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The desired products of the reaction are the methyl or ethyl esters of the fatty acids
initially contained in the fat or oil. Glycerine and alkali salts (using alkaline esterification) are
also obtained as by-products, which may be used as raw materials in the chemical industry.
Glycerine may be used in the pharmaceutical industry. The potassium salts are used for
production of potassium fertilizer.
One of the major disadvantages of homogeneous catalysts is that they cannot be reused
or regenerated, because the catalyst is consumed in the reaction and separation of catalyst
from products is difficult and requires more equipment which could result in higher
production costs.
Metal hydroxides, metal complexes, metal oxides such as calcium oxide, magnesium
oxide, zirconium oxide and supported catalysts have been investigated as solid catalysts. The
catalysts are not consumed or dissolved in the reaction and therefore can be easily separated
from the products.
One of the ways to minimize the mass transfer limitation for heterogeneous catalysts in
liquid phase reactions is using catalyst supports. Supports can provide higher surface area
through the existence of pores where metal particles can be anchored. Supports such as:
alumina, silica, zinc oxide and zirconium oxide have been used in biodiesel production.
In the last years research has been focused on use of an enzymatic catalyst for
production of biodiesel. Lipases used in biotechnology are normally of microbial origin and
produced by fermentation processes. The use of lipases makes the reaction less sensitive to
high free fatty acid (FFA) content which is a problem with the standard biodiesel process. A
number of commercial lipases are available for applied biocatalysis. Whilst some are
employed as free powders the majority are used as immobilised preparations.
Normally methanol is used because it is cheap in many countries and also the
esterification reaction is easy to perform. However successful and sustainable production of
biodiesel in the developing countries has to be produced from ethanol. It is less toxic, making
it safer to work with than methanol. Another advantage for ethanol is that it is produced from
biomass (from sugar cane or from corn starch) by fermentation while the methanol used from
production of biodiesel is now often fossil-fuel derived.
The biodiesel will be used as a fuel in stationary or mobile engines for water pumping
(irrigation), grain milling, transportation and electrical generation. Using biodiesel in a
conventional diesel engine substantially reduces emissions of unburned hydrocarbons, carbon
monoxide, sulphates, polycyclic aromatic hydrocarbons, nitrated polycyclic aromatic
hydrocarbons, and particulate matter.
(decreasing the air pollution from transportation and mitigating greenhouse gas emissions)
and socio-economic benefits.
This interdisciplinary project involves agriculture (production of the vegetable oils),
chemistry and chemical technology (production of biodiesel), mechanical engineering (use of
biodiesel in the engine), economical and social aspects referred particularly to the impact on
the population in the countryside and environmental issues.
3. Research plan
The major research tasks, included in the project are:
Literature studies. Months 1-6
Homogeneous two-step esterification procedure includes an acid esterification follow of
an alkali esterification. /months 3-12
Heterogeneous alkali catalyst such as metal oxides (CaO) and zeolites. /months 8-18.
Heterogeneous acid catalyst such as sulphated tin oxide. /months 14-26.
Use of catalyst support such as alumina, silica and zinc oxide. Months 8-26
Separation of glycerine from the ethyl esters. Separation of glycerine from the ethyl esters
is complicated. We are going to study this process in details. The glycerine by-product
contains unused catalyst and soaps that are neutralized with an acid and sent to storage as
crude glycerine. In some cases the salt formed during this phase is recovered for use as
fertilizer.
Removal of the excess of alcohol and the rest of the catalyst. /3-33/
Use of the by-products: glycerine, salts, etc /18-30/
Characterisation of the properties of the produced biodiesel: specific gravity, viscosity,
cloud point, pour point, flash point, heat of combustion, total acid value, presence of
catalyst, and fatty acid composition. /12-30/
4. Research cooperation
The department of Chemical Engineering and Technology has a well established close
cooperation with several Universities in developing countries.
The department has coordinated five training exchange projects, included in ALFA
programme supported by the European Commission, since 1996 in cooperation with
universities in Argentina, Brazil, and Cuba. The department has also coordinated an AsianSwedish Research project. The department is also performing two Linnaeus-Palme student
and teacher exchange project with universities in Latina America, since 2001.
The proposed project involves a close cooperation with ongoing activities at:
Universidad Mayor de San Simn, Cochabamba, Facultad de Ciencia y Tecnologia,
Bolivia. Lucio Alejo Espinoza.
So Paulo State University (UNESP), Campus of the Faculty of Engineering at
Guaratinguet, Brazil, Jose Luz Silveira.
Universidad de Pinar del Ro, Department of Chemistry, Faculty of Forestry and
Agronomy, Cuba. Francisco Marques Montesinos.
The cooperation with the universities of Bolivia, Brazil and Cuba increases the quality
of the research and allows the implementation of the results in the areas of Pantanal and Gran
Chaco in Bolivia, Mato Grosso do Sul in Brazil and Guantanamo in Cuba where projects on
biodiesel production are taking place.
5. Preliminary results
Biodiesel yield 76% was reported from FFA 22.6% in raw Jatropha oil by using the
methanol to oil molar ratio 6:1, NaOH 1%, reaction temperature at 65C and reaction time 60
min. A biodiesel yield of 73% was reported from FFA 8.8% in raw Jatropha oil by using
ethanol to oil molar ratio 8:1, and KOH 1%, reaction temperature at room temperature and
reaction time 5 hours.
Heterogeneous catalysts are promising for the transesterification reaction of vegetable
oils to produce biodiesel. Unlike homogeneous, heterogeneous catalysts are environmentally
benign and could be operated in continuous processes. Moreover they can be reused and
regenerated. However a high molar ratio of alcohol to oil, large amount of catalyst and high
temperature and pressure are required when utilizing heterogeneous catalyst to produce
biodiesel.
Effective factors on catalytic activity of solid catalysts are specific surface area, pore
size, pore volume and active site concentration on the surface of catalyst. Moreover type of
precursor of active materials has significant effect on the catalyst activity of supported
catalysts. The use of catalyst supports such as alumina, silica and zinc oxide could improve
the mass transfer limitation of the three phase reaction.
The biodiesel production through immobilised enzymes presents the following
advantages:
pressure and low temperature (20-40C); No by-products are formed. At the end of the
reaction only esters and glycerol are present. The main problem of the enzyme catalyzed
process is the high cost of enzyme. Although the possibility of recycling the enzyme, which
reduces the incidences of catalyst cost, is an important point to take into account.
Lipase-catalysed production of biodiesel is not yet an optimised process (low
conversion, cost of the biocatalyst, poor kinetics) and several aspects need to be
investigated. The reaction conditions must be studied to obtain higher conversions. Some
important parameters are: type of enzyme, immobilisation process, reaction time,
temperature, enzyme concentration, substrate molar ratio of alcohol to oil, and added water
content on percentage weight conversion.
6. References
A. K. Endalew, Y. Kiros, R. Zanzi, Inorganic heterogeneous catalysts for biodiesel
production from vegetable oils, Biomass and Bioenergy, 35 (2011) 3787.
A. K. Endalew, Y. Kiros, R. Zanzi, Heterogeneous catalysis for biodiesel production
from jatropha curcas oil, Energy, 36 (2011) 2693.
Berchmans, H.J., Hirata, S, Biodiesel production from crude Jatropha curcas L. seed oil
with a high content of free fatty acids, Bioresource Technology 99 (2008) 17161721
Devanesan, M.G., Viruthagiri, T. and Sugumar, N, Transesterification of Jatropha oil
using immobilized Pseudomonas fluorescens, African Journal of Biotechnology 6 (2007), 21,
2497-2501,
Kywe, T.T, Oo M.M., Production of Biodiesel from Jatropha Oil (Jatropha curcas) in
Pilot Plant , Proc. World Academy of Sciences, Engineering, and Technology, 38 (2009) 481487.
Lam M.K. Lee K.T., Mohamed A-R., Sulfated tin oxide as solid superacid catalyst for
transesterification of waste cooking oil: An optimization study, Applied Catalysis B:
Environmental 93 (2009) 134139
Lu, H., Liu, Y, Zhou H., Yang Y., Chen M., Liang, B., Production of biodiesel from
Jatropha curcas L. oil, Computers and Chemical Engineering 33 (2009) 10911096.
de Oliveira, J.S., Leite P.M., de Souza, L.B., Mello V.M., Silva, E.C, Rubim, J.C.,
Meneghetti, S.M.P., Suarez, P.A.Z., Characteristics and composition of Jatropha gossypiifolia
and Jatropha curcas L. oils and application for biodiesel production, Biomass and Bionergy
33 (2009) 449-453.
Patil. P.D., Gude V.G., Deng S., Biodiesel Production from Jatropha Curcas, Waste
Cooking, and Camelina Sativa Oils, Ind. Eng. Chem. Res. 2009, 48, 1085010856
Sahoo, P.K., Das, L.M., Process optimization for biodiesel production from Jatropha,
Karanja and Polanga oils, Fuel 88 (2009) 15881594
Sotolongo, J.A., Beatn, P., Daz, A., Montes de Oca, S., del Valle, Y., Garca Pavn,
S., Zanzi, R., 2007, Jatropha Curcas as a source for the production of biodiesel: a Cuban
Experience, 15th European Biomass Conference and Exhibition Proceedings. Mnchen :
WIP-Munich.
Tamalampudi, S, Talukder M.R., Shinji Hama, S, Numata T., Kondo A., Fukuda, H.,
Enzymatic production of biodiesel from Jatropha oil: A comparative study of immobilizedwhole cell and commercial lipases as a biocatalyst, Biochemical Engineering Journal 39
(2008), 185189.
Om Tapanes, N.C, Gomes Aranda, D.A.,*, de Mesquita Carneiro, J.W, Ceva Antunes,
O.A., Transesterification of Jatropha curcas oil glycerides: Theoretical and experimental
studies of biodiesel reaction, Fuel 87 (2008) 22862295.
Vyas, A.P., Subrahmanyam, N., Patel P.A., Production of biodiesel through
transesterification of Jatropha oil using KNO3/Al2O3 solid catalyst, Fuel 88 (2009) 625628
7. Budget
The costs for the project are summarized below:
Salaries
Travel costs
25 000 SEK
Equipment
30 000 SEK
20 000 SEK
Material
20 000 SEK
TOTAL
The salaries include 12% holiday compensation and 57.45 % increment for social costs.
The cost for Department overhead and KTH Administration is calculated as 35% of the costs.
The travel costs include a travel to Bolivia/Cuba/Brazil for participation in
conference/meetings for presentation of research results: 15 000 SEK for ticket and 10 000
SEK for hotel, food, local travels, etc.