Biodiesel Composition and Fuel

Properties

Gerhard Knothe
USDA / ARS / NCAUR
Peoria, IL 61604
U.S.A.

E-mail: [email protected]
 It All Began With…
… the Diesel Engine

Diesel’s Vision:

Develop an engine more efficient than the

steam engine, but …

...Rudolf Diesel did not originally

Diesel’s first engine
investigate vegetable oils as fuel.

Rather…
The Original Demonstration in
the Words of Rudolf Diesel

“At the Paris Exhibition in 1900 there was shown by the Otto
Company a small Diesel engine, which, at the request of the French
Government, ran on Arachide (earth-nut or pea-nut) oil, and worked
so smoothly that only very few people were aware of it. The engine
was constructed for using mineral oil, and was then worked on
vegetable oil without any alterations being made.

R. Diesel, The Diesel Oil-Engine, Engineering 93:395–406 (1912). Chem. Abstr. 6:1984 (1912).
The Original Demonstration in
the Words of Rudolf Diesel

The French Government at the time thought of testing the applicability to

power production of the Arachide, or earth-nut, which grows in
considerable quantities in their African colonies, and which can be easily
cultivated there, because in this way the colonies could be supplied with
power and industry from their own resources, without being compelled to
buy and import coal or liquid fuel.”

Diesel, R., The Diesel Oil-Engine, Engineering 93:395–406 (1912). Chem. Abstr. 6:1984 (1912).
Vegetable Oils as Alternative Fuel for
Energy Independence: Not a New
Concept
● 1920’s-1940’s: Many European countries interested in vegetable oils
as fuels for their African colonies in order to provide a local energy
source.
● Also interest in Brazil, China, India.

● A.W. Baker and R.L. Sweigert, Proc. Oil & Gas Power Meeting of the
ASME :40-48 (1947): “The United States is one of the countries in
the world fortunate enough to have large supplies of petroleum,
which its inhabitants have not always used wisely. With a possible
diminishing supply of oil accompanied by an increase in consumption,
the study of substitute fuels becomes of some importance. Vegetable
oils loom as a possibility for engines of the compression-ignition type.”
 The First Report on Biodiesel
Belgian Patent 422,877 (1937): Procédé de transformation d’huiles
végétales en vue de leur utilisation comme carburants.
An Extensive Report on Biodiesel
 “Old” Research:
First Cetane Number
Determination for Biodiesel
Bulletin Agricole du Congo Belge, Vol. 33, p. 3-90 (1942):
 (Potential) Sources of Biodiesel
• Vegetable oils
• Classical (edible) commodity oils (palm, rapeseed /
canola, soybean, etc.)
• “Alternative” (inedible) oils (jatropha, karanja, pennycress, etc.)

• Animal fats

• Used cooking oils

• “Alternative” feedstocks
• Algae

• Variety of feedstocks with considerably varying fatty acid profiles

• Fuel properties vary considerably
 Why biodiesel and not the neat oil?

CH2-OOCR1 R‫׳‬OOCR1 CH2OH

| Catalyst |
CH-OOCR2 + 3 R‫׳‬OH → R‫׳‬OOCR2 + CHOH
| |
CH2-OOCR3 R‫׳‬OOCR3 CH2OH

Vegetable Oil Alcohol Vegetable Oil Alkyl Esters Glycerol

(Triacylglycerol) (Biodiesel)

Viscosity!

27-35 mm2/sec 4-5 mm2/sec

Kinematic viscosity of petrodiesel fuels usually ≈ 1.8-3.0 mm2/sec.

 Major Ester Components of Most
Biodiesel Fuels
Fatty esters in from common vegetable oils (palm, soybean, canola/rapeseed,
sunflower, etc):
• Methyl palmitate (C16:0): CH3OOC-(CH2)14-CH3
• Methyl stearate (C18:0): CH3OOC-(CH2)16-CH3
• Methyl oleate (C18:1, ∆9c): CH3OOC-(CH2)7-CH=CH-(CH2)7-CH3
• Methyl linoleate (C18:2; all cis): CH3OOC-(CH2)7-(CH=CH-CH2)2-(CH2)3-CH3
• Methyl linolenate (C18:3; all cis): CH3OOC-(CH2)7-(CH=CH-CH2-)3-CH3

From other oils:

• Methyl laurate (C12:0): CH3OOC-(CH2)10-CH3
• Methyl ricinoleate (C18:1, 12-OH; cis):
CH3OOC-(CH2)7-CH=CH-CH2-CHOH-(CH2)5-CH3
• Algal Oils:
Methyl eicosapentaenoate (C20:5): CH3OOC-(CH2)3-(CH=CH-CH2-)5-CH3
Methyl docosahexaenoate (C22:6): CH3OOC-(CH2)2-(CH=CH-CH2-)6-CH3
 Minor Constituents in Biodiesel
• Can influence fuel properties
• Cold flow, oxidative stability, corrosion, combustion, catalyst
poisons, lubricity

CH2-OOCR1 CH2OOCR1 CH2OOCR

| | │
CH-OOCR2 CHOOCR2 CHOH
| | │
CH2-OOCR3 CH2OH CH2OH
• Triacylglycerols • Diacylglycerols • Monoacylglycerols

• Glycerol

• Free Fatty Acids: R-COOH

• Alcohol
• Na, K, Ca, Mg, P, (S)
• Sterol glucosides
 Technical Problems with Biodiesel
• Cold flow

• Oxidative stability

• NOx exhaust emissions

• May fade with time due to new exhaust emissions control

technologies.

• Other fuel quality issues:

• Minor components influencing fuel properties.

 Biodiesel Standard ASTM D6751-(11a)
Property Test method Limits Units
Flash point (closed cup) D 93 93 min oC

Alcohol control. One of the following must be met:

1. Methanol content EN 14110 0.2 max % volume
2. Flash point D 93 130 min 130 min
Water and sediment D 2709 0.050 max % volume
o
Kinematic viscosity, 40 C D 445 1.9-6.0 mm2 / s
Sulfated ash D 874 0.020 max % mass
Sulfur D5453 0.05 or 0.0015 max a) % mass
Copper strip corrosion D 130 No. 3 max
Cetane number D 613 47 min
Cloud point D 2500 Report oC

Carbon residue D 4530 0.050 max % mass

Acid number D 664 0.50 max mg KOH / g
Free glycerin D 6584 0.020 % mass
Total glycerin D 6584 0.240 % mass
Phosphorus content D 4951 0.001 max % mass
Distillation temperature, D 1160 360 max oC

Atmospheric equivalent temperature, 90% recovered

Sodium and potassium, combined EN 14538 5 max ppm (µg/g)
Calcium and magnesium, comb. EN 14538 5 max ppm (µg/g)
Oxidation stability EN 15751 3 min hours
Cold soak filterability D7501 360 max sec

a) The limits are for Grade S15 and Grade S500 biodiesel, respectively. S15 and S500 refer to
maximum sulfur specifications (ppm).
 Biodiesel Standard EN 14214
Property Test method Limits Units
Ester content EN 14103 96.5 min % (m/m)
o
Density; 15 C EN ISO 3675, 12185 860-900 kg/m3
o
Viscosity, 40 C EN ISO 3104, ISO 3105 3.5-5.0 mm2/s
Flash point EN ISO 2719, 3679 101 min oC

Sulfur content EN ISO 20846, 20884 10.0 max mg/kg

Carbon residue (10% dist. res.) EN ISO 10370 0.30 max % (m/m)
Cetane number EN ISO 5165 51 min
Sulfated ash ISO 3987 0.02 max % (m/m)
Water content EN ISO 12937 500 max mg/kg
Total contamination EN 12662 24 max mg/kg
o
Copper strip corrosion (3h, 50 C) EN ISO 2160 1
o
Oxidative stability, 110 C EN 14112, 15751 6.0 min h
Acid value EN 14104 0.50 max mg KOH / g
Iodine value EN 14111 120 max g iodine /100g
Linolenic acid content EN 14103 12 max %(m/m)
Content of FAME with ≥ 4 double bonds 1 max % (m/m)
Methanol content EN 14110 0.20 max % (m/m)
Monoglyceride content EN 14105 0.80 max % (m/m)
Diglyceride content EN 14105 0.20 max % (m/m)
Triglyceride content EN 14105 0.20 max %(m/m)
Free glycerine EN 14105, 14106 0.02 max %(m/m)
Total glycerine EN 14105 0.25max %(m/m)
Alkali metals (Na + K) EN 14108, 14109, 14538 5.0 max mg/kg
Earth alkali metals (Ca + Mg) prEN 14538 5.0 max mg/kg
Phosphorus content EN 14107 4.0 max mg/kg
 Some Fatty Acid Profiles

Vegetable Oil C16:0 C18:0 C18:1 C18:2 C18:3

Palm 45 4-5 38-40 10-11

Rapeseed / Canola 3-4 1-3 58-62 20-22 9-12

Soy 8-13 2-6 18-30 49-57 2-10

Sunflower 6-7 3-5 21-29 58-67

Jatropha 13-15 7-8 34-44 31-43

 Properties of Vegetable Oil Esters
Methyl Ester Cloud Point Cetane Number Kin. Visc.
(°C) (40°C; mm2/s)
Palm 16 68-70 4.4

Rapeseed / Canola -3 52-55 4.5

Soy 0 48-52 4.1

Sunflower 0 ≈ 55 4.4

Jatropha 4-5

Oxidative stability: usually antioxidants required to meet standard

specifications
 Properties to Consider
Two types of specifications in biodiesel standards (ASTM D6751; EN 14214):

Properties inherent to fatty esters:

• Cetane number
• Cold flow
• Viscosity
• Oxidative stability
(• Feedstock restrictions: Iodine value, viscosity, specific esters in EN
14214)
(• Density only in EN 14214)

Parameters related to production, storage, etc.

• Acid value
• Free and total glycerol
• Na, K, Mg, Ca, P, S
• Water and sediment, sulfated ash, carbon residue

Not in biodiesel standards: Exhaust emissions, lubricity

 Some General Observations on
Fatty Ester Fuel Properties

Fuel properties of fatty esters depend on

• Chain length (number of CH2 moieties)

• Number and position of double bonds

 Cetane Number
• Dimensionless descriptor related to the ignition delay time of a fuel
in a cylinder
• Higher cetane numbers indicate reduced ignition delay time,
“better” combustion.
• Hexadecane is the high-quality reference compound with assigned
CN = 100.

• CN can be correlated to NOx exhaust emissions

• Saturated compounds (higher CN) show reduced NOx exhaust
emissions.
 Cetane Numbers
Saturated methyl esters (ME)
Saturated ethyl esters
Mono-, di-, and triunsaturated ME
100 Highly polyunsaturated ME C18:0 / 101
90 C16:0 / 85.9

80
Cetane Number

70

60
C10:0 / 51.6 C18:1 9c / 59.3
EN 14214 =51 min
50
ASTM D6751 = 47 min
40
C18:2 9c,12c / 38.2
C20:4 / 29.6
30

20 C18:3 9c,12,15c / 22.7 C22:6 / 24.4

10
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Number of carbon atoms in the fatty acid chain

 Cetane Number
• Cetane numbers of mixtures:
CNmix = ∑ AC x CNC
(CNmix = CN of the mixture, AC = relative amount of an individual
neat ester in the mixture, CNC = CN of the individual neat ester)

• Most biodiesel fuels from vegetable oils meet CN requirements in

standards (ASTM D6751: 47 min; EN 14214: 51 min) as there are
usually sufficient amounts of esters with higher CN
 Why Triacylglycerol Feedstocks?

• Alkanes are “ideal” diesel fuels.

• Branched compounds and aromatics have low cetane numbers

• Structural similarity (long hydrocarbon chains) responsible for suitability

of fatty esters as diesel fuels.

• Compounds such as methyl palmitate and methyl stearate have CN

comparable to hexadecane and other long-chain alkanes

 Exhaust Emissions Studies
Average effect of biodiesel and B20 vs. petrodiesel on regulated
emissions (Source: USEPA report 420-P-02-001):

Petrodiesel
Petrodiesel
Biodiesel
B20
100
100

80
Relative emissions

80

Relative Emissions
60
60

40
40

20
20

0 0
NOx PM CO HC
NOx PM CO HC
Pollutant
Pollutant
 NOx and PM Exhaust Emissions of
Petrodiesel, Biodiesel, Their Components
2003 Engine; EPA Heavy Duty Test
3.0
Brake-Specific Emission Rate, g/hp-hr

2.5

2.0

NOx
1.5
PMx10

1.0

2007PM Standard
0.5

0.0
te

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G. Knothe, C.A Sharp, T.W. Ryan III, Energy & Fuels 20, 403-408 (2006).
 Change in NOx and PM vs. petrodiesel
Change in Exhaust Emissions Relative to Base Fuel (%)
-80

-70

-60

-50

-40

-30

-20

-10

10
0
Hexadecane

Dodecane

Me soyate

Me oleate

Me palmitate

Me laurate
PM
NOx
 Change in HC and CO vs. petrodiesel
Change in Exhaust Emissions Relative to Reference Fuel (%)
-60

-50

-40

-30

-20

-10

10
0
Hexadecane

Dodecane

Me soyate

Me oleate

Me palmitate

Me laurate
CO
Hydrocarbons
 Viscosity
8 Saturated methyl esters (ME)
Saturated ethyl esters C22:1 13c / 7.33
Kinematic Viscosity (40 C; mm /s)

Mono-, di-, and triunsaturated ME

2

7 Highly polyunsaturated ME

6 ASTM D6751 upper limit

o

C18:0 / 5.85
5 EN 14214 upper limit

C16:0 / 4.38 C18:1 9c / 4.51

4
C18:2 9c,12c / 3.65
EN 14214 lower limit
3
C18:3 9c,12c,15c / 3.14 C20:4 / 3.11 C22:6 / 2.97
C12:0 / 2.43
2
ASTM D6751 lower limit
C10:0 / 1.72
1

8 9 10 11 12 13 14 15 16 17 18 19 20 21 22

Number of carbon atoms in the fatty acid chain

 Viscosity

• Viscosity increases with chain length and increasing saturation.

• Kinematic viscosity of mixtures νmix

νmix = ∑ Ac x νc

• Virtually all biodiesel fuels meet ASTM D6751 specifications

• EN 14214 more restrictive

• Biodiesel fuels with greater amounts of lower-viscosity

components may not meet lower limit
Cold Flow: Melting Points of Fatty
Acid Esters
80
70
Saturated methyl ester 58.6
60 53.2
Saturated ethyl ester
50 46.4 55.9
37.7 48.6
40
Melting Point ( C)

28.5 41.3
30
o

33.0
18.5
20
23.2
10 4.3
11.8
0
22:1 13c / -3.1
-10 -13.5 -1.8
20:1 11c / -7.8
-20
-20.4 18:1 9c / -20.2
-30 -37.4
-40 16:1 9c / -34
18:2 9c,12c / -43.1
-50 -44.7 18:3 9c,12c,15c / <-50
-60
8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

Number of carbon atoms in the fatty acid chain

 Cold Flow
• Melting points of fatty acid esters depend on chain length and
unsaturation

• Cold flow properties determined by nature and amount of saturated

compounds

• Cloud point common and stringent test procedure

• “Soft” specification in biodiesel standards

• ASTM D6751: Cloud point by report, cold soak filtration
• EN 14214: Cold-filter plugging point, depending on time of
year and geographic location
 Cold Flow

• Minor constituents such as monoacylglycerols and sterol glucosides

also influence cold flow.

• Melting points of monopalmitin and monostearin > 70°C

• Melting points of sterol glucosides ≈ 240°C

• Effects often noticeable upon storage

 Oxidative Stability
• Oxidative stability is one of the major technical challenges facing
biodiesel.

• Affected by presence of air, temperature, light, extraneous

materials, container material, headspace volume

• Structural reason for the autoxidation of fatty compounds:

Allylic CH2 positions

↓ ↓
H3CO2C-(CH2)x-CH2-CH=CH-CH2-CH=CH-CH2-(CH2)y-CH3
↑
especially: bis -allylic CH2 positions
 Oxidative Stability

Relative rates of oxidation (E.N. Frankel, Lipid Oxidation, 2005):

• Oleates = 1 (two allylic positions)

• Linoleates = 41 (two allylic positions, one bis-allylic position)

• Linolenates = 98 (two allylic positions, two bis-allylic positions)

• Chains with > 3 double bonds have even higher relative rates

Is the oxidative stability of mixtures (vegetable oil esters) directly

proportional to the amount of unsaturated compounds or do small
amounts of unsaturated compounds have greater influence than their
amounts indicate?
 Oxidative Stability
• Rancimat test (110°C):
Saturated esters > 24 h
Methyl palmitoleate 2.11 h
Methyl oleate 2.79 h
Methyl linoleate 0.94 h
Methyl linolenate 0.00 h

Methyl eicosatetraenoate (C20:4) 0.09 h

Methyl docosahexaenoate (C22:6) 0.07 h

• ASTM D6751 minimum specification 3h

• EN 14214 minimum specification 6h
• Almost always antioxidant additives required
 Density
• Only in EN 14214
• Range of 0.86 – 0.90 g/cm3 (15°C)

• Not a problem for most biodiesel fuels.

• Only highly polyunsaturated fatty esters may be problematic:
C20:4 0.9064 g/cm3
C22:6 0.9236 g/cm3

• Density of a mixture: ρmix = ∑ Ac x ρc

 Biodiesel and Lubricity
• Neat biodiesel has excellent lubricity as do neat methyl esters.

• Low-level blends (~ 2% biodiesel in petrodiesel = B2):

• Lubricity benefits through biodiesel with (ultra-)low sulfur
petrodiesel which do not possess inherent lubricity
compared to non-desulfurized petrodiesel.
• Marginal cost impact.

• Not included in biodiesel standards.

• High-frequency reciprocating rig (HFRR) tester (ASTM D6079;
ISO 12156) in ASTM and EN petrodiesel standards.
• Maximum wear scars of 520 (ASTM) and 460 µm (EN).
 Biodiesel and Lubricity
Lubricity of low-level blends of biodiesel with petrodiesel to a great
extent determined by minor constituents, especially free fatty acids
and monoacylglycerols.
• In the neat form, even better lubricity than methyl esters.
• Glycerol has limited effect (insolubility in petrodiesel).

Example (HFRR wear scars):

• ULSD: 651, 636 µm
• w. 1% methyl oleate: 597, 515 µm
• 1% oleic acid in methyl oleate, then 1% thereof in ULSD: 356,
344 µm.
• w. 2% methyl oleate: 384, 368 µm

G. Knothe, K.R. Steidley; Energy & Fuels 19, 1192-1200 (2005).

 Biodiesel and Lubricity
• Higher lubricity with increasing number of double bonds and greater
chain length:
Methyl laurate 416, 408,
Methyl stearate 322, 277,
Methyl oleate 290, 342,
Methyl linoleate 236, 219,
Methyl linolenate 183, 185

• Effect of oxygenated functional groups:

COOH > CHO > OH > COOCH3 > C=O > C-O-C

G. Knothe, K.R. Steidley; Energy & Fuels 19, 1192-1200 (2005).

 Property Trade-off
Increasing chain length:

• Higher melting point (-)

• Higher cetane number (+)

Increasing unsaturation:

• Lower melting point (+)

• Decreasing oxidative stability (-)
• Lower cetane number (-)
 Five Approaches to Improving
Biodiesel Fuel Properties
Unchanged fatty Additives A
ester composition

Change B
alcohol

Physical procedures C

Modified fatty ester

composition
Change fatty acid
profile Genetic
D
modification
Inherently different
fatty acid profile
Alternative E
feedstocks

G. Knothe; Energy & Environmental Science, 2, 759-766 (2009).

 Additives, physical procedures
Additives

• Cold flow improvers

Do not affect cloud point
• Antioxidants
Oxidation delayers

Physical procedures

• Winterization for removing saturates to improve cold

flow
 Influence of Alcohol Moiety
Branched and longer-chain esters:
● Lower melting points, similar cetane numbers compared to methyl esters

Ester M.P. (°C) CN Ester M.P. (°C) CN

C16:0 Methyl 28.5 85.9 C18:0 Me 37.7 101
C16:0 Ethyl 23.2 93.1 C18:0 Et 33.0 97.7
C16:0 Propyl 20.3 85.0 C18:0 Pr 28.1 90.0
C16:0 iso-Propyl 13-14 82.6 C18:0 i-Pr 96.5

C18:1 Methyl -20.2 59.3 C18:2 Me -43.1 38.2

C18:1 Ethyl -20.3 67.8 C18:2 Et -56.7 39.6
C18:1 Propyl -30.5 58.8 C18:2 Pr 44.0
C18:1 iso-Propyl 86.6

● Disadvantage: Higher costs of alcohols

Source: Handbook of Chemistry and Physics; The Lipid Handbook, various publications.
 Fatty Acid Profile: Something
“Better” Than Methyl Oleate?
• Positional Isomers
No major advantages compared to methyl oleate

• Geometric Isomers (cis /trans)

Higher melting points, higher viscosity of trans

• Hydroxylated Chains
High viscosity, low cetane number, low oxidative stability

• Shorter Saturated Chains

• Shorter Unsaturated Chains

 Shorter-Chain Monounsaturates
Methyl palmitoleate (C16:1)
• Melting point: -34°C
• Cetane number: 51-56 (ASTM D6890)
• Kinematic viscosity (40°C): 3.67 mm2/s
• Oxidative stability: 2.11 h
• Extrapolation of exhaust emissions: Effect likely similar to methyl
oleate (slight chain-length effect)

Methyl myristoleate (C14:1)

• Melting point: -52°C
• Kinematic viscosity (40°C): 2.73 mm2/s

Major advantage compared to methyl oleate:

• Improved cold flow, lower kinematic viscosity

G. Knothe; Energy & Fuels 22, 1358-1364 (2008).

 Shorter-Chain Monounsaturates:
An Example
Macadamia nut oil methyl esters:

Two examples:
• 16 and 20 % C16:1;
• 59 and 55% C18:1 ∆9; 4% C18:1 ∆11.

• Cetane number: 57-59

• Oxidative stability: 2 h

• Kinematic Viscosity: 4.5 mm2/s

• Cloud Point: 7.0 / 4.5 °C

but: C16:0 ≈8.5%; C18:0 ≈3.5%; C20:0 ≈ 2.5%; C22:0 ≈ 0.8%.
G. Knothe; Energy & Fuels 24, 2098–2103 (2010).
 Shorter-Chain Saturates
M.P. Cetane Kin. Visc. Heat of comb.
(°C) number (40°C; mm2/s) (kJ/kg)
Methyl octanoate -37.3 39.7 1.20 34907
Ethyl octanoate -44.5 42.2 1.32
Methyl decanoate -13.1 51.6 1.71 36674
Ethyl decanoate -19.8 54.5 1.87
Methyl laurate 4.6 66.7 2.43 37968

High oxidative stability: All > 24 h.

Extrapolation of exhaust emissions for C10 esters:

NOx likely slightly reduced (ca. -5%); PM significantly reduced (80-
85%); CO reduced; HC increased
 Shorter-Chain Saturates:
Cuphea Methyl Esters
Fatty Acid Profile of Cuphea PSR 23 (C. Viscosissima × C. Lanceolata):

Fatty acid Cuphea Jatropha Palm Rapeseed Soybean Sunflower

PSR 23
C8:0 0.3
C10:0 64.7
C12:0 3.0
C14:0 4.5
C16:0 7.0 14.5 44.1 3.6 11 6.4
C18:0 0.9 7.5 4.4 1.5 4 4.5
C18:1 12.2 34-45 39.0 61.6 23.4 24.9
C18:2 6.7 29-44 10.6 21.7 53.2 63.8
C18:3 < 0.5 0.3 9.6 7.8 -
 Shorter-Chain Saturates:
Cuphea Methyl Esters
Properties of cuphea PSR23 methyl esters (CuME):

Cetane number: 55-56

Kinematic viscosity (40°C): 2.38-2.40 mm2/s
Oxidative stability: 3.1 – 3.5 h
Cloud point: -9 to -10°C

G. Knothe, S.C. Cermak, R.L. Evangelista; Energy & Fuels, 23, 1743-1747 (2009).
 Distillation Curve:
CuME vs SME and ULSD

B.T. Fisher, G. Knothe, C.J. Mueller, Energy Fuels, 24, 1563-1580 (2010).
 Castor Oil Methyl Esters
Fatty acid profile of castor oil 85-90% ricinoleic acid

Cetane Kinematic Viscosity Oxidative

Number (40°C; mm2/s) Stability (h)
Castor methyl esters 37.55 14.82 5.87

ASTM D6751 47 min 1.9-6.0 3 min

EN 14214 51 min 3.5-5.0 6 min

Cold flow related properties:

• Melting point of methyl ricinoleate: -5.8°C
• Pour point of castor methyl esters: -20°C

C18:1 12-OH 37 -5 15.29 0.67

 Biodiesel from Algae
• Claimed high production potential
• Order of magnitude greater than highest-yielding vegetable oils?

• Avoids food vs. fuel issue.

• Problems with growth and harvesting of algae, oil extraction.

• High production costs.

• Little to no technical information on biodiesel derived from algal oils.

• Potential properties need to be estimated from fatty acid
profiles and data on other biodiesel and neat compounds.
 Biodiesel from Algae: Fatty Acid
Profiles
• Most profiles contain high amounts of saturated and / or
polyunsaturated fatty acid chains
• Eicosapentaenoic (C20:5) and docosahexaenoic (C22:6) acids
most common highly polyunsaturated fatty acids in algal oils

• Palmitic acid most common fatty acid (m.p. of methyl

ester 28.5°C) in algal oils (and palm oil!);
• Myristic (C14:0) acid also present in many algal oils (m.p.
methyl ester 18°C).

• Some exceptions
Biodiesel from Algae: Fuel Properties
• Cetane numbers of most algal biodiesel likely lower to mid 40’s.
• Not all will meet CN specification in ASTM D6751; most will not
meet CN specification in EN 14214

• Kinematic viscosity (40°C) of most algal biodiesel likely in the range

3.0 – 4.0 mm2/s

• Oxidative stability low due to highly polyunsaturated fatty acids.

• Cold flow:
• Cloud point of palm oil (44% C16:0; 4% C18:0) around 16°C.
• Cloud point of soybean oil (10% C16:0; 5% C18:0) around 0°C.
• Cloud points of most algal biodiesel fuels likely between these
values.
 Biodiesel from Algae

• Claimed high production potential not (yet) realized → Uncertain

future.

• Any algal biodiesel will need favorable properties to compete in

the marketplace.

• Conversely, algae delivering fuels with favorable properties will need

actual high production.
• Property trade-off likely missing due to relatively low amounts
of monounsaturated fatty acid chains
 Fatty Acid Profiles of Algal Oils
• A different profile: Trichosporon capitatum
• 16:0 7.0%, 18:0 1.1%
• 16:1 1.0%, 18:1 / 79.8%, C18:2 / 8.0%
(H. Wu et al., Appl. Energy 2011, 88, 138-142) i

• Usually greater number of components than vegetable oils

• Fatty acid profiles of a species depend on growing conditions such as

• Temperature
• Light
• Nutrients.
 Renewable Diesel: Overview
• Closer in composition and properties to (ultra-low sulfur) petrodiesel.

• No / low sulfur, aromatics

• Higher oxidative stability

• Cold flow varies

• “Lighter” form: Aviation fuel

• Regulated exhaust emissions likely reduced compared to

“regular” petrodiesel (but not necessarily biodiesel).

• Feedstock availability and cost issues similar to biodiesel

• Low lubricity

• Energy use / energy balance? Likely less favorable than biodiesel

 Biodiesel vs. Renewable Diesel:
Mass (Energy) Balance of Products
Biodiesel - Methyl oleate from triolein:
C57H104O6 + 3 CH3OH → 3 C19H36O2 + C3H8O3
885.45 3 x 296.495 =889.458 = 100.5% mass
≈ 40000 kJ/kg x 1.005 = 40200 kJ 39547 kJ/L

Renewable Diesel - Heptadecane from triolein:

C57H104O6 + 6 H2 → 3 C17H36 + 3 CO2 + C3H8
885.45 3 x 240.475 =721.425 = 81.5% mass
≈ 47500 kJ/kg x 0.815 = 38305 kJ 41310 kJ / L

Glycerol and propane not accounted for here.

 Biodiesel / Renewable Diesel:
An Evaluation
Use each fuel where most appropriate for its properties?

• Biodiesel for ground applications?

• Utilize environmental and other benefits: Reduced exhaust
emissions, biodegradability, safer handling

• Renewable diesel (in “lighter” form) for aviation applications due to

cold flow?
• Energy balance may be of less interest here: “Sacrifice” some
other energy source(s) in order to have aviation fuel
available?
• No other (realistic) alternative jet fuel.
 Biodiesel / Renewable Diesel:
An Evaluation
• Consider limited amount of feedstock available.

• Feedstocks with high yield not (yet) available in sufficient

quantities (algae).

• Fuel property issues.

• Co-products: Renewable glycerol is preferable

• Complex issue: Advantages and disadvantages to both approaches.

 Summary / Conclusions
• Biodiesel with improved properties needed to take advantage of its
benefits

• Legislative and regulatory incentives may/do not

suffice if properties do not meet market demands

• Feedstocks with high supply potential (algae!) will need to address

the issue of fuel properties.
 Parting Thoughts:
Rudolf Diesel (1912)

“The fact that fat oils from vegetable sources can be used may seem
insignificant to-day, but such oils may perhaps become in course of time of
the same importance as some natural mineral oils and the tar products are
now. ... In any case, they make it certain that motor-power can still be
produced from the heat of the sun, which is always available for
agricultural purposes, even when all our natural stores of solid and liquid

fuels are exhausted.”

R. Diesel, The Diesel Oil-Engine, Engineering 93:395–406 (1912). Chem. Abstr. 6:1984 (1912).