Documenti di Didattica
Documenti di Professioni
Documenti di Cultura
Although biodiesel can be produced with traditional catalysts, new designer versions
are allowing higher glycerine yields, faster processing and greater efciency
biofuels international
november 2008 53
biofuels catalysts
react with an acid producing
an alkoxide and hydrogen. The
formula for sodium methylate is:
2CH3OH + 2Na2CH3ONa + H2
Sodium methylate is usually
prepared by specialists such
as BASF, Interstate Chemical
and Evonic (formerly Degussa)
and can be supplied either
as a powder or in a methanol
solution usually around 25%
by volume. It is estimated that
70% of US biodiesel production
relies on sodium methylate.
Why use anything else?
Popular as they are, base
catalysts have a couple
of disadvantages: soap
production and contamination
of the glycerine.
Soap consists of salts of fatty
acids, which are produced by
the action of a base on oil aided
or from the point of view of
biodiesel producers exacerbated
by the presence of FFAs
and water in the feedstock.
It is inevitable using a base
catalyst that some of the oil
will be saponied (turned into
soap). Drying and purifying the
feedstock can reduce soap
formation, but even the best
plants will make some usually
about 1% of the feedstock turns
into soap not fuel. Washing
biodiesel to remove soap (and
any remaining catalyst) requires
a lot of water, commonly four
gallons for every gallon of fuel.
Using a homogeneous
catalyst is undeniably efcient
in chemical terms but being
soluble in one alcohol
methanol means it is soluble
in others such as glycerine,
and this is where most of
the catalyst is found after
transesterication, though some
also remains in the biodiesel.
Glycerine is a marketable
by-product of biodiesel
production but as production
levels have risen the price
has fallen, particularly for
glycerine with high levels of
impurities. Once the costs of
neutralising and purifying it
have been factored in there is
not much prot to be had.
54 november 2008
Solid catalysts
Soluble catalysts such as the
acids and bases above are
referred to as homogeneous
because they dissolve
completely into the reaction
biofuels international
catalysts biofuels
biofuels international
november 2008 55
biofuels catalysts
56 november 2008
Source: Benefuel
representatives of other
major biodiesel producers
in the US to compare costs
of operation and capital
expenses for their respective
technologies and discuss
possible future business
developments. Though these
discussions were held under
non-disclosure agreements,
some details have emerged:
1. Based on the assumption
that the Ensel catalyst is
replaced every year then
operating costs of a Benefuel
plant would be very similar
to those of a conventional
homogeneous catalysed
plant. Conventional plants use
more catalyst, because the
liquid catalyst is destroyed in
the process of recovering the
biodiesel. The solid catalyst
remains in place and stays
active for thousands of hours,
perhaps even years. Though
a Benefuel plant would use
slightly more energy for
producing biodiesel, overall
production costs for biodiesel
with an Ensel reactor system
would be lower: lower cost
feedstocks, more efcient
catalysts and overall process
management costs.
2. Capital costs of a basic,
conventional biodiesel reactor
would be about the same.
An Ensel reactor runs at
between 190-240C and at a
correspondingly higher pressure
to prevent the methanol
boiling, which means some
equipment costs are higher.
to the environment.
Feedstock quality is also
very signicant, as some
conventional processors
require feedstock oil that is
higher than food grade. Our
catalysts are able to produce
high quality biofuel from
poor quality feedstock, less
rened oils and fats, including
waste fats and greases from
meat processing, which will
signicantly reduce costs.
Benefuel is currently
designing commercial
biodiesel plants for two
US-based companies, and
several other deals are in
its pipeline. The rst facility
announced is for Seymour
Biofuels of Indiana, where a
10 mgy plant is planned.
Benefuel is also in a
partnership with Diamond Valley
Ventures in Arkansas to provide
the Ensel reactor to complete
its new biodiesel facility.
Different way of thinking
Catilin was only set up as a
company in 2007, based on
the research work of Victor
Lin at Iowa State University.
Lin is an expert in
nanotechnology and unlike
other solid catalysts this
one is not designed to stay
in the reactor. It consists of
unimaginably small beads
which are mixed into the
reactants in a conventional
reactor, and ltered out
afterwards ready to be
biofuels international
catalysts biofuels
biofuels international
rate of transesterication
substantially, but it cannot
for now at least challenge
conventional base catalysis.
Non-catalytic methods
a professor of chemical
engineering at Tokohu
University, Sendai, Japan,
is working on a process
where a mixture of oils and
alcohol is fed to a xedbed reactor packed with a
cation-exchange resin, which
converts the free fatty acids
by esterication. Then the
product is transferred to a
second reactor packed with an
anion-exchange resin which
catalyses the transesterication
of the triglycerides.
In 2006 a team from the
Department of Chemical
Engineering, Tsinghua
University, Beijing published
their research into the use
of Strontium Oxide (SrO) as
a solid catalyst in biodiesel
production. Their work
demonstrated that using SrO
they could convert soyabean
oil to biodiesel achieving 95%
conversion in 30 minutes.
Enzymatic
transesterication
Many teams are working
on enzymatic processes.
These offer much the same
advantages as solid catalysts
they deal with FFA, do not
require water, do not produce
soap and the enzyme can be
reused many times. They also
operate at lower temperatures
than most solid catalysts.
Lipase the preferred
enzyme is isolated from
microorganisms. One major
problem of lipase-catalysed
transesterication is that
glycerol competitively inhibits
lipase activity by blocking the
Useful links:
Axens - www.axens.net
Benefuel - www.benefuel.net
Catilin - www.catilin.com
Diester Industrie (Soproteol) - www.prolea.com (in French)
Michigan State University summary of transesterication methods:
http://ejournal.vudat.msu.edu/index.php/mmg445/article/download/213/285
Sd-Chemie - www.sud-chemie.com
Technip - www.technip.com
november 2008 57