F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 7 40 –7 4 8

w w w. e l s e v i e r. c o m / l o c a t e / f u p r o c

Techno-economic study of different alternatives for

biodiesel production

J.M. Marchetti⁎, V.U. Miguel, A.F. Errazu

Planta Piloto de Ingeniería Química (UNS-CONICET), Camino Carrindanga Km. 7 (8000) Bahía Blanca, Argentina

AR TIC LE I N FO ABS TR ACT

Article history: Biodiesel has become an attractive diesel fuel substitute due to its environmental benefits
Received 29 June 2007 since it can be made from renewable resource. However, the high costs surrounding
Received in revised form biodiesel production remains the main problem in making it competitive in the fuel market
10 January 2008 either as a blend or as a neat fuel. More than 80% of the production cost is associated with
Accepted 20 January 2008 the feedstock itself and consequently, efforts are focused on developing technologies
capable of using lower-cost feedstocks, such as recycled cooking oils and wastes from
Keywords: animal or vegetable oil processing operations.
Biodiesel production The main issue with spent oils is the high level of free fatty acids found in the recycled
Economic analysis materials. The conventional technology employs sodium methoxide as a homogeneous base
catalyst for the transesterification reaction and illustrates the drawbacks in working with
feedstocks that contain high levels of free fatty acids. On the other hand, homogeneous
acidic catalysts are being used for exactly such feedstocks. Both acid and basic homogeneous
catalyzed processes require downstream purification equipment to neutralize the catalyst
and to purify the biodiesel as well as the glycerol.
Recent studies have been conducted to employ heterogeneous catalysts, such acidic or basic
solid resins, or immobilized lipases. These catalysts will allow the use of different feedstocks
that will permit operation at lower investment costs and will require less downstream
process equipment.
A conceptual design of these alternative production plants has been done with a techno-
economic analysis in order to compare these alternatives.
A process simulator was employed to carry out the conceptual design and simulation of
each technology. Using these models it was possible to analyze different scenarios and to
evaluate productivity, raw material consumption, economic competitiveness, and
environmental impacts of each process.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction compared to traditional fuel [1], such as lower toxicity and

almost zero sulphur emissions. Although fuel reserves are
The American Society for Testing and Materials (ASTM) defines decreasing, petroleum continues to be the major fuel worldwide.
biodiesel as monoalkyl esters of long chain fatty acids derived Kulkarni et al. [2] show that Canada consumes ≈23 million tons
from a renewable lipid feedstock, such as vegetable oil or animal of diesel. US consume 178 million tons of diesel annually, and the
fat. Biodiesel is a renewable and sustainable substitute of the world consumption is around 934 million ton/year of diesel.
diesel fuel traditionally obtained from petroleum. The main A lot of research has been done in order to search for other
benefit of this fuel is related to the environmental advantages alternative catalysts, such as homogeneous one (sulfuric acid),

⁎ Corresponding author.
E-mail address: [email protected] ( J.M. Marchetti).

0378-3820/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2008.01.007
 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 7 4 0–7 4 8 741

Nomenclature

Abbreviation Complete name

TG Triglycerides
DG Diglicerides
MG Monoglycerides
FAME Fatty acid methyl ester
M Methanol
G Glycerol
FFA Free fatty acid

heterogeneous catalyst (solid resins) as well as immobilized however not recommendable with oils with an amount of
enzymes [3–17]. However, because refined oils have a relatively FFA N 0.1% [5] however they did provide a good technical
high cost, efforts are focused on developing technologies description of the process. In a recent study, Dorado et al. [25]
capable of using lower-cost feedstocks, such as recycled cooking investigated the economics involved in biodiesel production
oils with high content of free fatty acids [18], varying from 3 to from Ethiopian mustard oilseed. This study shows a good first
40% in most cases and sometimes even higher than that. approach of the economics involved, however, a full descrip-
When oil with high amount of FFA is employed with a basic tion of the process and the cost was not provided.
homogeneous catalyst, the soap making reaction takes place Different economic criteria were used in each of the
simultaneously with the transesterification reaction. This previously described work; Nelson et al. [19] have used the
non-desirable sub product makes the downstream separation total capital cost as economic criteria for feasibility of the
of the biodiesel more difficult. process, while Noordam and Whiter [20] employed the total
Besides technical aspects, economics feasibility is also of biodiesel cost. As opposed to the other studies, Bender [22]
great importance to access process viability. A great number of used the capital equipment cost as a criterion for feasibility. A
researchers have been working within this topic: more complete criterion was employed by Zhang et al. [23];
Nelson et al. [19] have made an economic study of a plant that they employed fixed capital cost and total manufacturing cost.
could produce 100,000 ton/year of biodiesel with beef tallow and The previous works show that a large percentage of the
methanol in the presence of alkali catalyst as possible process operating costs are associated with the raw material, which is
scenario. Noordman and Whiter [20] have done similar work a key component when the economic viability of the process is
using Canola seed as raw material and their plant was of 7800 ton/ evaluated. Therefore, for our studies, we chose to employ an
year. Although both supply estimated equipment costs and give acid oil, defined as an oil with high level of FFA (5% of FFA in
some credit for the product, there is no detailed description of the our work) as feedstock.
process involved in relation to the equipment size. We present a conceptual design of processing plants for
The economics involved in a process to produce 38.8 three different technologies using different catalysts for
million liter/year of biodiesel was evaluated in Graboski and biodiesel production with a technical as well as an economic
McCormick [21]. In that study the credits from glycerol and analysis for each scenario. The main differences between each
biodiesel was taken into accounts as well as the cost of the process, the advantages and disadvantages of each of
associated with the feedstock, cost for equipment purchase, them are presented. The economic criterion used to estimate
and also costs associated with auxiliary services and main- which alternative was more economically sound was the net
tenance. Although the cost involved is much more detailed present value (NVP). However, fixed capital cost, operating
than the previous study [20], no description of the process and cost, depreciation, and auxiliary cost were also taken into
or the equipment was provided. account for the economic calculations. This work was based on
Bender [22] has done a more detailed research on different the production of biodiesel in Argentina with the aim of
alternatives to estimate the economics of a biodiesel plant supplying an alternative biofuel for this country.
with a better break down of each equipment cost involved and
with credits given also to glycerol produced. Several feedstocks
and different operational scale as well as continuous and batch 2. Reaction models
process scenarios were considered. Nevertheless, the produc-
tion plant in that work was integrated with the oil processing The main reaction that takes place during the process is the
plants, wherefore other expenses and costs needs to be taken transesterification reaction of TG to produce FAME. The overall
into account besides the biodiesel production plant. reaction is composed of three series of reactions that take place
Zhang et al. [10,23] proposed a technical and economic study sequentially one after the other. Simultaneously with these
on acid catalyzed process using waste cooking oil. The process reactions, direct esterification of FFA to FAME, saponification
description as well as the economical analyses was more of FFA and alcoholysis of TG might also take place depending
complete and additional costs were considered in that study. on the quality of the oil and the catalyst employed.
A very complete economic study for biodiesel production All reactions are shown on Fig. 1.
using alkali catalyst was evaluated for a complete whole plant The kinetics involved in each process step was obtained
using a commercial software [24]. The use of this catalyst is from literature. Methanol was used as alcohol; sodium
742 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 7 40 –7 4 8

Fig. 1 – Reactions involved in the biodiesel production.

hydroxide was used as alkaline catalyst and sulfuric acid was used as catalyst [3] to carry out the acid esterification of
constituted the acid catalyst evaluated. Because the reactions the free fatty acids. After the reaction, the product stream was
are equilibrium reactions, an excess amount of alcohol was passed through a decanter to separate the oil phase from the
used to improve the conversion to biodiesel [4,26,27]. water phase; water was subsequently mixed with other
streams to be fed to a neutralizer reactor.
In a parallel process, the oil phase was fed to the first
3. Study cases transesterification stage, where an alcoxy stream was also
provided. The alcoxy was made in a methoxide preparation
Three different processes were studied: 1) homogeneous reactor and distributed to both transesterification stages (Fig. 2).
alkaline catalyst with acid preesterification, 2) homogeneous After the transesterification reactor, the product was passed
acid catalyst and 3) heterogeneous solid catalyst. All the through a decanter to separate the glycerol phase and to purify
technologies were proposed as a continuous process in order the oil phase. The second transesterification stage was placed
to meet an industrial design scale of oil processing. after the separation, where the desired conversion was
The raw material for biodiesel production was a spent oil achieved. As in the first reaction stage, a decanter was added
with 5% of free fatty acid. In soapstocks, for example, the after the second transesterification reactor in order to purify the
amount of FFA can be as high as 30% of the feed stream [28]. product stream and to separate both phases. The oil phase was
washed with water to remove the small amounts of undesirable
3.1. Case I compounds and was fed to a decanter to separate the FAME
phase from the remaining products. The FAME was fed into a
For this case the alkaline process with acid preesterification of distillation column to remove any remaining water. From the
FFA was studied. A process flow diagram can be seen on Fig. 2. top of the distillation column water was removed with a small
The oil with high contents of free fatty acids, as well as the amount of methanol, and from the bottom, high purity (N99.5%)
methanol, was fed to a preliminary step where sulfuric acid FAME was obtained.

Fig. 2 – Case I process flow diagram: homogeneous process with preesterification.

 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 7 4 0–7 4 8 743

Fig. 3 – Case II process flow diagram: homogeneous acid catalyst process.

Both glycerol phases from the decanters after the transester- phase. The oil phase was washed with water to remove small
ification steps were fed into a neutralizer reactor with the water amount of undesired compounds. The separation of water and
stream for the preesterification reactor as well as with the FAME was done in a decanter and the excess alcohol was
washing water used to purify the biodiesel. To this equipment a removed from the FAME with a water stream. After this
liquid stream of acid was added in order to neutralize the separation step, the FAME stream was further purified from
remaining base catalyst from the process. The outgoing stream water by passing the stream through a distillation column.
was passed through a decanter to separate the raw oil phase The three bottom streams from the decanters were fed to a
from the rest for recycling. The product from the decanter was neutralizer reactor. A sodium hydroxide stream was fed to the
fed into a distillation column where methanol was obtained neutralizer in order to neutralize the remaining acid catalyst
from the top and was recycled. The bottom effluent passed from the process. The outgoing stream was passed through
through another distillation column to separate the water from another decanter to separate the raw oil phase from the rest for
the glycerol. The glycerol was approximately 77% pure, which recycling. The bottom effluent of the decanter was fed to a
will affect its selling price. distillation column where methanol was removed from the top
of the column and recycled in the process. The bottom effluents
3.2. Case II were passed through distillation column to separate the water
from the glycerol. This glycerol was approx. 80% pure.
In this case an acid catalyzed process was studied. The flow
diagram of the process is shown in Fig. 3. 3.3. Case III
In this process the acid catalyst (sulfuric acid) and the
alcohol (methanol) were premixed in a “catalysts preparation In the third case, a heterogeneous process scenario using solid
reactor” to be used in both transesterification stages later on. resins as catalyst was simulated. A flow sheet of this process is
The oil and the catalyst mix were fed to the first transester- shown in Fig. 4.
ification stage simultaneously. After the reaction, the product In this process the oil was fed into the first transesterification
stream was passed through a decanter to separate the glycerol reactor simultaneously with methanol. This reactor was a
phase, which was later fed to a neutralizer reactor, from the oil packed bed reactor; therefore, the catalyst was already inside.
phase which was fed to the second transesterification stage. The reaction was carried out at a higher temperature (150–
After the second reactor, the product stream was passed 230 °C) than the other technologies and in consequence, at
through a decanter to separate the oils from the glycerol higher pressure. Therefore, a distillation column was necessary

Fig. 4 – Case III process flow diagram: heterogeneous solid catalyst process.
744 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 7 40 –7 4 8

at the end of each reaction stage to separate the methanol from Table 2 – Equipment cost
the product. The incoming stream to this distillation column Equipment Case I Case II Case III
(Rec. Meth. 1) was methanol which was recycled to the process
Pre-mixer of the catalyst $50,000 150,000 N/A
to reduce the overall cost of alcohol used in the process.
Preesterification reactor $349,000 N/A N/A
After the first reaction step and the first distillation column,
1st transesterification reactor $350,000 $480,000 $410,000
the product stream without alcohol was passed through a 2nd transesterification rector $350,000 $480,000 $390,000
decanter for separation of the oil from the glycerol. The oil Neutralizer reactor $13,500 $35,000 N/A
phase was fed into the second transesterification stage. After Sum of all decanters used $116,000 $97,500 $50,000
this reactor, another distillation column was used to separate in the process
the methanol from the product. Finally, a decanter was used to Distillation column to $60,000 $62,000 $56,000
purifier biodiesel
separate the oil phase from the remains. As well as in the first
Distillation column to separate $40,000 $47,500 $78,500
transesterification stage, the methanol obtained from the top the methanol
of the distillation column was recycled to the process. Distillation column to separate $77,500 $82,000 $30,000
The oil stream leaving the final decanter was fed to a the glycerol
distillation column to purify the biodiesel from other impu-
rities. The biodiesel produced will exit from the bottom of the
equipment. 4.1. Main process results
All glycerol phases that were obtained from the decanters
were passed through a distillation column to separate the The entire study was done for a productive plant of
remaining alcohol from the glycerol. The purity of the glycerol 36,036 metric tons/year; for this, process simulation software
was above market requirements, making it a much higher (SuperPro Designer) was employed; it was an Academic Site
valued byproduct. License, provided by Intelligen Inc.
In all this cases storage tanks were not considered. It was In cases I and II the reaction temperature was set at 60 °C.
assumed that the fuel was to be sold immediately as it is When resins were used, the reaction temperature was increased
produced; however, if this assumption is not valid, then the to 150 °C to be able to achieve the desired final conversion of
effect of the price of the storage tanks will affect all process triglycerides into biodiesel in a competitive reaction time.
scenarios equally and therefore, it will not interfere when The amount of alcohol added in each case varied from one
comparing the process scenarios in relation to each other. technology to the other in order to select a molar ratio in
The amount of waste process generated in Cases I and II agreement with an industrial scale process, which might
was relatively low since part of the process water was recycled. however, be different from those proposed for lab scale reactions
Nevertheless, a minor waste effluent was generated after the [3,4,28]. In all cases the molar ratio of alcohol to TG ratio should
neutralizing step would need proper disposal. The cost of this be over 3:1; this is considered to be the stechiometric required.
waste stream treatment was not taken into account. In case III, For cases I and III it has been used 20% w/w of alcohol.
the spent solid resin can be regenerated and reused in the The amount of catalyst added varied from Case I to Case III.
process. In Case I both catalysts, sulfuric acid for the preesterification
as well as sodium hydroxide were taken into account. Case II
used a lower amount of catalyst since it does not require a
4. Results and discussion preesterification step.
Table 1 shows some of the results obtained from each
These models allowed the study of different process scenarios technology. All of them proved to be suitable possibilities for
using a raw material containing 5% of FFA. In the following biodiesel production. In the out coming biodiesel stream the
sections, the results of the simulation process technology are FAME is over 98% of the stream concentration (w/w). For the
revised and a comparative analysis between them is performed. processes described above, all cases except Case II, satisfied
the total free glycerol in the biodiesel. In Case II the amount of
Table 1 – Main technical aspects of each case free glycerol was higher than the maximum value allowed
Case I Case II Case III when satisfying the international standard ASTM. This could
be improved either by adding equipment to purify this stream
Operation temperature of reactors (°C) 60 60 150
further or modifying some of the process variable such as
Feed streams (kg/h) residence time in the reactor.
Oil 4550 4550 4550 For each metric ton of oil the worst case scenario would
% Of free fatty acids 5% 5% 5% produce 0.9881 metric tons of biodiesel (Table 1), while having
Alcohol (methanol) 750 1500 760 a good global performance. All process scenarios have a final
Catalyst (kg/h)⁎ — (metric ton)+ 84⁎ 42⁎ 12.13+
conversion of triglycerides to biodiesel over 98%.
Washing water 420 420 –

Out coming streams (kg/h) 4.2. Economic assumptions and results

Biodiesel (N 98%) 4497 4496 4568
Total glycerol in biodiesel 0.20% 0.53% 0.17% The costs of raw material, equipment, utilities, selling price of
Performance (metrics ton 0.9884 0.9881 1.0040 the biodiesel as well as glycerol, etc., were estimated based on
biodiesel/metric ton raw material) international prices and specific references [18,29,30]. Other
Glycerol (in solution) 625 540 434
operating cost, such as utilities (cooling water, electricity or
 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 7 4 0–7 4 8 745

Table 3 – Other cost associated with each equipment Table 5 – Operating cost
involved
Case I Case II Case III
Other costs Percent (%) of the
Total operating cost $18,109,000 $18,359,000 $18,896,000
purchase cost
Raw materials $16,044,000 $16,564,000 $15,919,000
Piping 35 Equipment dependant $1,130,000 $1,005,000 $684,000
Instrumentation 40 Labor dependant $547,000 $365,000 $365,000
Insulation 3 Utilities $305,000 $357,000 $1,874,000
Electrical facilities 10 Laboratory $83,000 $68,000 $54,000
Building 45 Insurance $55,984 $53,237 $33,340
Yard improvement 15 Factory expenses $279,920 $266,184 $166,700
Auxiliary facilities 40 Fringe benefits $95,040 $79,200 $63,360
Unlisted equipment installation 50 Supervision $47,520 $39,600 $31,680
Operating supplies $23,760 $19,800 $15,840
Administration $142,560 $118,800 $95,040
labor salary) were estimated according to the market and
prices in Argentina.
The total cost of equipment did not include utilities and
effluents treatment. Some of these costs are considered sepa- of the equipment in the lifetime of the project. The processing
rately from the cost price as described below. In the case of plant was assumed to operate in 100% of its capacity all the
heterogeneous process scenarios, the cost of the catalyst was time. The operation capacity has not been lower during the life
also included in the price of each reactor. time of the project since it was incorporated on the construc-
Low cost oils with high FFA content were employed as raw tion and start up of the plant that it was required 4 months to
material in the present analysis. The cost spent for the waste achieve a full operational capacity. The finance of the project
oils vary from 110 US$/metric ton [18] to 220 US$ per metric ton is considered to be from private investment and no loans have
[23]. In our case the price was estimated 400 US$ per metric ton been taken into account.
according to the internal Argentinean oil market [31]. The buying prices as well as the selling prices of the
products have no variations over time; this assumption has to
4.2.1. Fixed capital cost be removed in a second step but for a first conceptual design
In Table 2 all the purchase cost of the equipment employed for and comparison of the processing alternatives is suitable.
each technology is shown. In Table 6 the most relevant economic indicators as well as
Other costs associated with the equipment have also been a summary of the previous cost already shown are summar-
taken into account following the percentages described in ized. All the process scenarios have almost similar revenues
Table 3. The total fix cost for each process scenario is due to the biodiesel that is sold (Table 6); however, the
summarized in Table 4. heterogeneous alternatives has a much better selling price of
the glycerol due to its purity, making it a higher valued
4.2.2. Operating cost byproduct.
A break down of the operating cost involved in each process is
shown in Table 5. In addition, other costs associated with the
operation of each technology have also been included.
In Tables 5 and 6 the raw material cost was only associated Table 6 – Economic indicators
to the oil used while the total operating cost included the costs Case I Case II Case III
of the remaining the raw materials used in the process
Plant capacity 36,036 36,036 36,036
(alcohol, catalyst, etc). (metric ton/year)
Biodiesel revenues $16,029,000 $16,023,000 $16,281,000
4.2.3. Economic indicators (US$/year)
To compute the economics of each scenario some assump- Credits for glycerol $2,660,000 $2,548,000 $3,573,000
tions have been made. The life time of the project was (US$/year)
Total income (US$/year) $18,689,000 $18,571,000 $19,854,000
established in 15 years with one year for construction and
Equipment cost (US$) $1,503,000 $1,477,000 $1,010,000
start up of the plant, it was assumed a constant depreciation Total investment (US$) $7,415,000 $7,327,000 $5,151,000
Raw material cost $14,414,000 $14,414,000 $14,414,000
(US$/year)
% of the total 79.60% 78.51% 76.28%
operating cost
Table 4 – Summary of the fixed costs involved for each Total operating costs $18,109,000 $18,359,000 $18,896,000
process (US$/year)
Biodiesel unitary cost $0.5084 $0.5156 $0.5223
Case I Case II Case III
(US$/kg)
Total capital investment $7,415,000 $7,327,000 $5,151,000 Gross margin 5.50% 4.16% 7.74%
Equipment purchase cost $1,506,000 $1,434,000 $1,014,500 Return over investment 19.68% 16.69% 33.23%
Direct fixed capital (DFC) $5,598,000 $5,323,000 $3,333,000 (ROI)
Working capital $1,536,000 $1,677,000 $1,655,000 Net present value (7%) $1,797,000 $(1,275,000) $7,789,243
Start up and validation cost $280,000 $266,000 $163,000 Internal return rate (IRR) 11.17% 6.95% 31.95%
746 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 7 40 –7 4 8

Table 6 shows only the purchase cost of equipment. From

the total investment row, the heterogeneous process scenario
has the lowest capital investment cost due to the less amount
of equipment involved in the process.
The total operating costs are quite similar for all this
technologies; approximately 18.5 million US$. The operating
cost associated to the cost of the oil employed constituted 76–80%
of the total operating costs, similar results have been obtained by
Zhang et al. [23], Zhang [30] for biodiesel plants using sulfuric acid
and virgin and waste canola oils and by Haas et al. [24] for a crude
degummed oil with a homogeneous basic catalyst.
From the economical indicators, the heterogeneous alter-
natives (case III) appear to be more profitable and have the
highest NPV value with an interest of 7% compared to the
other process alternatives. The NVP is a financial measure-
ment of the value of money as a function of time while the IRR Fig. 6 – Variations on the NVP due to changes on the buying
is an indicator of the efficiency of a project. price of the raw oil (■) Case I (●) Case III.
As it can be seen from Table 6, the unitary cost of biodiesel
is around 0.51 US$/kilo or 0.57 US$/liter which is in good
agreement with the previous result showed by Haas [18] for a variations of the NVP for each technology have been plotted
crude degummed oil. on Fig. 5. It has to be noticed that these results show only the
The selling price in USA is around 2.7 US$ per gallon and variation of the NVP due to changes in the selling price of the
Europe is buying the biodiesel at around 0.8 Euro/liter. biodiesel, the remaining variables and assumptions have been
However, the selling price of biodiesel used in this work was maintained constant.
0.45 US$/liter; this assumption was based on the Argentinean Fig. 5 shows the variations of the NVP as a function of the
market because process designs were made to satisfy the selling price of the biodiesel produced. For both case scenarios
Argentinean biofuel requirements. as the price goes up the NVP increase as a linear functionality,
this is due to the fact that only the biodiesel price has been
4.3. Sensitivity study modified and its effect studied. The dotted line showed in
Fig. 5 shows only the tendency and allows to have an idea of
A sensitivity study will permit to add some uncertainty on the minimum selling price required to have a positive NVP.
those variables that could suffer changes due to the interna- This value is different for each technology, being around 0.42
tional situation of the market; those are the biodiesel selling US$/liter for the heterogeneous case and 0.445 for the
price and the price of the raw oil. This last one is associated homogeneous technology with preesterification.
with the quality of it, decreasing while the amount of FFA The second variable that has a big influence over the
increases. These studies have been performed for Case I and economics of a biodiesel plant is the price of the raw oil,
Case III which are those that have a positive NVP. normally associated to the purity of it. The buying price used
Variations on the biodiesel selling price have been done in on this work for the raw oil was 400 US$/metric tons, higher
order to have an idea of how changes on the international amount of FFA such as 10% and 20% of FFA will provide a lower
market might affect the economics of a biodiesel plant. buying cost. This sensitivity study has been performed from
Variations have been done from 0.48 to 0.405 US$/liter. The 425 to 350 US$/metric tons, equivalent to higher and lower
amounts of FFA in the feed stream.
Fig. 6 shows the variation of the NVP both case I as well as
case III. It has to be considered that the NVP value is due only
to changes on the price of the raw oil. If the amount of FFA
increases in high amounts the process as it is might not be the
best alternative and modification to it might be required. One
regular inconvenience is water formation because of the
esterification reaction that could lead to some deactivation
of the heterogeneous catalyst. Assuming that the technologi-
cal alternatives do not require any modifications and they can
be used as they are for any possible amount of FFA below 30%,
Fig. 6 shows that when the amount of FFA increase, which
make a cheaper oil, the NVP value increases as well.

5. Conclusions

Fig. 5 – Variations on the NVP due to changes on the biodiesel From the conceptual design of the three technologies con-
selling price. (■) Case I (●) Case III. verting spent oils with relative high amount of FFA, it is
 F U E L P R O CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8 ) 7 4 0–7 4 8 747

concluded that all process technology are suitable for biodiesel [6] U. Schuchardt, R. Sercheli, R.M. Vargas, Transesterification of
production and Case I and Case III with positive NVP values. vegetable oils: a review, JBCS 9 (1) (1998) 199–210.
[7] J.M. Marchetti, V.U. Miguel, A.F. Errazu, Homogeneous
The process scenario with the lowest cost per kilo of
catalyst for the esterification of high free fatty acid content's
product was Case I. However, the heterogeneous alternative
oils, 13° Congresso Brasileiro de Catálise3° Congresso de
appears as the possible future technologies for biodiesel Catálise do Mercosul, Foz do Iguaçu, Brazil, 2005.
production, not only because of lower amounts of effluent, a [8] M. Canakci, J. Van Gerpen, Biodiesel production from oils and
more environmental-friendly process, but also because the fats with high free fatty acids, Trans. ASAE 44 (6) (2001)
secondary product produced, glycerol, has a higher purity, 1429–1436.
allowing it to be sold on at more competitive price. [9] M.J. Haas, P.J. Michalski, T. Runyon, A. Nunez, K.M. Scott,
Production of FAME from acid oil, a by-product of vegetable
To process 36,036 metric ton/year of acid oils, a similar in-
oils refining, JAOCS 80 (1) (2003) 97–102.
vestment is required both homogeneous technologies. This is [10] Y. Zhang, M.A. Dubé, D.D. McLean, M. Kates, Biodiesel
higher than the investment needed for the heterogeneous case production from waste cooking oil:1. Process design and
related to the need for more equipment in those process technological assessment, Bioresour. Technol. 89 (2003) 1–16.
scenarios. [11] S. Zheng, M. Kates, M.A. Dubé, D.D. McLean, Acid-catalyzed
The NVP value show that the heterogeneous scenario production of biodiesel form waste frying oil, Biomass
Bionergy 30 (3) (2006) 267–272.
(case III) appear as the most profitable processes, it was used
[12] J.M. Marchetti, V.U. Miguel, A.F. Errazu, Heterogeneous
as an interest of 7% to calculate it, being this the lowest
esterification of oil with high amount of free fatty acids, Fuel
percentage required to invest on this alternative instead of 86 (2007) 906–910.
any other project. [13] G.R. Peterson, W.P. Scarrah, Rapeseed oil transesterification
In all cases 76–80% of the operating cost would still be by heterogeneous catalysis, JAOCS 61 (10) (1984) 1593–1597.
associated with the cost of raw material. These results [14] M. Kaieda, T. Samukawa, T. Matsumoto, K. Ban, A. Kondo, Y.
encourage future research to produce biodiesel from low cost Shimada, H. Noda, F. Nomoto, K. Ohtsuka, E. Izumoto, H.
Fukuda, Biodiesel fuel production from plant oil catalyzed by
raw material and the use of heterogeneous catalyst as a new
Rhizopus oryzae lipase in a water-containing system without
promising alternative.
an organic solvent, J. Biosci. Bioeng. 88 (6) (1999) 627–631.
From the preliminary sensitivity study it can be seen that [15] L.A. Nelson, T.A. Foglia, W.N. Marmer, Lipase-catalyzed
fluctuations on the biodiesel price as well as on the price of the production of biodiesel, JAOCS 73 (8) (1996) 1191–1195.
raw oil could lead to a more profitable business. Variations over [16] Y. Watanabe, Y. Shimada, A. Sugihara, H. Noda, H. Fukuda, Y.
the raw oil price have a more significant effect on the economics Tominaga, Continuous production of biodiesel fuel from
than modifications on the selling price of the biodiesel. vegetable oil using immobilized Candida antarctica lipase,
JAOCS 77 (4) (2000) 355–360.
[17] M.J. Haas, K.M. Scott, W.N. Marmer, T.A. Foglia, In situ
alkaline transesterification: An effective method for the
6. Disclaimer production of fatty acid ester from vegetable oils, JAOCS 81 (1)
(2004) 83–89.
The authors and Plapiqui do not accept responsibility for any [18] M.J. Haas, Improving the economics of biodiesel production
decision taken based on these model results. The model used through the use of low value lipids as feedstocks: vegetable oil
on this work is for research purpose only. For specific soapstocks, Fuel Process. Technol. 86 (2005) 1087–1096.
[19] R.G. Nelson, S.A. Howell, J.A. Weber, Potential feedstock
applications please contact the authors for recommendations
supply and costs for biodiesel production, Bioenergy '94
regarding the limitations and scope of the model.
Proceedings of the Sixth National Bioenergy Conference,
Reno/Sparks, Nevada, 1994.
[20] M. Noordam, R. Withers, Producing Biodiesel from Canola in
Acknowledgement the Inland Northwest: An Economic Feasibility Study, Idaho
Agricultural Experiment Station Bulletin, vol. 785, University
of Idaho, College of Agriculture, Moscow, Idaho, 1996.
Jorge Mario Marchetti would like to thank the National
[21] M.S. Graboski, R.L. McCormick, Combustion of fat and
Committee of Science and Technique of Argentina (CONICET)
vegetable oil derived fuels in diesel engines, Prog. Energy
for its financial support. Combust. Sci. 24 (1998) 125–164.
[22] M. Bender, Economic feasibility review for community-scale
REFERENCES farmer cooperatives for biodiesel, Biores. Tech. 70 (1999) 81–87.
[23] Y. Zhang, M.A. Dubé, D.D. McLean, M. Kates, Biodiesel
production from waste cooking oil: 2 Economic assessment
[1] A. Srivastava, R. Prasad, Triglycerides-based diesel fuels, and sensitivity analysis, Biores. Tech. 90 (2003) 229–240.
Renew. Sustain. Energy Rev. 4 (2000) 111–133. [24] M.J. Haas, A.J. McAloon, W.C. Yee, T.A. Foglia, A process model
[2] M.G. Kulkarni, A.K. Dalai, Waste cooking oil — an economical to estimate biodiesel production costs, Biores. Tech. 97 (4)
source for biodiesel. A review, Ind. Eng. Chem. Res. 45 (2006) (2006) 671–678.
2901–2913. [25] M.P. Dorado, F. Cruz, J.M. Palomar, F.J. López, An approach to
[3] G. Knothe, J. Van Gerpen, J. Krahl (Eds.), The biodiesel the economics of two vegetable oil-based biofuels in Spain,
handbook, AOCS Press, Champaign, Illinois, 2005, 302 pp. Renew. Energy 31 (2006) 1231–1237.
[4] J.M. Marchetti, V.U. Miguel, A.F. Errazu, Possible methods for [26] C.L. Levesque, A.M. Craig, Kinetics of an esterification with
biodiesel production, Renew. Sustain. Energy Rev. 11 (2007) cation-excahnge resin catalyst, Ind. Eng. Chem. 40 (1948)
1300–1311. 96–99.
[5] F. Ma, M.A. Hanna, Biodiesel production; a review, Bioresour. [27] R. Tesser, M. Di Serio, M. Guida, M. Nastasi, E. Santacesaria,
Technol. 70 (1999) 1–15. Kinetics of oleic acid esterification with methanol in the
748 F U E L P RO CE SS I NG T EC H NOL O G Y 8 9 (2 0 0 8) 7 40 –7 4 8

presence of triglycerides, Ind. Eng. Chem. Res. 44 (2005) [30] Y. Zhang. Design and economic assessment of biodiesel
7978–7982. production from waste cooking oil. M.A.Sc. Thesis, Department
[28] J. Van Gerpen, Biodiesel processing and production, Fuel of Chemical Engineering, University of Ottawa, 2002.
Process. Technol. 86 (2005) 1097–1107. [31] http://www.sagpya.mecon.gov.ar/new/0-0/programas/dma/
[29] Chemical Market Report, 2004–2006. 01_pindice.php.