Desalination 250 (2010) 10701072

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Desalination
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / d e s a l

A study using classical or membrane separation in the biodiesel process

Nicolae Sdrula
IPROCHIM S.A., Romania

a r t i c l e

i n f o

Available online 29 October 2009

Keywords:
Biodiesel
Membrane reactor
Glycerine purication

a b s t r a c t
Biodiesel is a clean burning biofuel produced from renewable resources (straight vegetable oil, animal oil/
fats, tallow and waste cooking oil), which can be blended at any level with petroleum diesel to create a blend
of biodiesel.
The EU has adopted a series of directives to promote and to represent some of the most important renewable
energy sources out of biofuels also covering biodiesel as well.
The main processing stages currently applied for biodiesel technology are represented by transesterication,
neutralization of mixture, phase separation, biodiesel and glycerine purications. The reaction, generally
occurring in a two-stage mixersettler unit, arises some difculties for clear cut separations.
A new alternative technology, using hydrophobic porous membranes, can be used to prevent bulk mixing of
the two phases and facilitate contact and mass transfer of species between the two phases.
The glycerine side stream (roughly representing 10% of biodiesel) typically contains a mixture of many
components, which are generally difcult to separate. Current methods for glycerine purication are
complicated and conducted with higher costs.
In this case, the new technology provides an economical solution for the purication of crude glycerine
stream combining the high efciency of electro-dialysis and nano-ltration processes.
A comparative cost approach based on available information is sketched. Also, some examples sustain the
aim of the study.
2009 Elsevier B.V. All rights reserved.

1. Generalities
Biodiesel is a clean burning biofuel, produced from renewable
resources. Biodiesel contains no petroleum; however it can be blended
at any level with petroleum diesel to create a biodiesel blend. It can be
used in compression-ignition (diesel) engines with no modications.
Biodiesel is simple to use, biodegradable, non-toxic, carbon neutral and
essentially free of sulphur and aromatics. Biodiesel is an alternative fuel
similar to conventional or fossil diesel. Biodiesel can be produced from
straight vegetable oil, animal oil/fats, tallow and waste cooking oil.
The process used to convert these oils to biodiesel is called transesterication. The largest possible source of suitable oil comes from oil
crops such as rapeseed, palm or soybean. Though oil straight from the
agricultural industry represents the greatest potential source it is not
being produced commercially simply because the raw oil is too expensive. After the cost of converting it to biodiesel has been added on it is
simply too expensive to compete with fossil diesel. Waste vegetable oil
can often be sourced for free or sourced already treated for a small price.
The result is biodiesel produced from waste vegetable oil can compete
with fossil diesel.

Presented at the 12th Aachener Membrane Kolloquium, Aachen, Germany, 29-30

October, 2008.
E-mail address: nicoloae.sdrula@iprochim.ro.
0011-9164/$ see front matter 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.desal.2009.09.110

The EU has adopted a series of directives to promote renewable

energy sources and to encourage energy efciency. The biofuels
directive sets indicative targets for the biofuel share of all transport
fuels at 2% from the 1st of October 2005 and 5.75% by 2010. Member
States have to set their own targets for biofuel substitution. In addition
as it is exempt of mineral taxes biodiesel is cheaper than mineral diesel
so the users of 100% biodiesel are growing rapidly. In such circumstances
any improvement in the biodiesel technology can represent an
advantage for the producers.
2. Background
The transesterication process is the reaction of a triglyceride (fat/oil)
with an alcohol such as methanol and base such as potassium or sodium
hydroxide (forming sodium or potassium methoxide with methanolas
catalyst for the process), resulting in a methyl ester biodiesel stream and a
glycerine side stream to form esters and glycerol. A triglyceride has a
glycerine molecule as its base with three long chain fatty acids attached.
The characteristics of the fat are determined by the nature of the fatty acids
attached to the glycerine. The nature of the fatty acids can in turn affect the
characteristics of the biodiesel.
This reaction is generally effected in a two-stage mixersettler unit.
Transesterication takes place in a mixing section, while the subsequent
settling section allows for separation of methyl esters as the light phase

N. Sdrula / Desalination 250 (2010) 10701072

Fig. 1. Schematic diagram of the biodiesel process.

from glycerine water as the heavy phase. A subsequent countercurrent

washing step for the methyl ester removes minute by-product components and gives a biodiesel ready for use after the nal drying step. The
surplus methanol contained in the glycerine water is removed in a rectication column, which assures for methanol the required quality to be
reused in the process. For further glycerine water purication, additional
steps of chemical treatment, evaporation, distillation and bleaching may
follow optionally.
In Fig. 1, the classical main process phases and raw materials and
products as well are given.
3. Glycerine purication
The glycerine side stream typically contains a mixture of glycerine,
methanol, water, inorganic salts (catalyst residue) free fatty acids,
unreacted mono-, di-, and triglycerides, methyl esters, and a variety of
other matter organic non-glycerol in varying quantities. The methanol
is typically stripped from this stream and reused, leaving behind, after
neutralization, what is known as crude glycerine. Removing all the
contaminating glycerine as well as other water-soluble impurities
such as free fatty acids and salts of free fatty acids is either slow or
expensive and always reduces the overall yield of biodiesel.
In raw form, crude glycerine has high salt and free fatty acid content
and substantial colour (yellow to dark brown). Consequently, crude
glycerine has few direct uses due to the presence of the salts and other
species, and its fuel value is also marginal. The biodiesel industry generates
millions of tons of crude glycerine waste each year, and the amount
produced is growing rapidly along with the dramatic growth of biodiesel
production.
One initial step common to all glycerine purication processes is
that fat, soap and other organic impurities need to be chemically
separated and removed by ltration and/or centrifugation. Final
purication is typically completed using vacuum distillation followed by activated carbon bleaching for large operations or ion
exchange followed by ash drying to remove water for smaller
capacity plants. Vacuum distillation is very expensive in terms of

Fig. 2. Common steps to obtain pure glycerine.

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capital cost and energy consumption and cannot always be carried

out continuously and is accompanied by considerable losses of
glycerol. In order to separate glycerol from higher boiling point
impurities the mixture needs to be additionally subjected to severe
thermal stresses conducting to losses of glycerine due to decomposition. Because of the high salt content, ion exchange is not economically practical, unless it is used to polish a diluted low salt content
glycerol-in-water solution.
As per such technology the schematic diagram can be those
presented in Fig. 2.
A cited technology (EET Corporation) [1] provides economical solution
for the purication of crude glycerine streams in the biodiesel production
industry combining the high efciency electrodialysis and nanoltration
to purify and recover glycerine. EET's High Efciency Electro-Pressure
Membrane (HEEPM) system can be operated in a batch, semi-batch, or
continuous ow arrangement for the desalination of liquids. In all of these
arrangements, the HEEPM integrated approach provides these numerous tangible benets for many applications.
The patents-pending High Efciency Electro-Pressure Membrane
(HEEPM) process takes advantage of the respective differences and
advantages of electrodialysis and nanoltration or reverse osmosis by
combining both processes in a manner optimizing the separation
characteristics of each. Use of the integrated HEEPM approach overcomes inherent limitations of both membrane-based technologies,
allowing these to operate optimally and economically, thereby achieving
improved efciencies, product recovery, and nished product quality.
The specications for this new system are the following:
Available capacities from 2 to 5000 m3/day.
Feed water salinity from 100 to 50,000 ppm.
Product purity to 2 ppm total dissolved solids (TDS).
Feed water temperature to 40 C (104 F) using standard stack
components.
Up to 99+% water recovery. Up to 99.9+% salt removal.
pH 2 to 9 continuous, 1 to 11 for cleaning.

The recovered glycerine, after polishing with ion exchange (if necessary) and water/methanol removal by evaporation, can meet glycerine U.
S. Pharmacopeia (USP) standards.
General scheme for such purication is given in Fig. 3.
4. Membrane biodiesel reactor
Another new alternative technology, generally applied for extracting water-soluble components from organic liquids, can be applied to
biodiesel. In this technology, hydrophobic porous membranes can be
used to prevent bulk mixing of the two phases and facilitate contact
and mass transfer of species between the two phases. One of the novel
reactors [2] is enabled to separate the reaction products (FAMEfatty
acid methyl ester-/glycerol in methanol) from the original vegetable
oil feed. Due to the immiscibility of lipid feedstock and alcohol, lipids
form droplets (dia. = 201800 m) which are excluded from passing
through the membrane pores (dia. = 1.4 m). The micro-porous
inorganic membrane selectively permeates FAAE, alcohol and glycerol
while retaining the emulsied oil droplets.
As a result, no lipids (TG, DG, MG) are found in the permeate stream
which implies that high conversions typically necessary in conventional
biodiesel processes are not required here. The free and total glycerine
contents of the biodiesel easily meet international standards for purity.

Fig. 3. General scheme by HEEPM technology (EET process).

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N. Sdrula / Desalination 250 (2010) 10701072

or articles. One of these articles [4] makes a comprehensive analysis of

production cost of B100 having a plant capacity of 38,000 tons/year. The
resulting production cost was 0.52 USD/kg. The market prices are higher
as per available information [5]. Thus the prices of B100 biodiesel balanced
between 0.7 and 0.9 USD/kg. In order to have an objective comparison of
prices, depending on the applied technology, the following should be
taken into account:
Fig. 4. Schematic view of prototype biodiesel membrane separation plant.

Furthermore, any soaps produced in the reactor are retained and the
permeate readily dephases at room temperature. This enables the recycling of the polar phase from the permeate.
Schematic ow for this technology is given in Fig. 4.
Some other attempts were performed in the area of membranebased technology for biodiesel production. One of them belongs to
WIMCO company [3].
The advantages of WIMCO biodiesel production system:
1. Feedstock for biodiesel production including recycled cooking oil,
pure vegetable oil, animal fat, and some solid oils; production
process is able to handle very high level of free fatty acid content in
the feedstock.
2. Several kinds of membranes have been developed to handle
various types of feedstock. Membrane design calls for very little
amount of chemical to be added into process.
3. Membrane purication making high quality biodiesel, meeting
ASTM-D-6751 and EN-14214.
4. Glycerine as a by-product is puried in a membrane purication
system to meet USP standard.
5. No requirement of chemical additive that causes environmental
concerns.
6. Low operation cost.
As per web information, WIMCO biodiesel production systems incorporate a catalyst membrane. A 10 ton/day system was delivered to REX
Services Inc. A 60 ton/day system has been completed and will go into
production in early October, 2007. The process is similar with reference [2]
but includes glycerine purication, based on membrane system.
5. Comparative costs approach
The prices for pure biodiesel B100, as basis for commercial biodiesel
grades, can be found of many sources, including Bursa, specialized reviews

refer to only one kind of raw material oil and similar capacity plant
determine the processing costs with classical versus membrane
systems for biodiesel main product
establish for each main process (classical or membrane-based) the
glycerine modus of turning in account i.e. by no purication,
classical purication up to 80% purity, purication at USP grade by
classical or membrane technology.
It is known that actual prices of B20 biodiesel (containing 20%
biodiesel as blended diesel fuel) save more than other alternative fuels
(natural gas or methanol) even though still the petroleum diesel is a
little bit cheaper. Deeper comparisons referring to applied technologies
will be developed in the next study, based on cited principles, when
more practical data will be available.

6. Conclusions
The study is an attempt to put on the table the importance of membrane technologies which can rapidly extend, based on economical and
operating advantages, in the domain of biodiesel industry, since the
importance of biodiesel as renewable alternative fuel source became a
rule not only for the EU community. Although the applications are
generally still a few, the market demands will force the producers to
apply this membrane technology which seems to be more suitable for
environmental protection and having reduced production costs.

References
[1] 2007 EET Corp., web information, HEEPMTM Technology.
[2] M.A. Dub, A.Y. Tremblay, J.A. Liu, Novel membrane reactor for the continuous
production of biodiesel, Bioresource Technology 98 (2007) 639647.
[3] WIMCO (World Industrial Membrane)web Information: www.wimco1989.ca.
[4] J.M. Hass, J.A. McAloon, W.C. Yee, T.A. Foglia, A process model to estimate biodiesel
production costs, Bioresource Technology 97 (2006) 671678.
[5] ENDERBiodiesel Market Prospectus, ENDER Management Team, October 2005.