Toward High Performance Biodiesel

Tatang H. Soerawidjaja
Member of Indonesian Academy of Science, President of Indonesian
Association BioEnergy Scientists and Technologists, Associate Professor of
Chemical Engineering, Institute of Technology at Bandung (ITB)

Workshop on higher blending of biodiesel (H-FAME)

for automotive utilization in ASEAN
September 17 – 18, 2015, Centara Grand Ladprao, Bangkok, Thailand
 Biodiesel

• Fuel for diesel engine that consist of mixtures of

methyl ester of fatty acids (FAME : Fatty Acid
Methyl Ester).
• The number of constituents composing a biodiesel
is limited ( 7 – 14 components).
• Most important are methyl ester of lauric,
myristic, palmitic, stearic, palmitoleic, oleic,
linoleic and linolenic acids.
• Properties of biodiesels are relatively easily
guesstimated from the content of these FAMEs. 2
 Properties of pure FAME
Iodine Value, Rancimat Kinematic
Cetane Melting
Methyl ester I.V., Induction Viscosity at
Number Point, oC.
g-I2/(100 g) Period, hrs. 40 oC, cSt.
Laurate, Me-C12:0 0 58,2 3.7 > 20 2.35
Myristate,Me-C14:0 0 70,0 17.1 > 20 3.24
Palmitate, Me-C16:0 0 79,8 28.8 > 20 4.35
Stearate, Me-C18:0 0 90,6 39.0 > 20 5.66
Palmitoleate, Me-C16:1 94.6 50,0 -48.9 >2 3.07
Oleate, Me-C18:1 85.6 58,5 -19.5  14 4.42
Linoleate,Me-C18:2 172.4 40,2 -35 1.0 4.46
Linolenate,Me-C18:3 260.3 22,0 -57 0.2 3.11
Source : Phommavongsa (2012); except Rancimat Induction Periods, from Goto et.al. (2008) and Moser (2009).

 Methyl oleate has more or less “optimum” properties : good cetane value, low
melting point, proper viscosity, and good oxidation stability (Rancimat IP).
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Methyl ester of polyunsaturated fatty acids (linoleate, linoleate) have catalytically
detrimental effects on oxidation stability!.

Source : Goto et.al. “EAS-ERIA Biodiesel Fuel Trade Handbook :

2010”
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Fatty acid compositions of various vegetable oils
Fatty acid Coconut Palm Olive J. curcas Rapeseed Soybean
Caprylic,C8:0 5 – 10
Capric, C10:0 5 – 10
Lauric, C12:0 43 – 53 Trace
Myristic, C14:0 15 – 21 0–2 Trace 0–½ Trace Trace
Palmitic, C16:0 7 – 11 30 – 48 7 – 16 12 – 17 3–6 7 – 12
Stearic, C18:0 2–4 3–6 2–4 5–7 1–3 2–6
Oleic, C18:1 6–8 38 – 44 64 – 86 37 – 63 52 – 66 20 – 30
Linoleic, C18:2 1–3 9 – 12 4 – 15 19 – 40 17 – 25 48 – 58
Linolenic, C18:3 - - ½-1 - 8 – 11 6 – 12

I.V., g-I2/(100 g) 8 – 12 44 – 54 80 – 88 93 – 107 81 – 112 120 - 140

Note : The compositions of (used) cooking oils will depend on the vegetable oil sources.
 Polyunsaturated fatty acids lead to poor oxidation stability but excellent fluidity!.
 Saturated fatty acids lead to excellent oxidation stability but poor fluidity!
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Boiling curves
diesel versus
biodiesels
[Krahl et.al. (2007)]

 An Increasing boiling
curve is beneficial for
good fuel injection and
combustion in the
cylinder.
 Coconut methyl ester
(CME) has the best
boiling curve!.

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 The ideal (or high performance) biodiesel?.

• Do not contain methyl ester of polyunsaturated fatty acids

(PUFA) : linoleate, linolenate, etc.
• Mainly consists of methyl oleate and methyl ester of
saturated acids.
• Contains some percentage of lauric oil methyl ester
(coconut, palm kernel, babassu, etc).
• The saturated fatty acid chain is preferably not
normal/linear but methyl-branched ( result in much
lower pour/cloud point!).
 High performance : good cetane value, low cloud point,
proper viscosity, excellent oxidation stability, and
favorable boiling curve. 7
 Research challenges

• Elimination of polyunsaturated fatty acid chains.

Through hydrogenation ( H-FAME) approach
or molecular biology approach.
• Methyl branching (or isomerization) of the
saturated fatty acid chains.
 Saturated fatty acid that contain methyl branch
in the middle of the alkyl chain has a melting
point 40 – 50 oC lower than the corresponding
linear counterpart.
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 Challenges to molecular biologists
• Most desirable from fuel consideration : saturated
fatty acids, preferably methyl-branched in the
middle of the alkyl chain.
• In plant lipid biosintesis pathway, the unsaturated
fatty acids (palmitoleic, oleic, linoleic, linolenic/
eleostearic) are actually synthesized from saturated
fatty acids (palmitic & stearic acids) wiyth the aid
of fatty acid desaturases enzymes.
• Deactivation of these fatty acid desaturases
enzymes could lead to exlusive production of the
desirable saturated fatty acids or saturated fats.
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 The saturated monoglyceride (SMG) issue
• Saturated monoglyceride (SMG) precipitation is the most
important recent technical issue confronting palm oil
biodiesel.
• SMG is part of the monoglyceride (MG) impurity in
biodiesel (EN limit : max. 0.8 %-mass).
• SMG portion of monoglyceride (or SMG/MG) is higher,
the higher the saturated fatty acid content of the vegetable
oil raw materials.
• ASTM now limits MG content at max. 0.4 %-mass. New
Indonesian biodiesel standard : maximum 0.8 %-mass.
• Mulstistage ( 2) transesterification process gives more
assurance to lower content of MG (and therefore SMG).
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 THANK YOU VERY MUCH

for your attention

Indonesian Association of BioEnergy Scientists and Technologists

tatanghs@che.itb.ac.id thsoerawidjaja@gmail.com