216 April 2007, Vol.

18 (4)

beyond
biodiesel
Salmiah Ahmad, Parthiban Siwayanan,
Zulina Abd Murad, Haliza Abd Aziz,
and Hoong Seng Soi

The anticipated decreasing supply of fossil fuel

but increasing demand and concern for the envi-
ronment have led the developed countries to in-
troduce policies to encourage the use of alterna-
tive fuels, especially bio-based fuel. Several
types of biofuels are now available as substi-
tutes for gasoline (petrol) or diesel. These include
oil/fat (either crude, processed, or used), methyl
ester from oil/fat, and ethanol or liquid fuel from
biomass. Fatty acid methyl ester (ME) has been
identified as a suitable substitute for blending
with diesel or to be used in diesel engines with-
out the need to modify the engines. The Euro-
pean Union (EU) encourages the use of ME as
diesel substitute (biodiesel) as are many other
countries, including Malaysia.
Production of biodiesel or methyl ester from
oils/fats involves the conversion of the free fatty acids and
oils/fats using methanol and a catalyst to produce ME and
crude glycerine.The glycerine is separated and the ME is
washed and then distilled. Many types of oils/fats have
been used for the production of ME (biodiesel), including
rapeseed oil, soybean oil, tallow, and palm oil. ME from
liquid oils such as rapeseed and soybean may be used
during winter; those from palm oil solidify in cold tem-
peratures, and some Malaysian manufacturers have in-
stalled an additional process in order to produce winter
biodiesel. Another unique feature of palm oil is that in
crude form it is red owing to the presence of carotenes
 HEADER/inform 217
BIOFUELS

METHYL ESTERS AS THE

ROUTE FOR THE PRODUCTION
OF SURFACTANTS FEEDSTOCK
as well as vitamin E. These vitamins can be extracted
after the crude palm oil (CPO) is converted to ME and TABLE. Uses of Methyl Esters
the ester distilled. Uses Types of esters Status
Palm oil biodiesel producers therefore have the op- Biodiesel All types but C18:1 Todays hot topic
tion to produce not only summer biodiesel, winter bio- for winter
diesel, and crude glycerine but also vitamins and saturat- Fatty alcohol C12C14, therefore Widely practiced
ed methyl esters. production lauric oil-based
Soap Mixture of C1618 and Practiced in Japan
SATURATED METHYL ESTERS AS C1214
Methyl ester C14, C16, C18, or their Practiced in USA
FEEDSTOCK FOR THE PRODUCTION sulfonates (MES) mixtures. Need to be and Japan
OF SURFACTANTS fully saturated
Esterquats C16, C18 for softening, Practiced in
Surfactants are surface active agents that are active at in-
and C18:1 for developed countries
terfaces, reducing the interfacial tension and thereby al-
rewetting power
lowing several reactions to take place.There are at least
four types of surfactants:

Anionicssurfactants having negative charges
at the end of the molecules; usually used as active ingre-
dients for cleaning purposes. METHYL ESTER AS FEEDSTOCK FOR

Cationicssurfactants having positive charges THE PRODUCTION OF METHYL ESTER
at the end of the molecules; usually used as active ingre-
dients in softening and conditioning products.
SULFONATES (MES)

Nonionicssurfactants lacking a distinct charge One of the most interesting alternative uses of saturat-
but containing water-soluble head groups; usually used ed ME is in the production of the anionic surfactants,
together with anionics to reduce irritancy. called methyl ester sulfonates (MES). MES is one the

Amphotericssurfactants having both positive cheapest surfactants that can be derived from oleo-
and negative charges on the molecule; frequently used chemicals. It is definitely cheaper than fatty alcohol
to enhance the performance of other surfactants. derivatives since it does not have to undergo high-tem-
Besides biodiesel, ME have long been used as the perature and high-pressure hydrogenation. Because of
starting material for the production of fatty alcohol- this, MES has the potential to compete with LAS (linear
based surfactants such as alcohol sulfates (anionics), al- alkyl benzene sulfonates), a very important petrochemi-
cohol ether sulfates (anionics), and alcohol ethoxylates cal-based surfactant that has been used by the cleaning
(nonionics). industry for more than 30 years. However, increase in
However, the desired chain lengths are C1214, and petroleum prices also has resulted in increasing LAS
therefore, the ME are usually lauric oils-based. Methyl prices, making substitutes competitive.
esters can also be used for the production of soap, MES is formed by reacting saturated methyl ester
methyl ester sulfonates (anionics) and esterquats with sulfur trioxide. This reaction is rather complicated,
(cationic).The last two surfactants merit further discus- and it took researchers and equipment manufacturers
sion. more than 20 years to understand the mechanism and

to develop appropriate plants. In 2000, the Malaysian Palm Oil
Board (MPOB) purchased a 20 kg/h sulfonation pilot plant
from Chemithon (Seattle,Washington, USA), a MES technolo-
gy supplier, to produce palm oil-based MES. The pilot plant
was commissioned in late 2001, several metric tons (MT) of
MES were produced, and the quality was evaluated. The pro-
cess to produce palm oil-based MES investigated by MPOB
includes conversion of SO2 to SO3, which is then used to sul-
fonate saturated palm oil-based methyl ester. This is then fol-
lowed with digestion, bleaching, neutralizing, and drying to pro-
duce high-active dried MES.
Dried MES have an active matter content of more than
85% and are of good color. High active matter content is of
great importance since this provides opportunity for the sur-
factant to be exported competitively. Surfactants are used to
formulate finished products such as detergents and shower
preparations. Initially they were available only in solutions, but
the high cost of transportation reduced their competitiveness.
The ability to produce high active MES now makes it possible
to produce surfactants in countries where there is adequate
supply of feedstock, to transport it to various regions in the
world where there are markets for the finished products, and
to be competitive.
Many studies conducted by Lion Corporation, headquar-
tered at Tokyo, Japan; Stepan Chemical Company, based in
Northfield, Illinois, USA; and MPOB revealed that MES offers
an environmentally friendly and viable alternative to the old
workhorse anionicsLAS. MES has the ability to biodegrade
faster and better than LAS. In addition, it has good calcium tol-
erance, thus greater detergency and less sensitivity to water
hardness than other anionic surfactants.
MES can easily be formulated into finished products: a
powder product requires MES to be ground into powder, fol-
lowed by the addition of the rest of the additives. For a liquid
product, MES is dissolved and other additives are mixed in. In
MPOB, the products have been tested against different types
of stains, and in most cases, the products formulated with MES
218 April 2007, Vol. 18 (4)
are either better than or comparable with the best product
available in the Malaysian market.
Palm oil contains about 50:50 saturated and unsaturated
fatty acids. Fatty acid composition reveals that the saturated
fraction comprises mainly C16 and C18, and to a much lesser
extent C12 and C14. During the production of winter biofuel,
the greater the removal of the unsaturated fraction from the
C16 mixture, the better the feedstock will be for the produc-
tion of MES. Besides, many studies have shown that C16 MES
has the best detergency. The solid fraction obtained as co-
product from the palm oil winter biofuel process will there-
fore make an ideal feedstock for the production of MES.
Demand for LAS feedstock has been estimated to be 3.4
million MT (MMT) by 2010. An assumption of 30% substitu-
tion implies demand for 1 MMT of ME for MES production.
With the anticipated development of biodiesel in Malaysia and
Indonesia there will be enough feedstock for the production
of this surfactant.
METHYL ESTER AS FEEDSTOCK
FOR THE PRODUCTION OF ESTERQUATS
Distearyldimethyl ammonium had earlier found application as
an important active ingredient for softening purposes. How-
ever, its unfavorable biodegradation characteristics limited its
commercial usefulness. Today, esterquats are becoming the
surfactant of choice due to their excellent environmental
profile and fabric-softening effect. Moreover, the vegetable-
based esterquats, derived from a renewable source, are gaining
acceptance over the animal-based raw material since animal-
based materials such as tallow are associated with mad cow
disease, as well as being unacceptable to a few religions.
Palm oil-based esterquats can be derived from abundantly
available feedstock, and the saturated hydrocarbon chain in the
raw material provides good softening power especially with
the presence of C18 chain length. Palm oil-based esterquats
were found to have better softening performance than the
commercial tallow-based esterquats owing to the higher satu-
 inform 219
ration of the feedstock.The saturated ME from palm biodiesel
can therefore be a good feedstock for the production of es-
terquats. However, to increase the rewetting power, some un-
saturated hydrocarbon chains must be added.
Esterquats are produced via a two-stage process involv-
ing the preparation of esteramines from triethanolamine and
palm oil-based fatty acid or ester in the first stage and quater-
nization with an alkylating agent in the second stage in order
to introduce the positive charge on the esterquats molecule.
Research at MPOB has revealed that the production of es-
terquats using ME as feedstock requires milder processing
conditions than for surfactant derived from fatty acids.
The major potential market for esterquats is, as men-
tioned previously, in the textile industry, as it has become the
worldwide leading ingredient for fabric softener. Apart from
fabric care, other applications of esterquats include uses as
hair conditioner, as an antistatic agent in polymers, and as an
ingredient in bacterial and sanitizer products.
GLYCERINE AS FEEDSTOCK FOR
THE PRODUCTION OF SURFACTANTS
In the oleochemicals industry, the production of soap, fatty
acids, and ME for fatty alcohol manufacture is accompanied by
the production of glycerine as a by-product. In 1999 the sup-
ply of glycerine due to the manufacture of these products was
approximately 41, 13, and 25% respectively, with biodiesel ac-
counting for only 7%. However, in 2004, the supply of glycer-
ine from biodiesel production increased to 18%.
In 2004, the capacity for the production of glycerine was
about 1.3 MMT while the world consumption was about 0.97
MMT. By 2008, consumption is expected to increase to only
1.1 MMT while the production capacity will increase to 1.6
MMT. Increased supply without a parallel increase in the con-
sumption/demand has led to price decreases. Average glycer-
ine prices have declined from $1003 to $840 per MT during
the 20012004 period.
BIOFUELS
From a technical point of view, glycerines multifunctional
structure makes it an ideal starting material for a very large
number of products.
Currently, glycerine is used in several fields of applications.
When cold, supercooled glycerine can resist freezing and
therefore finds use as anti-freeze. Due to its miscibility with
water and alcohol, it is a good solvent especially for many in-
dustrial applications. It is also widely used as a solvent or drug
carrier in pharmaceutical and medicinal products, as a humec-
tant in cosmetics, toiletries and personal care products, as an
emulsifier in foods, in the making of explosives, and in many
other applications.
Palm oil biodiesel producers have
the option to produce not only
summer biodiesel, winter biodiesel, and
crude glycerine but also vitamins
and saturated methyl esters.
The increased production of glycerine as a co-product of
biodiesel plants has led the EU to finance programs dedicated
to the research and development of new uses for glycerol.
One of the promising projects is the production of 1,2- or 1,3-
propanediol through fermentation of glycerol. These com-
pounds are becoming important raw materials for the manu-
facture of polymers. Polyglycerol was derived previously from
epichlorohydrin or from dehydration of glycerol. Now glyc-
erol is used to produce epichlorohydrin.
Polyglycerol is used to produce polyesters, and these are
used as emulsifiers in cosmetics and pharmaceutical products
as well as in textiles and lubricants. About five years ago there
was only one producer in the world for this material, but
today there are three. Due to limited supply the current de-
mand is approximately 20,000 MT a year. However, the de-
mand will increase when there is further supply.

As mentioned, the commercial production of polyglycerol
involves the use of epichlorohydrin or dehydration of glycerol.
MPOB decided to use dehydration of glycerol to produce
polyglycerol; however, instead of conventional heating, mi-
crowave heating is used. The use of microwave heating helps
to increase the reaction rate, with the advantage of no possi-
ble contamination with chlorine.
METHYL ESTER AS THE ROUTE
TO EXTRACT PRO-VITAMIN A AND
VITAMIN E FROM PALM OIL
CPO is rich in minor components that can impart unique nu-
tritional properties. The most important of these are palm vi-
tamin E (tocopherols/tocotrienols) and carotenoids (especial-
ly alpha- and beta-carotenes). Many research publications have
indicated that palm vitamin E acts as a potent biological an-
tioxidant, protecting against oxidative stress and the athero-
sclerotic process in humans. Tocotrienols, the major compo-
nents in palm vitamin E, exhibit blood cholesterol-lowering
attributes. Studies have also shown that tocotrienols can in-
hibit growth of human cancer cell lines in culture.
CPO is also the richest source of natural carotenoids
with a concentration of about 5001000 mg kg-1, which is
about 15 times that in carrots. The main components are
beta-carotene (55%) and alpha-carotene (35%), with a smaller
220 April 2007, Vol. 18 (4)
amount of lycopene. Research has shown that these natural
carotenoids possess antioxidant and anticancer properties
and serve as precursors of vitamin A.
These vitamins can be recovered from CPO during the
production of biodiesel. The recovery of these valuable vita-
mins offers new opportunities to enhance profitability of the
palm oil-based biodiesel investments.
BEYOND BIODIESEL: BIOREFINERY
The development of biodiesel and expansion in oleochemicals
production capacity are welcome developments in the oil
palm industry. However, while there are benefits to be har-
nessed, the industry stands to lose certain revenue if supply
and demand are not properly balanced. Developing new uses
for the co-products produced by intervention and diversion
will remove the excess supply, therefore maintaining the price.
However, greater importance is attached to removal of the
excess supply through the production of higher value-added
products.
Salmiah Ahmad, Parthiban Siwayanan, Zulina Abd Murad, Haliza
Abd Aziz, and Hoong Seng Soi are all affiliated with the Advanced
Oleochemical Technology Division (AOTD), Malaysian Palm Oil
Board (MPOB).