Contents
1. Introduction.........................................................................................................................3
2. Problem statement..........................................................................................................5
2.1. Objectives of the project............................................................................................6
2.2. Specific objectives of the project are:................................................................6
3. Research methodology.................................................................................................7
3.1. Materials..............................................................................................................................7
3.2. Experimental design.....................................................................................................8
3.3. Catalyst preparation.....................................................................................................8
3.4. Transesterification.........................................................................................................8
3.5. Characterization technique and Equipment..................................................10
4. Fuel properties.................................................................................................................10
5. Budget estimate..............................................................................................................12
6. Time frame..........................................................................................................................13
7. Expected output..............................................................................................................13
8. Reference............................................................................................................................14
List of Tables
Table 1: Materials, Chemicals and their Potential Supplier...................................................7
Table 2: Equipment and Uses.........................................................................................................10
Table 3: Fuel properties and ASTM standard............................................................................10
Table 4: Budget estimate.................................................................................................................12
Table 5: Estimated time...................................................................................................................13
List of figures
Figure 1: Experimental procedure to be followed in this research.....................................9
1
ANNEXURE 4
1. Introduction
Recently, there has been depletion of fossil fuels causing instability in the price of
petroleum and also environmental concern due to air pollution caused by vehicles,
therefore biodiesel is receiving increasing attention as an alternative, non-toxic,
biodegradable, renewable diesel fuel produced from fresh or waste vegetable oils
and animal fats (Yisu-Hsu, 2005). Study conducted in Turkey showed that the fossil
fuel production peak has already been reached and indicated that fossil fuel
production for Turkey will diminish in 2038 (Edigeraet al., 2006; Edigera, 2007).
Sources of feed stocks that can be used in biodiesel production are generally
classified into edible and non-edible oils. Edible vegetable oils like canola, soybean
and corn have been used for biodiesel production and found to be good as a diesel
substitute (Freedman et al, 1986). The non-edible oils such as animal fats,
Jatrophacurcas, and waste oils such as soybean soapstock and yellow grease have
been used in the production of biodiesel (Leung, 2006; Wang et al., 2007;
Alcantaraet al., 2000; Mittelbach, 2004).
There are several South African trees that can be used as feed stocks for biodiesel
production these include: marula(Sclerocaryabirrea), Baobab (Adansoniadigitata)
and manketti/mongongo (Ricinodendronrautanenii). These are deciduous trees that
grow naturally in many parts of South Africa, Botswana and Namibia (Leakey,
1999). The edible oil can generally be extracted from their nuts which are nutrious
and rich in proteins and minerals. The oils also contain active anti-oxidants (Vitamin
E) which makes them useful active ingredients in cosmetic products (Peters, 1987).
Since the oils contain anti-oxidants, these oils can be used in small amounts to
improve the oxidation stability of other biodiesel such waste vegetable oil. The
production of biodiesel is performed through transesterification of triglyceride using
alcohol. The products of the reaction are fatty esters and glycerin. Homogenous and
heterogeneous catalysts are main types of catalysts that can be used to produce
biodiesel from feedstock. Homogeneous catalysts act in the same phase as the
reaction mixture, whereas heterogeneous catalysts act in a different phase from the
reaction mixture. Homogenous catalysts can be classified into two main classes’
namely homogenous bases and acids. Strong alkaline catalysts are widely used in
2
the industry for mass biodiesel production (Cananet al., 2009). Potassium
hydroxide, sodium hydroxide, sodium methoxide are the commonly used
homogenous basic catalysts (Surbhiet al., 2011). Sulphuric acid is the most common
homogenous acid catalyst that has been used to esterify excess free fatty acids
(Schuchardtaet al., 1998).
The drawbacks of using homogenous catalysts are that they cannot be recovered,
intolerance of high free fatty acid (FFA) and also require washing of biodiesel with
pure water to remove the catalyst present. This results in wastewater generation,
water contamination and loss of biodiesel as a result of water washing and this
increases cost on municipal water treatment plants. Heterogeneous catalysts can
be classified into two main classes’ namely heterogeneous acid and heterogeneous
base catalysts. Heterogeneous acid catalyst for example, heteropolyacid
impregnated on different supports (silica, zirconia, alumina, and activated carbon),
SO4-ZrO2 and WO3-ZrO2 as solid acid catalyst were indicated as catalysts for the
transesterification of canola oil with methanol to produce biodiesel (Canakci, 1994;
Kulkarniet al., 2006; Laosiripojanaet al., 2010). Unfortunately, these catalysts had
drawbacks including longer reaction time and higher temperatures which make
them unfavourable. Heterogeneous solid base catalyst such as calcium oxide has
some advantages over homogeneous catalyst because the catalyst can be reused
(cost effective), has a tolerance of moisture and free fatty acids (which allows the
use of lower-quality used/waste oils), is inexpensive (obtainable from waste shells),
has low methanol solubility, is non-corrosive and is environmentally friendly.
Fuel properties of biodiesel such as cold filter plugging point (CFPP), cloud point,
pour point and oxidation stability can be improved and modified by blending
biodiesel from different oils. Previous studies shows that the CFPP of palm oil methyl
ester was improved up to 15 °C through blending with canola methyl ester, iodine
value and oxidation stability index of soybean methyl ester was improved to satisfy
European standard EN 14214 specifications through blending with canola and palm
or sunflower methyl esters (Moser, 2008). Transesterification process is affected by
many process variables such as temperature, reaction time, methanol to oil ratio
and the amount of catalyst. These factors can be optimized by statistical method or
3
by a one factor-at-a time method. The surface response methodology is a powerful
statistical method, usually it includes the application of design expert software that
can be used to test multiple process variables because few experimental runs are
needed compared to a one factor-at-a time method (Montgomery, 2001). In
addition, interactions between variables can be identified and quantified.
Although biodiesel has been produced from edible and non-edible oils no study has
been conducted on the production of biodiesel from South African oil producing
trees focusing mainly on marula and baobao. Biodiesel has been produced using
canola, sunflower, palm, jatropha oils but no study has been found on marula and
baobao oils (Gerhard, 1997). There are abundant and cheap minerals in South
Africa this includes: dolomite, limestone, bentonite, kaolin, etc. These materials can
be employed as heterogeneous catalysts and catalyst support in biodiesel
production. However, information about the utilization of these materials in
biodiesel production in South Africa and the rest of the world is scarce. The aim of
this work is to produce biodiesel and evaluate heterogeneous catalysts using South
African oil producing trees (marula, baobao and manketti).
2. Problem statement
South Africa has joined hands together with the Kyoto protocol to reduce usage of
fossil fuels energies as the world is experiencing a huge demand for different
sources of energy and its environmental impact and the search is increasing to
discover the alternative fuels. Among those energy sources, biodiesel has attracted
many countries as a promising alternative fuel which can be used to replace fossil
fuel such as diesel. Biodiesel has been produced for many years mainly focusing on
waste vegetable oil, edible oils (sunflower, canola etc) and non-edible oils (jatropha,
karanjaetc) especially in European countries. The main objective of the project is to
produce biodiesel and evaluate heterogeneous catalysts using South African oil
producing trees (baobao, manketti and marula). Currently no researchers or only
few had produced biodiesel using baobao, marula oil and the effect of blending both
biodiesel using different feedstock’s to improve fuel properties such as oxidation
4
stability, pour and cloud point. This project will focus on producing biodiesel from
these oils and characterize their fuel properties. A major amount of biodiesel
produced in South Africa uses homogeneous catalysts (potassium hydroxide and
sodium hydroxide) as the main catalysts and no study has been conducted
producing biodiesel from marula, baobao and manketti oils focusing on different
types of heterogeneous catalysts which are less expensive, but can produce good
quality biodiesel.
2.1. Objectives of the project
The main aim of the project is biodiesel production and evaluation of heterogeneous
catalysts using South African oils (marula, baobao and manketti).
2.2. Specific objectives of the project are:
a. To transesterify South African oils (manketti, marula and baobao oils) to
biodiesel using homogenous and heterogeneous catalyst.
b. To determine and compare the important fuel properties of biodiesel with
ASTM.
c. To determine and optimize the effect of transesterification process variables
(reaction time, reaction temperature, amount of catalyst and methanol to oil
ratio) on the yield of fatty acid methyl ester using response surface
methodology.
d. To determine and to evaluate a potential heterogeneous catalysts by
heterogenizing a homogeneous catalyst using bentonite, kaolin, dolomite and
limestone.
e. To improve fuel properties of biodiesel by blending different biodiesels
(marula, baobao and manketti biodiesels) and determine the optimum
blending amount.
5
3. Research methodology
3.1. Materials
The following list of materials, chemicals and minerals shown in Table 1, will be
used in the project.
Table 1: Materials, Chemicals and their Potential Supplier
Materials Potential supplier
Baobao oil Eco products
Marula Eco products
Manketti oil Eco products
Waste vegetable oil Royal Sechaba restaurant
Chemicals Grade Supplier
Potassium hydroxide Analytical Merck
Phenolphthalein Analytical Merck
Sodium hydroxide Analytical Merck
Methanol Analytical Merck
Ethanol Analytical Merck
Minerals Grade Supplier
Limestone Industrial grade GW Base Minerals
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Dolomite Industrial grade GW Base Minerals
Bentonite Industrial grade GW Base Minerals
Kaolin Industrial grade GW Base Minerals
3.2. Experimental design
A Central Composite Design (CCD) will be chosen for the experimental design to
investigate the linear, quadratic, cubic and cross-product effects of the four
experimental parameters (temperature, amount of catalyst, time and methanol to
oil ratio) on the yield of fatty acid methyl ester (FAME).The response surface plots
will be analyzed using multiple regression analysis which will be obtained from
Design-Expert (version 6.0.6) software.
3.3. Catalyst preparation
KOH and heterogeneous catalyst will be mixed at different ratios. The ratios
between KOH and heterogeneous will be 1:2, 1:4, 1:6, 1:10, 1:15, and 1:20. The
preparation of catalysts will be conducted in a three-neck round bottom flask
(250mL) equipped with a reflux condenser, temperature indicator, and mechanical
stirrer. The impregnation of heterogeneous with KOH will be conducted at different
temperature and time.
3.4. Transesterification
Titration method will be used to determine free fatty acids (FFA) contents in the
vegetable oils, if FFA<2.5% transesterification will be done and if FFA>2.5%
esterification process will be done using sulphuric acid to reduce FFA contents then
followed by transesterification process (two stage process). Reflux condenser will be
used to condense methanol evaporating during transesterification. Crude mixture of
biodiesel and glycerin (glycerol) will be transferred into a 500 ml decanter to
separate, since glycerin has greater density than biodiesel it will settle at the
bottom and biodiesel will be at the top of decanter. After 8 hrs, crude glycerol will
7
be separated from biodiesel. Biodiesel will be washed to remove amount of
impurities or glycerin in the form of wastewater remaining during separation. Fatty
acid methyl ester (FAME) yield conversion will be determined using gas
chromatography and fuel properties such as cloud point, pour point, oxidation
stability will be measured and compared using ASTM and South African biodiesel
standards. Transesterification experimental procedure is shown in figure 1.
8
Figure 1: Experimental procedure to be followed in this research.
3.5. Characterization technique and Equipment
The following equipment in Table 2 will be used to characterize the biodiesel and
catalysts.
Table 2: Equipment and Uses
Equipment Use
Gas To analyze fatty acids methyl ester
chromatograph
y
XRF and TGA To determine the amount of active species on the prepared
catalysts and used to determine the bulk composition of a
catalyst
FTIR To determine functional groups
SEM To determine surface morphology
BET To determine the surface areas of the catalyst
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4. Fuel properties
Some of the fuel properties which will be measured using biodiesel standard are
listed below (Gerpen, 2002):
Table 3: Fuel properties and ASTM standard
Fuel properties Biodiesel standards
Total and Free glycerol ASTM D6584
Kinetic viscosity ASTM D445
Oxidation stability ASTM D7545
Cetane number ASTM D613
Water and Sediment ASTM D2709
Flash point ASTM D93
Cloud point ASTM 2500
Pour point ASTM 2500
Acid value ASTM D664
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5. Budget estimate
Items Quantity Amoun
t (R)
a Minerals: 1. Limestone 2kg 500
2. Dolomite 2kg 1000
3. Kaolin 1kg 400
4. Bentonite 2kg 500
Chemicals Phenolphthalein, 5000
Methanol, Ethanol,
NaOH, KOH
b Materials: Manketti, Baobao and 5kg each 3000
Manketti oils
c Analysis: ASTM from Bioshixnet 200 samples 30000
d Travels: Road Transport Travels from VUT to 3000
Johannesburg Pretoria and
and Pretoria Johannesburg more than
4 times
e TOTAL 43,400
Table 4: Budget estimate
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6. Time frame
Table 5: Estimated time
Jan- Mar- May- Jul- Sep- Nov- Jan- Mar- May-
Feb Apr Jun Aug Oct Dec Feb Apr Jun
2011 2012
Literature
survey
Project
Proposal
Collection of
Materials
Experimental
work
Characterizati
on of test
materials
This project is estimated to take 1 and half year to completion and the additional
time of 6 months will be added if needed especially for the thesis and the
agreement will be between me and my supervisor.
7. Expected output
1. Fuel properties of Ternary Biodiesel blends of Jatropha-Waste Vegetable Oil-
Marula Using surface response methodology.
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2. Production of biodiesel from Baobab oil using homogenous and
heterogeneous catalyst.
3. Production of biodiesel from Marula oil using KOH-Baggase ash as a
heterogeneous catalyst.
4. Oxidation stability and cloud Point of Ternary Biodiesel blends from Manketti-
Baobab-Marula.
5. Production of biodiesel from Manketti using KOH-expanded diatomite as a
heterogeneous catalyst.
8. Reference
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Catalytic production of biodiesel from soybean oil used frying oil and tallow,
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Canakci, M., & VanGerpen, J.H., 1999. Biodiesel production via acid catalysis.
Transactions of American Society of Agricultural Engineers, 42 (5), 1203–1210.
Canan, K., Candan, H., Akin, B., Osman, A., Sait, E.,& Abdurrahman, S., 2009.
Methylester of peanut (Arachis hypogea L.) seed oil as a potential feedstock for
biodieselproduction. Renewable Energy 34, 1257–1260.
Edigera, V.S.,& Akar, S., 2007. ARIMA forecasting of primary energy demand by fuel
in Turkey. Energy Policy 35, 1701–1708.
Edigera, V.S., Akar, S., & Ugurlu, B., 2006. Forecasting production of fossil fuel
sources in Turkey using a comparative regression and ARIMA [Link] Policy,
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Freedman, B., Butterfield, R., & Pryde, E.H., [Link] kinetics of
soybean [Link] of American Oil Chemists’ Society, 63, 1375–1380.
13
Gerhard, K., Dunn, R.O., & Bagby, O.B., 1997. Biodiesel: The use of vegetable oil
and their derivatives as alternative diesel fuels. Fuels and chemicals from
[Link] Chemical Society Symposium Series, 666.
Gerpen, J.V., Shanks, B., & Pruszko, R. Biodiesel Production Technology. Subcontract
report August 2002–January 2004,Iowa State University, 23.
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biodiesel production by simultaneous esterification and transesterification. Green
Chemistry. 8, 1056–1062.
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[Link] of methyl esters from relevant palm products in near-critical
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Leakey, R.R.B., 1999. Potential for novel food products from agroforestry trees: a
review, Food Chemistry, 66 1-14.
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Mittelbach, M., & Remschmidt, C., 2004. Biodiesel: The comprehensive handbook,
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Montgomery, D.C., [Link] and analysis of experiments. New York: John Wiley
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Moser, B.R., 2008. Influence of Blending Canola, Palm, Soybean, and Sunflower Oil
Methyl Esters on Fuel Properties of Biodiesel, 4301.
Peters,C.R., 1987. Ricinodendronrautanenii (Euphorbiaceae): Zambezian wild food
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Surbhi, S., Ajay, K.A., Rajendra,P.B., Deepak, K.T., 2011. Biodiesel production using
heterogeneous catalysts. Bioresource Technology, 2151-2161.
Schuchardta, U., Serchelia, R., and Rogério, M.V., 1998. Transesterification of
Vegetable Oils: a [Link] of the Brazilian Chemical Society, 199-210.
Wang, Z.M., Lee, J.S., Park, J.Y., Wu, C.Z., Yuan, Z.H., 2007. Novel biodiesel
production technology from soybean soapstock. Korean Journal of Chemical
Engineering, 1027–1030.
Yi-Hsu Ju., & Shaik, R.V., 2005. Rice bran as a potential resource for biodiesel.
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