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PROJECT DESCRIPTION

Production of biodiesel from Jatropha Curcas and Waste Cooking Oils.

1. Background and goal of the project

The objective of this project is to study production of biodiesel, for successful and

sustainable application in developing countries starting from Jatropha Curcas and Waste

Cooking Oils.

Biodiesel is an attractive alternative fuel for diesel engines, that is made from new or

used vegetable oils or animal fats, which are non-toxic, biodegradable, renewable resources.

The biodiesel advantages over conventional fuels are its lower toxicity, high

biodegradability, substantial reduction in SOx emissions, considerable reduction in carbon

monoxide (CO), polyaromatic hydrocarbons, smoke and particulate matters. Biodiesel is also

safe to transport because it has a high ignition temperature

Both Jatropha Curcas and Waste Cooking Oils are promising alternative to edible

vegetable oil. They do not compete with food provision.

Jatropha curcas is a plant of Latin American origin which is now widespread

throughout arid and semiarid tropical regions of the world. It can growwithout irrigation in

arid conditions and it does not require land usage which can be use for food production. It is

not eaten by animals and thus it protects food crops as a living fence, it can provide biannual

yields as a plantation. Jatropha seeds contain about 35% of non-edible oil.

The area under cultivation of Jatropha is expanding several countries such as India,

Brazil, Guatemala, some Africans countries. A project involving Jatropha curcas plantations

within the concept of sustainable rural development, offering an interesting option for

reducing poverty is taking place in the Bolivian Pantanal. El Pantanal, Swampland, is one of

the largest inundated areas in the world. The Bolivian part is located to the east of the Santa

Cruz district. There is another project to develop the Jatropha curcas plantation in the region

Gran Chaco. The Gran Chaco is a sparsely populated, hot and semi-arid lowland region,

divided between eastern Bolivia, Paraguay, northern Argentina and a portion of the Brazilian

state of Mato Grosso. In Guantanamo province, Cuba, research on biodiesel production from

Jatropha Curcas is being performed for direct application in the area. In Brazil cultivation of

Jatropha Curca is taking place in the city of San Carlos (close to Sao Paulo) and in state of

Mato Grosso do Sul aiming the commercial production of biokerosene. TAM, the Brazilian

airlines has been tested in experimental flight biokerosene produced from Jatropha Curca, at a

50% blend with conventional kerosene.

The development of the cultivation of Jatropha as energy source is aiming also:


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To reduce poverty, especially that of women, by stimulating economic activities in rural

areas by using the products of such plants for the manufacture of soap, medicines,

lubricants, chemicals, fertilizers, insecticides. Since the planting, growing and refining of

Jatropha seeds requires manpower, its cultivation will generate large numbers of jobs.

Prevention of water erosion. Improvement of soil fertility.

Improvement of the quality of life in rural areas, encouraging the use of plant oil as a

viable renewable energy option for cooking, lighting and heating.

A reduced consumption of firewood and residues in rural areas.

Expanded options for carbon dioxide abatement.

A reduction of expenditure of imported fuels for rural consumption,

The establishment of decentralized technology chains based on the use of plant oil.

Energy production in rural areas as well as rural mechanisation promoting the use of plant

oil as a fuel in stationary or mobile engines for water pumping (irrigation), grain milling,

transportation and electrical generation.

Waste cooking oil is much less expensive or sometimes available at free of cost. Waste

cooking oil and fats set forth significant disposal problems in many parts of the world. This

environmentally threatening problem could be solved by proper utilization and management

of waste cooking oil as a fuel

To produce biodiesel, fat and oils are chemically reacted with an alcohol such as

methanol or ethanol in presence of a catalyst. Significant amounts of work have been carried

out on homogeneous acid and base catalysis transesterification of vegetable oils. Most of the

biodiesel produced today is obtained with the base catalysed reaction for several reasons: It is

a low temperature and low-pressure reaction. It yields high conversion (98%) with minimal

side reactions and short reaction time. It is a direct conversion to biodiesel with no

intermediate compounds. Biodiesel production from feed stocks with high FFA (free fatty

acids) is extremely difficult using alkaline catalyzed transesterification. The alkaline catalysts

react with FFAs to form soap that prevents the separation of the glycerine and ester.

Sulphuric acid and hydrochloric acid are normally used as acid catalysts especially when the

oil contains high amount of free fatty acids and water.

In the two-step method a pre-esterification operation is applied to eliminate free fatty

acids (FFAs)by reacting the oil with alcohol in the presence of an acid catalyst. The purified

oil was further reacted with alcohol in the presence of an alkali catalyst.

Waste Cooking Oil s and Jatropha oils use to have high concentration of free fatty

acids.


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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 andproduced 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, makingit 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.


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Goal of the project

The objective of this project is to study production of biodiesel, for successful and

sustainable application in developing countries, starting from Jatropha Curcas and waste

cooking oils. Transesterification procedures to be used include the two-step homogenous

esterification procedure (an acid esterification follow of an alkali esterification) as well as

both alkali and acid heterogeneous catalysts. The enzymatic transesterification will be also

studied. The introduction of this technology in the areas of Pantanal and Gran Chaco in

Bolivia, Mato Grosso do Sul in Brazil as well in Guantanamo province in Cuba is aimed.

The biodiesel will be obtained using a laboratory scale reactor at our department.

Important reactions parameters for the transesterification are: ratio of alcohol to

vegetable oil, temperature, rate of agitation and amount of water present in the reaction

mixture, amount of catalysts and excess of alcohol as well as type of the enzyme,

immobilization procedure, pH, use of solvent, enzyme concentration when enzymatic catalyst

is utilized. The effects of these parameters will be studied to find optimum conditions for

transesterification of the selected vegetable oils to ethyl ester that is a major objective of this

project.

In heterogeneous catalyst the influence on catalytic activity of factors such as surface

area, pore size, pore volume and active site concentration on the surface of catalyst is goingto be studied.The use of catalyst supports such as alumina, silica and zinc oxide in order to

improve the mass transfer limitation of the three phase reaction will be included.

Characterization of the produced biodiesel is also an objective of the proposed project.

Both the physical and chemical properties such as specific gravity, viscosity, cloud point,

pour point, flash point, heat of combustion, total acid value, presence of catalyst, and fatty

acid composition as well as other properties related to its use in diesel engines will be

determined. Viscosity levels are a comparative indicator of biodiesel quality.

The suitable utilization of the by-products, glycerine and salts will also be studied in

this project.

The present project is of high relevance for the developing countries where the demand

of transport fuels is already very high and it is continuously increasing. The project promotes

high-quality research in support of a sustainable development of the society. The project

covers subjects of strategic importance to economic and social development. The project aims

at achieving greater energy self-sufficiency and security in addition to environmental


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(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.

2. Relation to other research

Relation to the research at the Department of Chemical Engineering and Technology

The proposed project is related to the research and teaching at the department on

conversion of energy and matter, chemistry and technology of biofuels as well as

environmental technology and catalysis, especially in the Chemical Engineering laboratory

course, in the future named Experimental Process Design.

The present project is also related to the exchange of students, researcher and teachers with

universities in the developing countries involved in the Linnaeus-Palme projects.

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/


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Enzymatic catalyst. Selection of the lipases to be used, immobilisation procedure. Supply

of the materials. Study of the effect of main parameters such as the temperature, the added

water content, type of the enzyme, immobilization procedure, pH, use of solvent, enzyme

concentration, reaction time, substrate molar ratio of ethanol to oil. Characterisation of the

properties of the produced biodiesel.Months 24-34

Preparation of the final report, plans for further research and development. Presentation of

report. Months 30-36

The results will be published in scientific journals and presented at suitable conferences

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 Asian-

Swedish 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


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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: Mild operative conditions; the reaction can be carried out at atmospheric

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,


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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) 481-

487.

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 fromJatropha 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 immobilized-

whole 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 throughtransesterification of Jatropha oil using KNO3/Al2O3solid catalyst, Fuel 88 (2009) 625628

7. Budget

The costs for the project are summarized below:

Salaries 429 900 SEK/year

Travel costs 25 000 SEK

Equipment 30 000 SEK

Computer and analysis 20 000 SEKMaterial 20 000 SEK

Dept. overhead and KTH Administration 183 700 SEK

TOTAL 708 600 SEK

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 000SEK for hotel, food, local travels, etc.

biodiesel zanzi 12

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