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lower the emissions in the air with the exception of Directive 2003/30/EC or the ‘Biofuel Directive’ was
NOx is, which increases as the ratio of biodiesel adopted in 2003 by the European Parliament in order
increases. Although B100 provides the best emission to promote biofuels for transport issues, and it set
reductions compared with petroleum diesel, lower targets of 2% and 5.75% market share of biofuels by
blends are also environmentally beneficial; for 2005 and 2010 respectively. The European
instance, B20 is able to reduce PM emissions by 10%, Commission, in order to promote the cultivation of
CO by 11%, and unburned HC by 21% (US energy crops, introduced a 45€ per hectare programme
Environmental Protection Agency, 2002; U.S. for farmers in 2003, providing them with the
Department of energy, 2012). motivation to grow the raw materials for biofuels
production. All of the European countries have
adopted the EU Directives, where tax exemptions and
biofuel obligations are the basic principles for the
European countries to implement with the legal
framework objectives (Karagiannidis et al., 2007).
Greece is one of the first EU countries that provided
tax exemptions policy for biofuels. According to the
the Hellenic Republic Ministry of Development in 2006,
Greece’s most popular biomass raw materials for the
FIG 2. AVERAGE EMISSIONS IMPACT OF BIODIESEL FOR industrial sector were waste wood, straw and cotton
HEAVY-DUTY HIGHWAY ENGINES b residues. The total annual consumption was estimated
Moreover, compared to petroleum diesel, using at around 150k tonnes of oil equivalent (toe), whereas
biodiesel in a conventional petroleum diesel engine Greek households used to use a total of 0.7 M toe of
substantially reduces tailpipe emissions of unburned wood annually for heating and cooking purposes.
hydrocarbons (HC), carbon monoxide (CO), sulphates, Table 2 provides a typical summary of Greece’s energy
polycyclic aromatic hydrocarbons, nitrated polycyclic profile.
aromatic hydrocarbons, and particulate matter (PM) TABLE 2 GREECE COUNTRY AND ELECTRICITY PRODUCTION
(US Department of Energy., 2012). PROFILE IN 2012 de
b US Environmental Protection Agency, 2002 d Central Intelligence Agency World Factbook, 2012
c European Biodiesel Board, 2010 e International Energy Agency, 2012
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Qbiodiesel = 7.267 tonnes /hour = 7,267 kg/hour (1) RCOOH + R’OH RCOOR’ + H2O
Using the average biodiesel efficiency of 70 Since base catalysts are much more efficient for
kg/stremma summarised in Table 5 above, it can be transesterification than acids, they are the natural
computed that: choice when no esterification reaction is required to
convert FFA.
Required stremma = 85,714.3 ha/year (2)
Since rapeseed produces double crops per year, the Free fatty acids and water always produce negative
required hectares are divided into 42,857.14 ha or impacts during the process as both of them together
428,571.4 stremma, which is a bit less than the can cause soap formation (increase viscosity,
available 500,000 stermma; it is reasonable to use a difficulties in glycerol separation etc.). There are three
number less than 500,000 stermma to account for any known base catalysts which can be used in the
error in the assumptions. transesterification: Sodium Hydroxide, Potassium
Hydroxide and Sodium Methoxide (also known as
Chemistry of Biodiesel Production Sodium Methylate). Sodium Hydroxide (NaOH) has
Transesterification is the main chemical reaction for much slower dissolution in Methanol compared to
the production of biodiesel. Currently, it is considered Potassium Hydroxide and Sodium Methoxide.
to be the most efficient process because of the low Potassium Hydroxide (KOH) is more expensive than
temperature (65oC) and pressure (20psi) requirements NaOH due to its higher potential yields for biodiesel
for the process, as well as the high and direct with lower waste disposal cost. Sodium Methoxide
conversion rate (98%) of methyl ester (Skarlis et al., (NaOCH3) is more expensive than the hydroxides but
2007). The overall process is made up of a sequence of a lower concentration of NaOCH3 is required to
three consecutive and reversible reactions. During the achieve a good reaction. It is estimated that 70% of US
first reaction, a triglyceride which is the main content biodiesel production relies on Sodium Methoxide
of the vegetable oil and animal fats, reacts with an (Thane., 2008).
alcohol in the presence of a catalyst, producing a An acid catalyst can be used in the pre-treatment stage
mixture of fatty alkyl esters and glycerol. for esterification of FFA and then followed by
CH2-OOC-R1 R1-OOC-R’ CH2-OH transesterification (with base catalyst). There are two
| | | common acid catalysts for esterification: Hydrochloric
CH2-OOC-R2 + 3R’OH R2-OOC-R’ + CH2-OH acid (HCl) which has the ability to access the sugar of
| | | multiple feedstocks with little water use, and
CH2-OOC-R3 R3-OOC-R’ CH2-OH Sulphuric acid (H2SO4) which is much cheaper than
Triglyceride Alcohol Fatty Acid Glycerol
the first one; HCL currently costs around 100€/ton (U.S.
Alkyl Esters
Department of energy, 2012).
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Methanol
Mixer Methanol
recycle
NaOCH3
Methanol
Crude Glycerol recycle
Fatty Glycerol
acids Glycerol
purification
Overall, the process consists of six major components. a continuous centrifuge, FF-101, in order for the
1. The Acid-alcohol esterification pre-treatment glycerol to be removed and sent to the mixing tank, M-
and water/acid removal units: Esterification 101. Methanol, sodium methoxide and unreacted
(complete conversion of FFA) where the molar substances coming from FF-101(stream 7) are the feed
ratio of alcohol to oil is 6:1, catalyst to oil ratio for the second reactor. The mixture of methyl esters,
is 1 wt%, temperature is around 60-70°C, glycerol, unreacted substrates and catalyst coming out
reaction lasts up to 1.5 hours and water and of the bottom of R502 (stream 9) enters a second
acid are to be removed-by washing with continuous centrifuge FF-102. The glycerol-rich
glycerol-before entering the next step. bottom product from FF-102 goes to the glycerol
recovery section, whereas the top product is sent to
2. Base alcohol transesterification units:
the biodiesel refining section in order to be purified
Transesterification (90-98% conversion of TAG)
and dehydrated. The top product of FF-102 is washed
where the molar ratio of alcohol to oil is 6:1,
with water to neutralise the catalyst and convert any
catalyst to oil ratio is 1 wt%, temperature is
soap to free fatty acids. Another centrifuge, FF-103, is
around 45-60°C, reaction lasts up to 1 hour.
then employed to separate the biodiesel from the rest
3. Biodiesel drying unit: for the product to meet of the liquid phase. The bottom output of FF-103 is
the quality standards, crude biodiesel needs to sent to the mixing tank, M-101. The top product,
be washed with water to remove the catalyst which contains mostly water and biodiesel, enters a
and finally purified by distillation and drying. vacuum dryer, VD-101, where water and biodiesel are
4. Catalyst recovery unit: Catalyst has to be separated. The glycerol from the reactors and the
neutralised by acid in this stage. biodiesel wash are gathered in the process tank, V-202,
5. Alcohol recovery unit: Unreacted alcohol is and treated with HCL to convert soaps to free fatty
separated by distillation and then recycled. acids; these are then removed with the centrifuge, FF-
6. Glycerol unit: Glycerol may be recovered at 104.
different grades of purity depending on the This fatty acid is disposed of as sewage for the whole
intended use and the accepted level of costs. industry. The remaining glycerol is neutralisd with
As can be seen from the process flowsheet (Fig. 8), sodium hydroxide (NaOH) and then distilled in
there are two sequential transesterification reactors, R- alcohol recovery distillation, T-101, in order to reduce
501 and R-502. The reactions are both conducted at its water content. Methanol is recovered by another
60oC. The first one is continuously fed with rapeseed alcohol recovery distillation, and T-102, is recycled in
oil, methanol and sodium methoxide. the transesterification process. The fraction of water in
the glycerol process is recycled in the wash operations
The glycerol- rich product from the first reactor enters (Haas et al., 2006).
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A provision of the biodiesel production cost is Steam is required mainly in the reactors and
presented in this section. The costs are broken down distillation columns. It is known from our simulation
into capital costs, which consists of the equipments to that 1.4 GJ steam is needed to produce 1 tonne of
be used in the plant (e.g. biodiesel tank, rapeseed tank, biodiesel. Thus 81,527.6 GJ of steam is required per
methanol tank, centrifugal, mixer etc.), as well as year for the plant. This comes to 403,317.04€ based on
operation costs which are the raw material, catalyst, a unit cost of 4.947€ per GJ of steam. Similarly,
steam, electricity and labour costs. electricity is required in the reactors and centrifugal
vessels. Again, it is known from process simulation
Raw Material and Catalyst Costs that 30 kW electricity is required to produce 1 tonne of
In Europe, over the last decade, the price of rapeseed biodiesel, which gives a total amount of 1,747,020 kW
oil decade has ranged from 0.4 €/kg to 1.1 €/kg per year for electricity needs, which in turn costs
(International Monetary Fund, 2012). Thus for this 142,207.43€ per year, based on 0.0814€ per kW of unit
research, the price of rapeseed oil is set at 0.7 €/kg. electricity cost.
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Thus the new volume is 1.9897 m3. Based on this, the Table 8. Based on the calculation, the real number of
diameter of the vessel is 1.082 m and the height is trays needed for the distillation column is 11, the
2.164 m. However, the diameter and height should distance between the trays is 0.6 m and the height of
comply with the restrictions where 0.305 m ≤ D ≤ 3.05 the column is 6.6 m. The weight of the column comes
m and 1.22 m ≤ H ≤ 30.5 m respectively. The cost of the to 1,374.5 kg. Using the above result, the cost of the
vessel comes to 7,525€. The cost of the installed installed equipment without trays is 85,240€ as of 2012,
equipment is 31,830€, using FBM=4.23, FM=1, FP=1. where FBM=4.23, FM=1, FP=1. The cost of the tray is
15,880€. Thus the final total cost for the distillation
Vaccum Dryer Costs column T-101 is 101,120€. The same principle is
The result of the simulation for the stream applied to calculate T-102 as well.
characteristics of the vacuum dryer is shown in Table 7. TABLE 8 DISTALLATION COLUMN DATA
For the design of the vacuum dryer, which contains
Parameter Value
gas and liquid, the required volume of the retained Steam flow rate (V) 8,324 kg/h
liquid VL will be 1.44 m3, assuming the resident time t Density of gas (ρV) 1.5091 kg/m3
equal to 10 minutes. Then the required diameter, Speed of gas (μV) 1.63 m/s
according to the speed of the gas and since the vessel λ 0.88
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materials, utilities and workforce. (Law 3299/2004). Under the new incentive scheme, the
TABLE 10 TOTAL ANNUAL COST OF RAW MATERIALS,
following incentives are available (Greece Ministry of
UTILITIES, AND WORKFORCE Development, 2012; KPMG, 2011):
Material Required Quantity Annual Cost € • Tax relief: Exemption from payment of income tax
Raw Materials on pre-tax profits.
Rapeseed Oil 58,477.3 ton/year 40,934,073
Methanol 6,571.8 ton/year 1,504,942 • Cash grants provided by the State that cover part of
Base Catalyst (NaOCH3) 584.8 ton/year 3,192,696 the expenses of the investment project.
Acid Catalyst (HCL) 753.2 ton/year 80,221
Water 11,095.4 ton/year 594.7
• Leasing subsidies provided by the State that cover
Total Cost: 45,712,526.7€ part of the payable instalments related to the leasing
Utilities of new equipment. However, the leasing subsidies
Steam 81,500 GJ/y 403,317 do not exceed a seven-year period.
Electricity 1,747,000 kW 142,208 Since there is no income tax on pre-tax profits, no
Total Cost: 545,525€ other costs (e.g. income tax) will be considered in the
Workforce break-even analysis. In this research, it is assumed that
Workers 16 260,000 the break-even periods are three years(i.e. the
Total Cost: 260,000€ biodiesel plant will start to make profit after three
years).
Break-even Analysis
Biodiesel Price vs. Diesel Price in Greece
In order to assess the economic feasibility of investing
in a 60,000 tonnes biodiesel plant, a break-even In order to compare the biodiesel price of the
analysis is conducted. This is a technique used to find proposed plant against the diesel price in Greece, the
cost price of the biodiesel is first calculated. The total
the break-even point (BEP), at which costs or expenses
cost for the first three years of operation is
are equal to revenue. A profit or a loss has not been
142,768,689€, and the proposed biodiesel plant is able
made, although opportunity costs have been “paid”,
to produce 199,728,061.5 litres of biodiesel (1 tonne
and capital has received the risk-adjusted, expected
biodiesel = 1,143.25 litres) during this period. Based on
return (David and Boldrin., 2008). The objective of the
the above results, the cost price for producing the
analysis is to compare the cost price (before taxation)
biodiesel in our proposed plant is 0.715 €/litre.
of the biodiesel produced by the plant against the cost
price of diesel sold in Greece, to see the profitability of Fig. 9 shows the average Greece diesel cost price for
our biodiesel plant in the long run. The cost price of the period of 10 years (01/2002 – 12/2012). (European
the biodiesel is also compared against the WTI crude Comission, Statistics and Market observatory, 2012)
oil price, to see if the crude oil price gives availability The cost price of diesel in Greece is between 0.25€ to
for the investment of the biodiesel technology. 0.93€. Based on Fig. 9, the cost price of diesel has risen
above our proposed biodiesel price (0.715 €/litre) since
Currently in Greece, a number of taxes are imposed on the beginning of 2011. The price of diesel in Greece is
diesel that is to be sold in the market, and they are rising with respect to time. Thus it can be concluded
applied as follows (Greece Ministry of Development, that the use of biodiesel has great potential in Greece,
2012): and the deployment of such a biodiesel plant is
1. 412€ per 1000 litres of diesel fuel. profitable based on the proposed biodiesel cost price
and the incentives given by the government and the
2. Additional 0.5% of tax on the total amount in step 1. states.
3. 0.20 €/m3 of fuel tax on top of the total amount in
step 2.
4. 1.2% of the initial diesel cost (i.e. before step 1).
5. Finally, 23% of VAT is added to the total sum of
steps 3 and 4 before diesel is sold in the Greece
market.
In 2011, Greece passed the Investment Incentives (Law
3908/2011), which replaces the previous incentive Fig 9. UNIT COST PRICE vs. DATE FOR BIODIESEL IN GREECE
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Fig. 10 shows the relationship between Greece diesel analysis of 92.21 $/barrel for crude oil price,
cost price and the WTI crude oil price over the period investment in the biodiesel plant is still profitable in
of 10 years (01/2002 – 12/2012). From the figure, it can the last two years (01/2011 – 12/2012), as the average
be concluded that the price of the diesel in Greece is cost of crude oil is 94.49 $/barrel. However, looking at
linearly proportional to the WTI crude oil price. Using the immediate future, the crude oil price is close to our
the proposed biodiesel cost price of 0.715 €/litre as break-even point. With the incentives given by the
calculated in 5.1, we try to find the break-even point of government and the state, investment in the biodiesel
the crude oil price, which comes to 92.21 $/barrel. plant will still be profitable in Greece.
FIG 10. CORRELATION BETWEEN DIESEL COST PRICE, CRUDE FIG 12. CORRELATION BETWEEN WTI CRUDE OIL PRICE AND
OIL PRICE IN GREECE AND TIME j TIME l
Observatory, 2012; US Energy Information Administration, At the same time, although rapeseed oil is the
2012
k Adapted from: European Comission, Statstic and Market
Observatory, 2012; US Energy Information Administration, lAdapted from: US Energy Information Administration,
2012 2012
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preferred energy crop in Greece, even higher biodiesel Production of Solid and Liquid Biofuels for Greece, 2006.
yields can be achieved if cultivation of different seeds Centre For Renewable Energy Sources. National Report on
such as sunflowers, cotton, etc. can be used. Since
Biodiesel Use in Greece, n.d.
waste cooking oils are generated by households every
day, it will further improve the biodiesel production Centre For Renewable Energy Sources. Promoting Favourable
rate and quantity if these are used as well. Such Conditions to Establish Biodiesel Market Actions, 2007.
investments can be planned by multiple parties, with Christou, Myrsini. “Biodiesel in Greece” no. January (2007).
the government and state as the promoters. EBB Stastics. “The EU Biodiesel Industry,” 2012.
Due to the current economic status of the country, http://www.ebb-eu.org/stats.php.
such an investment may be withheld until the Edition, Fourth. “Biodiesel Handling and Use Guide” no.
situation improves. Government and policy are also
January (2009).
factors which will significantly influence the biodiesel
European Comission. “Statistics & Market Observatory,”
industry, to the extent that such an industry in Greece
will be policy driven. However, an industry project of 2012.
such scale will provide opportunities for improvement European Renewable Energy Council. Renewable Energy
for the nation as a whole. Policy Review, 2004.
The development of such industries requires major European Renewable Energy Council. Renewable Energy
breakthroughs in technologies, successful Policy Review - Greece, 2007.
commercialisation, and the development of Gess, M.A., Danner, R.P., Nagvekar, M. Thermodynamic
infrastructure. On the other hand, its clean emissions
Analysis of Vapor–Liquid Equilibria: Recommended Models
profile and ease of use make biodiesel one of the
and a Standard Data Base. New York: American Institute
fastest growing alternative fuels in the world. With the
subsidies given by the government and the state, the of Chemical Engineers, 1991.
cost of biodiesel is competitive with that of petroleum Greece Ministry of Development. “Daily Statistic on Fuel
diesel in Greece. The future of biodiesel lies in the Prices,” 2012.
world’s ability to produce renewable feedstocks such
Haas, Michael J, Andrew J McAloon, Winnie C Yee, and
as vegetable oils and fats to keep the cost of biodiesel
Thomas a Foglia. “A Process Model to Estimate Biodiesel
competitive with petroleum, without supplanting land
necessary for food production, or destroying natural Production Costs.” Bioresource Technology 97, no. 4
ecosystems in the process. Creating biodiesel in such a (March 2006): 671–8. doi:10.1016/j.biortech.2005.03.039.
manner will allow this clean, renewable, and cost Hellenic Republic Ministry of Development. 2nd National
effective fuel to help ease the world through Report on the Promotion and Use of Biofuels and Other
increasing shortages of petroleum, while providing
Renewable Fuels for Transport in Greece (2005-2010). Athens,
economic and environmental benefits well into the 21st
century. 2006.
Hellenic Republic Ministry of Development. 3rd National
REFERENCES Report on the Promotion and Use of Biofuels and Other
Barahona, F and Jensen, D. “Plant location with minimum Renewable Fuels for Transport in Greece (2005-2010), 2006.
inventory.” Mathematical Programming 83, (1998): 101-111. Hellenic Republic Ministry of Development. 6th National
Bisen, Prakash S, Bhagwan S Sanodiya, Gulab S Thakur, Report on the Promotion and Use of Biofuels and Other
Rakesh K Baghel, and G B K S Prasad. “Biodiesel Renewable Fuels for Transport in Greece (2005-2010), 2010.
Production with Special Emphasis on Lipase-catalyzed Hellenic Statistical Authority. Distribution of Utilized
Transesterification.” Biotechnology Letters 32, no. 8 Agricultural Area by Basic Categories of Land Use and by
Central Intelligence Agency. “The World Factbook,” 2012. International Energy Agency Stastics. Share of Total Primary
Centre for Renewable Energy Sources. Energy Crops for the Prices,” 2012.
90
Advanced Chemical Engineering Research Vol. 2 Iss. 4, December 2013 www.seipub.org/acer
Karagiannidis, A, M Theodoseli, and Z Samaras. “Biofuels US Energy Information Administration. “WTI Crude Oil
Market in Greece and the Potential Role of Captive Spot Price Chart,” 2012.
Fleets” (2007): 1973–1978. Zhang, Y. “Biodiesel Production from Waste Cooking Oil: 1.
Koukous, I. Industrial Design. 1st ed. University of Patra, Process Design and Technological Assessment.”
2008. Bioresource Technology 89, no. 1 (August 2003): 1–16.
Levine, D. and Boldrin, M. Against Intellectual Monopoly. doi:10.1016/S0960-8524(03)00040-3.
New York: Cambridge University Press, 2008.
Mingyen Yu earned his BSc degree in Electrical Engineering
Melkote, S. and Daskin M.S. “Capacitated facility
in 2006 from Purdue University (Indiana, USA). He then
location/network design problems”. European Journal of moved to UK to continue his postgraduate study and
Operation Reaseach 129, (2001): 481-495. obtained his MSc in Information and Business Systems
Engineering from University of Surrey in 2007. In 2008, he
Melo, M.T., S. Nickel, and F. Saldanha-da-Gama. “Facility
started working as an academic staff in Republic
Location and Supply Chain Management – A Review.” Polytechnic, Singapore, specialising in supply chain and
European Journal of Operational Research 196, no. 2 (July logistics, unitil 2010.
2009): 401–412. doi:10.1016/j.ejor.2008.05.007. Mingyen is now a PhD research student at Department of
Reeds Business Information Limited. ISIC Pricing Hydrocloric Chemical Engineering, University of Surrey. His current
research interests include biomass supply chain modeling,
Acid, 2012.
distribution and transportation optimization, as well as
Regnier, Eva. “Oil and Energy Price Volatility.” Energy sustainable systems design in terms of life cycle analysis.
Economics 29, no. 3 (May 2007): 405–427.
doi:10.1016/j.eneco.2005.11.003.
Seyed Ali Hosseini earned his BSc in Chemical Engineering
Rigalos, C., Moiragia, A., Tsoumani, A. and Papadopoulou, in 2005 from Sharif University of Technology (Tehran, Iran).
C. Production of Biodiesel, Greece, 2008. After graduating, he worked as a market analysis for
pharmaceutical products of Akzo Nobel in Iran. He then
Sahin, G and Süral, H. “A review of hierarchical facility
moved to UK to continue his postgraduate studies. In 2007,
location models.” Computer & Operation Research 34, he was awarded his master’s in Advanced Chemical
(2007): 2310-2331. Engineering from the University of Birmingham.
Immediately following, Ali joined the Centre for Process
Skarlis, Str, E Kondili, and J K Kaldellis. “Design and
Systems Engineering (CPSE) at Imperial College London to
Feasibility Analysis of a New Biodiesel Plant in Greece” complete his PhD. He attained a PhD in two years and
(n.d.): 1–11. continued his research at Imperial College London as an
States, United. “Analysis of Biodiesel Impacts on Exhaust associate research fellow. At the same time, he did a master’s
in Finance at the London School of Economics (LSE).
Emissions Draft Technical Report” no. October (2002).
Ali is now a lecturer at Department of Chemical
Thane, Phil. “Breaking Away from Potassium Hydroxide”
Engineering, University of Surrey. His current research
no. november (2008): 53–57. interests cover a variety of topics relevant to mathematical
US Department of Energy. “Biodiesel Benefits and modeling, including design and analysis of energy and
bioenergy systems, supply chain modeling and
Consideration,” 2012.
optimization, design of sustainable systems for water and
US Department of Energy. “Biodiesel Blends,” 2012. resources recovery, and energy finance.
http://www.afdc.energy.gov/fuels/biodiesel_blends.html.
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