catalysts biofuels

A sample of Axens Esterp-H catalyst

Although biodiesel can be produced with traditional catalysts, new designer versions
are allowing higher glycerine yields, faster processing and greater efciency

Breaking away from

potassium hydroxide
by Phil Thane

here are four groups

of catalysts in use or
under development in
the biodiesel industry:
base catalysts such as sodium
(NaOH), potassium hydroxide
(KOH), and sodium methylate
(2CH3ONa); acid catalysts such
as sulphuric acid (H2SO4),
phosphoric acid (H3PO4), and
calcium carbonate (CaCO3); and
solid catalysts and enzymes.
There are also non-catalyst
systems under investigation
such as supercritical and
co-solvent technologies, but
most biodiesel production
uses a base catalyst. These
are usually NaOH or KOH,

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or 2CH3ONa, also known as

methoxide, dissolved in the
alcohol (usually methanol).
NaOH is the norm for small
producers because it is cheap
and readily available. Supplied
as granules or akes that are
reluctant to dissolve in methanol
it presents a handling challenge,
one reason larger plants prefer
sodium methoxide supplied
as a solution in methanol.
KOH is widely used in
commercial biodiesel plants
because it dissolves more
easily than NaOH, and is more
tolerant of free fatty acids (FFA)
in the oil. However it is needed
in higher quantities and is

more expensive. KOH is more

hygroscopic than NaOH and
is best stored in a vacuum.
Both NaOH and KOH
are found in the glycerine
by-product following
transesterication together with
water and soap. It is possible to
separate NaOH and purify the
glycerine but the equipment is
relatively expensive compared
to the price of the resultant
glycerine. Using KOH as a
catalyst and subsequently
neutralising it with sulphuric acid
produces potassium sulphate
as a by-product, which can be
used as an agricultural fertiliser.
Because of its crystalline

structure, it is relatively easy

to isolate from the glycerine.
Dissolving hydroxides in
methanol is exothermic and
on a large scale can result in
the temperature rising above
the boiling point of methanol
creating a re and explosion
hazard. Keeping the mixture cool
and carrying out the operation
under nitrogen to reduce the
re risk adds complexity to the
plant and cost to the operation.
Sodium methylate is one of
a group of chemicals known as
alcoholates or alkoxides. Alkali
metals such as sodium react
with alcohol in much the same
way as a more common metals

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

Base catalysts are true

catalysts in the sense that they
remain unchanged by the target
reaction, but some is lost in
soapmaking side reactions and
the remainder is destroyed when
the glycerine is puried. The
reaction needs a continuous
supply of fresh catalyst, which
is another substantial cost.
Acid catalysts
Acid catalysts are sometimes
preferred to bases as they can
convert FFAs in the feedstock
into usable fuel rather than
soap. However they work
more slowly1 than bases and
require a very large proportion
of alcohol, typically around 40
times the volume of FFA. During
esterication of the FFA water
is produced, and with high
FFA oils the water can stop the
reaction unless it is removed.
Despite the disadvantages
acid catalysis can be
competitive with base catalysis
when used to process cheap
oils high in FFA. There are no
large scale plants exclusively
using homogeneous acid
catalysis but it is sometimes
used as a rst stage in plants
dealing with oils such as waste
oil from food processing.
Once the FFA has been
esteried the oil is neutralised
then passed to a second stage
using base catalysis. It can also
be used as a rectication stage,
dealing with soap produced by
base catalysed processing.
Large doses of powerful
acid, usually sulphuric acid,
are needed (5-25%) so the
plant has to be constructed
from expensive acid-resistant
materials. After processing the
acid remains in the glycerine
which has to be neutralised
and puried before it has any
commercial value. As with
bases a continuous supply
of fresh catalyst is needed.

media. This increases the

contact between the reactants
enabling the reaction to
proceed at a reasonable
rate in an easily managed
environment with no need for
high temperatures or pressures.
But there are drawbacks to
both base and acid catalysts.
A heterogeneous catalyst on
the other hand is one which
is not soluble in any of the
compounds in the reaction. It
remains a solid. Heterogeneous
catalysts are the norm in
chemical engineering, being
solid they can be retained in the
reactor vessel, but the reactions
only involve molecules on the
surface of the catalyst which
is intrinsically less efcient.
To circumvent this difference,
the catalyst should have a
large surface area to volume
ratio. Dividing the catalyst into
ne particles (powder) would
work but this would make it
hard to retain in the reactor.
Solid catalyst manufacturers
usually prefer to adjust the
porosity of the catalyst, so that
it can be produced in various
shapes (spheres, pellets,
etc.), which are large enough
to stay in the reactor but still
offer good surface area.
Another way to compensate
for the intrinsic lower activity
of solid catalysts is to run
the reaction at a higher
temperature, but this increases
utility costs and requires a
pressurised reactor to prevent
the methanol from boiling.
The challenge is to balance
these factors. To nd a catalyst
which works at modest

temperatures and pressures,

does not need huge reactors
or complex methods to retain
it and is not too expensive to
install in the rst place. And it
should not produce soap, or
cause any other side reactions.
French revolution
The Institut Franais du
Ptrole (IFP) based in RueilMalmaison France began
to develop a conventional
homogeneous catalyst
biodiesel process in 1984.
During 1987-89 it ran a pilot
plant to verify its research
ndings and to produce enough
fuel for vehicle testing. The
process known as Esterp, was
lisensed to Diester Industrie
SA, Compigne, France, which
began commercial production
in 1992. The plant initially
produced 20,000 tonnes/
year and was upgraded to
90,000 tonnes/year in 1997.
Diester is now synonymous
with biodiesel in France.
Since 2001, IFPs wholly
owned subsidiary, Axens,
has pushed forward
commercialisation of IFPs
R&D and concluded licensing
contracts with producers.
Axens rst breakthrough was a
solid catalyst transesterication
process known as Esterp-H.
Michel Bloch, biofuels
product line manager in Axens
technology department,
explains that Axens carries out
the basic engineering design
for plants it licences, and works
with engineering contractors
selected by the plant owners.

Solid catalysts
Soluble catalysts such as the
acids and bases above are
referred to as homogeneous
because they dissolve
completely into the reaction

Soya-based FAME and glycerine from an Esterp-H plant

biofuels international

catalysts biofuels

used in a conventional plant

are completely eliminated.
Bloch outlines three
main advantages of the
Esterp process:
First, the purity of the
glycerine is above 98% and
contains no salts. Second,
the yield is higher than with
homogeneous catalysts.
There are no side reactions
producing soap. Best-in-class
conventional plants have yields2
of about 99%, but with EsterpH the yield is above 100%, i.e.
close to theoretical yield. And
nally, the catalyst remains in
the reactor for many years,
keeping the catalyst cost below
4 per tonne of fuel produced.

A schematic diagram of Axens Esterp-H process

Axens inspects the nished

plants constructed by the
contractors to ensure they
meet Axens specication,
supplies the catalyst, and helps
the client to start the plant.
The rst Esterp-H plant in
Ste, France, was licensed
to Diester in 2004 and began
operations in 2006. Diesters
Esterp-H plant now produces
more than 200,000 tonnes/
year of biodiesel starting
from various vegetable oils.
Perstorp BioProducts
in Perstorp, Sweden, has
also selected Esterp-H
biodiesel technology for a
160,000-tonne/year plant in
Stenungsund, Sweden, about
50 km north of Gothenburg.
The plant produces
rapeseed methyl ester and
complies with strict Swedish
biodiesel specications
introduced to cope with the
cold Swedish winters.
A total of eight Esterp-H
plants have been designed
by Axens for projects
around the world.
The largest one (250,000
tonnes/year) is nearing
completion in Kuantan,
Malaysia, for Mission
NewEnergy, formerly known
as Mission Biofuels.
Axens manufactures
the catalyst at its plant at
Salindres, France, from a
combination of metal oxides,
primarily zinc and aluminium,
extruded into pellets.

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The layout of an EsterpH plant is relatively simple:

there are two reactors each
containing an equal amount of
catalyst; the partially processed
liquid is allowed to settle after
passing through the rst reactor
and some glycerine is removed
in order to shift the equilibrium
of the reaction towards
FAME production and ensure
complete transesterication
in the second stage.
The Esterp-H process
carries out transesterication

at a slightly higher temperature

than that used by conventional
processes, in the presence of
an excess of methanol, which is
later removed by vapourisation
and recycled to the reactors.
The two reactors are identical
and use the same catalyst,
reducing design and build
costs. Water is not added to
the process as washing the
fuel is not necessary. The
glycerine needs no further
processing to reach technical
grade, so several stages

Late entrant shows

promise
Illinois-based Benefuel is
a newcomer to the solid
catalyst business of biodiesel
production. Formed by the
merger of New Century
Lubricants and Gripp Biofuels
in 2007, Benefuel combines
Gripps background in biodiesel
production for the US trucking
market and New Centurys
exclusive, worldwide license
from the National Chemical

The Diester Industrie Esterp-H plant at Ste, France

november 2008 55

biofuels catalysts

56 november 2008

Source: Benefuel

Laboratory (NCL) on a novel,

solid catalyst technology
for transesterication.
Like Axens, Benefuels
Ensel catalysts are based on
metal oxides, but they are
chemically quite different.
Its rst catalyst, a dual metal
catalyst (DMC), was discovered
in 2005 and patented by NCL.
It has already been superseded
by another metal oxide catalyst
jointly developed by NCL and
Sd-Chemie India. Details
of this newer catalyst were
not disclosed, other than it
was a derivative of a solid
catalyst from the petroleum
industry. Patents on all
catalysts and processes have
been applied for and some
are expected to be allowed
before the end of 2008.
Benefuels catalysts are
produced in powder or
extruded forms: extrusions
for xed-bed continuous
processing reactors, and
powders for use in batch
processing. Solid catalysts are
used extensively throughout
the petroleum and chemical
industries in hydro treating and
cracking and Benefuel sees itself
building on that experience to
provide the biodiesel industry
with an efcient and continuous
biodiesel production technology.
Both Ensel catalysts are able
to convert lower grade (less
rened) oils than the Axens
process or conventional liquid
catalyst technologies: higher
FFA levels and water have no
impact on Ensel catalysts
capacity for transesterication.
NCL pilot plants using both
classes of Ensel catalysts
have over 4,000 hours of
successful conversion of
various oils like crude palm
oil, yellow grease and chicken
fat with minimal rening into
specication grade biodiesel.
Minimal rening, says
William Summers, CSO for
Benefuel, is not much more
than sieving the chicken
pieces out. Even palm fatty
acid distillate which is 85%
FFAs can be converted
using Benefuels process.
Benefuel has recently
held discussions with

Biodiesel production process using an Ensel catalyst

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.

However, the simpler process

has fewer moving parts than
a conventional operation
and no requirement for postproduction biodiesel polishing
steps. Adding to this there is
less pre-treatment required
and a washing or glycerine
treatment plant is not needed.
The overall capital cost of a
Benefuel facility is estimated to
be lower than a conventional
plant that is capable of
processing high FFA feedstock,
which has many more unit
operations applied to raw
material and product recovery.
Summers adds: In practice
the difference will come down
to three factors, favouring
Ensel: glycerin quality, water
consumption and oil rening
costs. Glycerin from the Ensel
process contains only traces
of water and ranges between
95-97% pure. Conventional
biodiesel produces a glycerin
containing water, residual
methanol and salts from the
destroyed liquid catalyst. This
glycerin is mostly unattractive
to the global glycerin market,
selling in the $0.05-0.10/
lb (0.04-0.08) range.
There is no water in Ensel
glycerin because no process
water is required by the solid
catalyst process. Water is costly
and in some regions so scarce
that not needing water provides
a real competitive advantage
for biodiesel operators, a
signicant contribution to
the bottom line and a benet

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

returned to the start.

At this early stage in
its development Catilin is
understandably coy about the
chemistry of the catalyst, at
least until it has been granted
patents but Larry Lenhart,
CEO of Catilin, explains: Our
solid catalyst has the same
advantages as others in terms
of dealing with a range of
oils containing FFA and in
avoiding water washing, but
is unique in that it doesnt
need high temperatures or
pressures. In fact it can be
used in existing plant designed
for homogeneous catalysts
with very few changes.
There are minimal costs
in modifying a plant and the
payback time could be as
little as 30 days. Our whole
objective is to make sure this
works well within an existing
plant environment. It reduces
operating costs by around
$0.20 per gallon and produces
high quality biodiesel and
high quality glycerine.
Lenhart also points out that
a plant built from scratch to
use the Catilin catalyst would
be cheaper to construct than
other solid catalyst plants,
and cheaper to run since
there is no need to heat the
reactor. The catalyst can be
re-used up to 20 times, which
is substantial cost saving. It is
safe to handle and non-toxic
so disposal of used catalyst
is not a problem, he adds.
Catilin is currently running
a batch production pilot plant
in Ames, Iowa, which will be
modied in the next few months
to a continuous process. The
company is continuing to
research other catalysts too.
The rst version works well
with canola and palm oil, and
has been tested with yellow
grease. In the long term it
expects to develop catalysts
to deal with any feedstocks.
Rival technologies
Several universities and
research institutes are
also currently investigating
solid catalysts:
Toshikuni Yonemoto,

biofuels international

rate of transesterication
substantially, but it cannot
for now at least challenge
conventional base catalysis.
Non-catalytic methods

Benefuels catalysts are produced in powder or extruded forms: extrusions for

xed-bed continuous processing reactors, powders for use in batch processing

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

active sites. Methanol also

has a negative impact on
the stability of the enzyme.
There is a lot of research
into ways of avoiding these
problems, using alternatives
to methanol and different
enzymes that result in different
glycerides but enzymatic
transesterication has not
been demonstrated on
an the industrial scale.
The cost of lipase is
signicant, and large scale
production using methanol,
which inhibits the activity
after only a few cycles, is not
feasible. Use of methyl acetate
or ethyl acetate would allow
lipase to be used repeatedly,
signicantly reducing the
cost of production.
Co-solvent
transesterication
It is well known that
vegetable oil and methanol
are immiscible, hence all the
mixing tanks, high shear and
ultrasonic reactors designed
to bring them together. An
alternative is to use a cosolvent, a compound such as
dimethyl ether (DME) which
will produce a homogeneous
solution. This has been
tested using acid catalysis
and shown to increase the

Catalysts are not the only way

of promoting transesterication
extreme heat and pressure
can also do it. In the lab
conversion rates of more than
95% in only four minutes have
been claimed but the conditions
required, a temperature of
350C and a pressure of
30 Mpa mitigate against
large scale use.
Where are we now?
Around 90% of current
biodiesel is made using
homogeneous catalysts more
than 80% of this quantity
is made with methylates,
the rest with hydroxides.
Of the remaining 10% most
are made with heterogeneous
catalysts and a small fraction
also by enzyme catalysis. The
larger the plant capacity the
more likely the plant will run on
alkoxides like sodium methylate
or potassium methylate.
Things change though and
biofuels is still a fast-moving
industry in its infancy. Axens
has shown that solid catalysts
work on a commercial scale
and this technology looks
particularly attractive for small
plants using local feedstock
and meeting local demand,
which with rising transport
costs is a market that will
grow in importance.
1 Up to 4000 times slower according
to research by Srivastava and Prasad
cited in Synthesis of Biodiesel
via Acid Catalysis Edgar Lotero
et al, Department of Chemical
Engineering, Clemson University,
Clemson, South Carolina, 2005.
2 Mass yield, which can depending
on the molecules involved
(slightly) exceed 100%

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