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biodiesel production: process and characterization

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 Materials and processes for energy: communicating current research and technological developments (A. Méndez-Vilas, Ed.)
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Biodiesel production: process and characterization

N.L. Da Silva, L.F. Rios, M.R. Wolf Maciel and R. Maciel Filho
Faculty of Chemical Engineering, State University of Campinas (UNICAMP), Campinas, Brazil

Biodiesel is a fuel made of vegetable oils, animal fats and microbial oil (algae, bacteria and fungi). The raw materials are
converted to biodiesel through a chemical reaction involving ethanol and catalyst. This reaction is called transesterification
or ethanolysis. This work presents the biodiesel production using three systems: batch stirred tank reactor (BSTR), reactive
distillation (RD) system with a column with ten plates and reactive distillation system with a column filled with glass.
Experimental design was used to study the influence of process variables on ethyl ester conversion. The biodiesel was
made using bioethanol and sodium hydroxide as the catalyst on a laboratory scale. The best ethyl ester (biodiesel)
conversion was 99.84 wt % after 6 minutes of reaction, obtained with the RD system with plates.

Keywords: Biodiesel, ethyl esters, transesterification, bioethanol, reactive distillation, experimental design.

1. Introduction
Biodiesel is one of the renewable and clean burning fuels, which can be used in diesel engines. Biodiesel is usually
generated from food-grade vegetable oils using the transesterification process. Using the food-grade vegetable oils is
not economical since they are more expensive than diesel fuel. Therefore, it is said that the main obstacle for
commercialization of biodiesel is its high cost. The kind of feedstock which is used is the most effective factor on the
biodiesel characteristics and the price [1].
This renewable fuel is usually produced by using a basic catalyst such as sodium hydroxide or potassium hydroxide;
that reaction provides a relatively high reaction rate and low catalyst costs [2]. However, the use of this catalyst is
limited only to oils that contain less than 0.5 wt% of free fatty acid (FFA) or with acid values of less than 1 mg KOH/g
[3].
The use of vegetable oils as an alternative fuel for diesel engines is accelerated by the energy crisis due to the
depletion of resources and increased environmental problems. A consistent supply of feedstock is being faced as a
major challenge by the biodiesel production industry [4]. The usually used raw materials, refined vegetable oils, have a
higher cost, thus creating a major hurdle in the commercialization of biodiesel. The utilization of inexpensive feedstock
(such as waste cooking oils and non-edible oils) appears as an attractive option since it would improve the economic
feasibility of biodiesel production. However, low-cost oils usually contain high levels of undesired components, such as
FFA and water [5].
Continuous stirred tank reactor (CSTR) is commonly used in industrial biodiesel production but the conventional
technique involves a long reaction time; higher molar ratio of alcohol to oil; long residence times; high operating cost
and energy consumption are required to purify biodiesel and recover excess amounts of alcohol and catalyst during
downstream processing. Other less conventional equipment has been studied in order to increase the biodiesel
conversion rate and the reaction speed, while decreasing the processing cost. This equipment includes reactive
distillation (RD), rotational packed bed, microwave reactors and ultra shear reactors [6-8].
The RD process is a complex operation because it is influenced by several parameters, such as: size and location of
reaction zone, reflux ratio, hold up, pressure, temperature, and feeding trays of reactants, among others. Therefore, the
application of commercial process simulators results is important to quantify the effects of operating conditions on the
process performance and thus to allow its optimization [9]. According to Gomez-Castro (2013), the use of reactive
distillation reduces the total heat input required by the process, due to the constant removal of the by-products and the
excess methanol [10].
This work presents a comparative study of biodiesel production using the following process: two types of reactive
distillation systems and batch stirred tank reactor. The experimental design was used because this methodology
permitted a careful evaluation of the process variables.

2. Materials and Methods

2.1 Raw materials

The soybean oil was obtained from Aboissa (São Paulo, Brazil). The sodium hydroxide and anhydrous ethanol were
obtained from Synth (São Paulo, Brazil). All the standards were supplied by Sigma-Aldrish Chemical Company, Inc.
(St. Louis, Mo), n-heptane (HPLC-grade, Merck), polytetrafluorethylene filter (PTFE filter) supplied by Millipore
(USA), HPLC-grade THF (Tetrahydrofuran) from B&J/ACS (USA).

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2.2 Analysis
Free Fatty acids: The free fatty acid content was determined according to the AOCS official method Ca 5a-40 as oleic
acid.
Fatty acid compositions: The fatty acid composition of soybean oil was determined by gas chromatography (CG)
analysis. The GC was equipped with a flame ionization detector (FID) and with a DB 23 column. Injector and detector
temperatures were set at 250 and 300 °C, respectively. The carrier gas used was helium at 46 mL/min. Air and
hydrogen flow rates were 334 and 34 mL/min, respectively. Oven temperature programming was as follows: starting at
50 °C for 2 min; from 50 to 180 °C at 10 °C/min; 180 °C was held for 5 min; from 180 to 240 °C at 5 °C/min.
Identification of different fatty acids of ethyl esters (FAEEs) were based on a reference standard.
Characterization of transesterification reaction: The composition of transesterification reactions was determined by
high-performance size-exclusion chromatography (HPSEC) supplied by Waters (U.S.). The HPSEC equipped with two
columns Styragel HR 0.5 and HR 2 were connected in series and with a differential refractometer detector model 2410.
The mobile phase was tetrahydrofuran.
Viscosity and density: The density and viscosity were determined by Stabinger Viscometer SVM 3000 (Anton Paar).
This property was measured at 40 °C (313 K) according to the ASTM D-445.

2.3 Experimental design

The experimental design was chosen to study the optimization of two selected parameters: ethanol : soybean oil molar
ratio and catalyst concentration. The experiments were carried out according to a 22 complete factorial design plus three
central points and axial points, called star points. The factors were set independent from one another within the
following limits: catalyst concentration: 0.5 % wt ≤ C ≤ 1.5 % wt; ethanol : soybean oil molar ratio: 3:1≤ MR ≤ 9:1.
Table 1 shows the variables levels of experimental design. The software Statistica (Statsoft, v.7) was used to analyze the
results.

Table 1: Variable level for the full factorial design

Variable -1.41 -1 0 1 1.41
Molar ratio (alcohol:oil) 3.0 3.92 6.0 8.0 9.0
Catalyst concentration (%) 0.5 0.65 1.0 1.34 1.5

2.4 Experimental conditions and Procedures

Initially, the reactor was loaded with soybean oil, preheated to the desired temperature, the catalyst was dissolved in
ethanol and the reaction started when the alcoholic solution was added to the vegetable oil. Reaction time was 6 minutes
and the reaction temperature was 78 °C in RD columns and 70 °C in BSTR. During the reaction, samples were collected
through the dilution of 0.1g of the reaction products in 10 ml of tetrahydrofuran (THF). This large dilution readily stops
the reaction course. Then, the samples were filtered using a PTFE filter and analyzed using HPSEC (high-performance
size-exclusion chromatography). After the reaction, the ethanol excess was evaporated then, the ester and glycerol
layers were allowed to be separated in a separator funnel, and the ethyl esters layer was purified. In order to remove the
residue from raw materials and the catalyst, the ester layer was washed and dried. The glycerol layer could be
neutralized and distilled using a patent process (PI0906818-0) and this process leads to glycerol with 99 % of purity.
The glycerol could be purified by molecular distillation [11]. This equipment works under low pressure and uses an
extremely short residence time period. The molecular distillation is an evaporative distillation where a compound in the
liquid state evaporates without boiling, because the upper vacuum removes the effects of the atmospheric pressure.
Some advantages can be observed in this technique such as: high product percentage yield; elimination of color bodies
and minimized thermal hazard (a necessity for heat sensitive compounds). Figure 1 shows a process flow for biodiesel
process.

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Figure 1: Process flow for biodiesel process.

Batch stirred tank reactor (BSTR): A 1 liter (BSTR) equipped with a reflux condenser, a mechanical stirrer and a
stopper to remove samples, Figure 2. The agitation was kept constant at 400 rpm and reactions temperatures were
70 °C.

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Figure 2: Batch stirred tank reactor

Reactive distillation columns (RD): Two systems were used in order to present the most efficient process. The main
equipment used in the first system was a pre-reactor (plug flow reactor - PFR) and reactive distillation column with ten
plates and the main equipment in the second system was a pre-reactor (batch stirred tank reactor - BSTR) and a packed
reactive distillation column filled with glass rings. The pre-reactor was used because it permitted the perfect contact
between the reactants and the ester conversion during the first minute of the process. Figure 3 and 4 show these
systems.
The reaction temperatures in RD columns were 78 °C because these equipments work at ethanol boiling point. The
reactive distillation is a process that combines the reaction and separation in single equipment. The difference between
the boiling temperature of ethanol and the product mixture, ethyl esters and glycerol, is so large that the separation of
the alcohol from the product mixture became easy.

Figure 3: System 1 (plug flow reactor – PFR and reactive distillation column with ten plates)

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10
9

P-03
E-8
17
2

P-01 3 11 P-05

14
8
7

T-01 4

1 13
R-01 E-11
P-02
P-04

C-01 T-04
12

T-02

V-1

T-03

Figure 4: System 2 (batch stirred tank reactor and a packed reactive distillation column filled with glass rings)

1) T-01: Ethanol tank of 1 liter; 2) T-02: Soybean oil tank of 1 liter; 3) R-01: Pre – reactor; 4) C-01: Packed reactive
distillation column; 5) E-08: Water - cooled condenser; 6) E-11: Ester / Glycerol separator; 8) T-04: Ester (biodiesel)
tank; 9) T-03-13: Glycerol tank.

3. Results
Table 2 shows the fatty acid composition of soybean oil. The free fatty acid content of refined soybean oil was 0.3%.
Soybean oil density and viscosity were 38.2 ± 0.03 and 0.8908 ± 0.0001, respectively. After transesterification the
viscosity decreased about 8.8%, then soybean oil ethyl ester viscosity and density were 4.343 ± 0.013 and
0.8623 ± 0.0001, respectively.

Table 2: Fatty acid content of soybean oil

Molar Composition
Fatty acid name Structure
mass (wt.%)
Palmitic C16:0 256.43 11.0
Stearic C18:0 284.43 5.1
Oleic C18:1 282.47 27.2
Linoleic C18:2 280.45 51.3
Linoleic C18:3 278.44 5.4

3.1 Experimental design results

The experimental design was chosen to study the influence of ethanol: soybean oil molar ratio and catalyst
concentration on ethyl ester conversion or biodiesel production. The same plan was used in two systems in order to
compare experimental data. The software Statistica (Stat soft, v.7) was used to analyze the results with a confidence
level of 95%.

3.1.1 Batch stirred tank reactor (BSTR):

Figure 5 shows that the linear effect and the interaction between the catalyst concentration and the molar ratio were
significant, because these effects were shown to the right of the p-value, with a confidence level of 95%. Catalyst is the
most important variable because this effect is about 4 times higher than the effect of molar ratio.

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C (%) 54.28

MR 12.00

C x MR -4.59

p=0.05

Effect

Figure 5: The Effects of catalyst (C) and soybean oil: ethanol molar ratio on ethyl ester conversion

3.1.2 Reactive distillation columns (RD) filled with glass rings:

Figure 6 shows the effect and interaction of process variable on ethyl ester conversion. Among the two parameters
studied, the molar ratio is the most important variable of the transesterification reaction. However, all of them increase
the ester conversion because they have a positive influence on ethyl ester conversion.

MR 170.61

C (%) 77.16

C x MR -34.96

p=0.05

Effect

Figure 6: The Effects of catalyst (C) and soybean oil: ethanol molar ratio on ethyl ester conversion.

3.1.3 Reactive distillation columns (RD) filled with plates:

The effect of the catalyst content (C) and ethanol: soybean oil molar ratio (MR) on the ethyl ester conversion is
presented in Figure 7 (Pareto graph). Molar ratio is the most important variable, as shown in Figure 7.

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MR 68.65

C (%) 31.08

C x MR -12.31

p=0.05

Effect

Figure 7: Effect of C and MR on ethyl ester conversion.

Figure 8 shows the experimental design results of three systems. These systems present good ethyl ester conversion
in 6 minutes of reaction time. The lowest conversion using BSTR was 78.01wt % (run 5), with 0.5 wt % of catalyst and
molar ratio of 6:1 and the highest was 99.01 wt % (run 6) with 1.5 wt % of catalyst and molar ratio of 6:1. It is in
agreement with experimental design results (Figure 5). The BSTR system catalyst is the most significant variable.
The lowest conversion rate using RD system was 73.93 wt % (run 1) with system 2 (molar ratio of 3.92:1 and
catalyst concentration of 0.65 wt %) and the highest rate was 99.79 wt % (run 8) with system 1 (molar ratio of 9:1 and
catalyst content of 1 wt %). It is in agreement with the experimental design analysis to RD systems.

120

100
Ethyl ester conversion

80

System 1
60
System 2
BSTR
40

20

0
1 2 3 4 5 6 7 8 9 10 11
Run

Figure 8: Experimental design results to three systems using catalyst concentration from 0.5 to 1.5 wt %, molar ratio from 3:1 to 9:1,
and reaction time of 6 min.

where: System 1 is RD with plates, system 2 is RD filled with glass rings.

4. Conclusion
Within the two parameters studied, molar ratio is the most important variable of transesterification reaction, in the
reactive distillation process. Catalyst concentration is the most important variable in BSTR. However, all of them

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increase the ester conversion, because they have a positive influence on ethyl ester conversion. On the other hand, the
increase of both variables simultaneously leads to a decrease in the rate of ethyl ester conversion in all processes. The
best rate of biodiesel conversion was obtained in run 4 (99.84 wt %) with the system 1.

Acknowledgements The authors acknowledge the financial support provided by the São Paulo Research Foundation (FAPESP) and
the National Council of Technological and Scientific Development (CNPQ).

References
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[4] Tanawannapong, Y.; Kaewchada, A.; Jaree, A.; Biodiesel production from waste cooking oil in a microtube reactor. Journal of
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