuphea Viscosissima

• Microalgae That Produce Lipids…

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Production of Fatty Oils: These are conservative estimates -- crop yields can vary widely.

Crop kg oil/ha litres oil/ha lbs oil/acre US gal/acre

corn (maize) 145 172 129 18

cashew nut 148 176 132 19

oats 183 217 163 23

lupine 195 232 175 25

kenaf 230 273 205 29

calendula 256 305 229 33

cotton 273 325 244 35

hemp 305 363 272 39

soybean 375 446 335 48

coffee 386 459 345 49

linseed (flax) 402 478 359 51

hazelnuts 405 482 362 51

euphorbia 440 524 393 56

pumpkin seed 449 534 401 57

coriander 450 536 402 57

mustard seed 481 572 430 61

camelina 490 583 438 62

sesame 585 696 522 74

safflower 655 779 585 83

rice 696 828 622 88

tung oil tree 790 940 705 100

sunflowers 800 952 714 102

cocoa (cacao) 863 1026 771 110

peanuts 890 1059 795 113

opium poppy 978 1163 873 124

rapeseed 1000 1190 893 127

olives 1019 1212 910 129

castor beans 1188 1413 1061 151

pecan nuts 1505 1791 1344 191

jojoba 1528 1818 1365 194

jatropha 1590 1892 1420 202

macadamia nuts 1887 2246 1685 240

brazil nuts 2010 2392 1795 255

avocado 2217 2638 1980 282

coconut 2260 2689 2018 287

oil palm 5000 5950 4465 635

Biodiesel yield = oil yield x 0.95 (approx.)

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Melting Range deg C Type of Oil

Oil / Fat Methyl Ester

Ethyl Ester

Iodine number

Cetane number

Rapeseed oil, h. eruc. 5 0 -2 97 to 105 55

Rapeseed oil, i. eruc. -5 -10 -12 110 to 115 58

Sunflower oil -18 -12 -14 125 to 135 52

Olive oil -12 -6 -8 77 to 94 60

Soybean oil -12 -10 -12 125 to 140 53

Cotton seed oil 0 -5 -8 100 to 115 55

Corn oil -5 -10 -12 115 to 124 53

Coconut oil 20 to 24 -9 -6 8 to 10 70

Palm kernel oil 20 to 26 -8 -8 12 to 18 70

Palm oil 30 to 38 14 10 44 to 58 65

Palm oleine 20 to 25 5 3 85 to 95 65

Palm stearine 35 to 40 21 18 20 to 45 85

Tallow 35 to 40 16 12 50 to 60 75

Lard 32 to 36 14 10 60 to 70 65

Jatropha 16 0-5 100 59

Oils and (Biodiesel) Esters Characteristics

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Jatropha• Jatropha, like the oil palm, grows

as a tree that produces fruit with oil-bearing seed

• not eaten by animals and is a vigorous, drought and pest resistant plant

• low cost and high yielding– 40-60 g oil/100 g seed kernels– Grown in many places

• methyl esters from Jatropha oil meet the standards for biodiesel

•Goldman Sachs cites Jatropha curcas as one of the best candidates for future biodiesel production

•Jatropha, biodiesel crop, will make money at crude oil prices a third below their current level, according to U.K.-based D1 Oils Plc teamed up with oil giant BP

•“Archer Daniels Midland Company, Bayer and Daimler to cooperate in Jatropha biodiesel project”

•Jatropha diesel “already fulfills the EU norm for biodiesel quality".

SAFTechSAFTechChallenges

• Jatropha oil is hydroscopic - absorbs water and needs nitrogen blanketing on steel tanks.

• Right from the time of expelling, the oil needs to be kept in storage conditions that prevent undue degradation. Exposure to air and moisture must be minimized - hence the need for nitrogen blanket on the tanks.

• Makes Jatropha high in acid, therefore tendency to degrade quickly, particularly if not handled properly through the supply chain. Will affect catalyst use increasing cost?

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LESQUERELLA

•24% of seed is oil

•60% hydroxylated fatty acids

•Gum with high value produced with oil

CASTOR• 48% of seed is oil• high uniformity and consistency in a naturally material • 90% hydroxylated fatty acids• Allergens and ricin not present in oil• high yielding, as much as 350-650 kg oil /hectare • requires moderate rainfall and can withstand long

periods of drought • uncomplicated crop that requires little attention

SAFTechSAFTechLubricity of Castor Fatty Acid Methyl Esters

EMA/ISO Lubricity Limit

.045mm

Castor FAME based additive significantly improves the pour point of other vegetable biodiesel without greatly affecting other properties such as density, viscosity and flash point

SAFTechSAFTechCastor Biodiesel

• Castor and Lesquerella oil prices are relatively high making them impractical for use as biodiesel feedstock.– castor oil (food grade) is used in food additives, flavorings, and candy

(i.e., chocolate)

– esters are important ingredients in various cosmetics and toiletries.

• However, increased lubricity at low levels (<1%) may provide an effective lubricity enhancer for low sulfur diesel fuels.

• Castor FAME products can act as cold flow improver additives for biodiesel– Low volume, high value markets

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Cuphea•Plant indigenous to North America, can be grown in many US regions

•Produces predominantly short-chained fatty acids C8:0 and C10:0

•This is not FAME Biodiesel but a straight vegetable oil (SVO) fuel

Cuphea Oil Viscosity

•Small, sticky seeds

•Agronomics not yet developed – harvesting difficult

SAFTechSAFTechViscosity and Fuel Performance• Normal Vegetable oils have

high viscosity which leads to injector coking and eventual engine failure.

• Reduced viscosity of Cuphea oil makes it a candidate for a fuel without transesterification

• Cuphea oil and mixtures with #2 Diesel performed well in engine durability tests.

• Performance exceeded food vegetable oils and petroleum #2 Diesel.

SAFTechSAFTechSimple extraction of materials

Biomass

Extraction

Purification

Usage

Palm oil press

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Algae—the other biomass

• Grows wherever you won’t find terrestrial biomass• Grows where few other plants could survive

– Hot climes

– Salt water

• Macroalgae– Seaweed, kelp

– Fast growing marine and freshwater plants that can grow up to 60 m in length

• Emergents– Plants that grow partially submerged in bogs and marshes

• Microalgae– Microscopic photosynthetic organisms

– Single cell plants - Efficiency of microbes combined with the ability to capture CO2 photosynthetically

• Produce up to 60% of their body weight as natural oil or lipids• Lipids as feed for biodiesel production

Solar bioreactor microalgae oil biodiesel

SAFTechSAFTechAlgae-to-biofuel with CO2 Sequestration

• 90% by weight of the algae is captured ("sequestered“) carbon dioxide

• Produces approximately 20 times the normal production volume for field crops

• Requires 5% of the normal water requirements for field crops

• Can be built on non arable lands and close to major city markets

• Can work in a variety of environments: urban, suburban, countryside, desert etc.

• Does not use herbicides or pesticides • Will have very significant operating and capital

cost savings over field agriculture • Will drastically reduce transportation costs to

market resulting in further savings, • Will be easily scalable

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The percentage of oil in a microalga may reach a level as high as 80% of its dry weight, but an average figure would be

nearer 40%. No higher plant makes that much oil.

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Challenges

• Algae look deceptively concentrated

• The ponds tend to have about ~0.2 to 0.4 gram/ liter

•Even at $70 per barrel oil, algal oils are a tough sale for dedicated biofuels facilities

•unknown) cost for oil extraction

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SAFTechSAFTechConclusion?

•The feed ingredient game has changed•Limiting resource: feedstocks, not demand•Feedstock prices bid up to energy value

•Higher petroleum prices = biofuels profits•Even without federal support biofuel production would be increasing

•Common near term answer to the initially high cost of non-food biofuels is to aim for niche coproduct opportunities

•METSS focus on additive values•SAFTech is to make algae the coproduct of existing viable business

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Sustainable Processes

• Attempt to satisfy…– Investor demand for unprecedented capital productivity

– Social demand for low present and future environmental impact

• While producing…– Highest quality products

– Minimum use of raw material

– Minimum use of energy

– Minimum waste

• In an ethical and socially responsible manner

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Lipodiesel

• LipoDiesel, clean-burning, renewable energy form that is harvested from the organic fat deposits suctioned away during liposuction.

• A perfect synthesis of economy, environmental awareness, and painless cosmetic surgery– something the American consumer has been crying out for

– We‘d go from an obesity epidemic to an obesity solution

• "LipoDiesel is a win-win, a slam dunk, Americans will have the bodies they desire, and enjoy total energy independence.

– Congress could authorized a bill to subsidize mandatory liposuctions with funding from a new tax on gym memberships.

– The Ford Lipodiesel, the Ford Flabgrabber SUV, will be unveiled in 2009

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Strategic Adipose Reserve Q: What is the diesel fuel equivalent of a pound of excess human fat?

A 8.74 lb fat/gallon.

Now you're thinking about the immense energy trapped in the nation's collective gut. (extra fat lbs. of avg. American) x (# of Americans) = lbs. available fat(lbs. available fat) / (8.74) = "Strategic adipose reserve, in diesel gallons.

20lb x 300,000,000 people/ 8.74 = 686 million gallonsthe stored fat energy wouldn't be enough to run our nation's vehicles for 2 days. That is absolutely mindboggling.

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Biodiesel Production Costs

$21 million facility

30 Million Gallon Per-unit costs Total

Fixed costs (10 years 8% APR) -$0.27 -$8.2 m

Variable costs -$0.071 -$2.1 m

Vegetable oil costs (per gallon) -$1.00 -28.9 m

Methanol (per gallon) -$0.95 -$3.4 m

Glycerol offset (per gallon) $7.50 $18.1 m

Total (per gallon) $0.816 -$24.5 m

SAFTechSAFTechThree Biodiesel Generations

• Most commonly produced biodiesel is first generation methyl ester (FAME = Fatty Acid Methyl Ester).

• Neste Oil's NExBTL renewable diesel is second generation biodiesel - production of middle distillate from vegetable oils pure hydrocarbons which by their properties and quality are chemically similar to fossil diesel -- "green diesel". Wider feedstock base can be utilized in the production process. Due to quality, it is possible to blend tens of percents into diesel.

• Third generation utilizes gasification and Fischer-Tropsch technology and any feedstock which contains carbon can be utilized.

SAFTechSAFTechEstimated changes 2008/2009 vs. 2007/2008

Item % Change

Corn production -3%Corn supply -2%Ethanol corn use 25%Corn feed use -4%Corn price 18%Soybean production 10%Soybean supply -10%Soybean meal feed use -7%Soybean meal price 25%Broiler production -2%Turkey production -2%Egg production -1%Pork production -10%Fed beef production -5%Milk production -1%

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Matching Raw Material and Desired Product Oxidation States

Meth

ane

Eth

ane

Eth

yle

ne,

Poly

eth

yle

ne

Natu

ral G

as

Oil

Coal

Carb

ohydra

tesP

oly

styre

ne,

Poly

vin

ylc

hlo

ride

Poly

est

er

Ace

tic

Aci

d

Carb

on D

ioxid

e

Carb

on M

onoxid

e

Meth

anol, E

than

ol

Ace

tone

Eth

yle

ne G

lyco

l, E

thyl A

ceta

te

Gly

ceri

n,

Phenol

Lim

est

on

e

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Conclusions

• By a factor of 105, most accessible carbon atoms on the earth are in the highest oxidation state

• However, there is plenty of available carbon in lower oxidation states closer to that of most desired chemical products

– High availability and the existence of photosynthesis does not argue persuasively for starting from CO2 or carbonate as raw material for most of the organic chemistry industry

– But, the same might not necessarily be true for the transportation fuels industry, especially if the energy carrier is carbonaceous but onboard CO2 capture is not feasible