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ENERGY PRACTICE REPORT

SOSE 2014
Biodiesel production 2: Oil Refining

Diego Felipe Mendoza Osorio;Luis Daniel Pineres Gomez


diegofelipe.mendozaosorio@haw-hamburg.de; luisdaniel.pineresgomez@haw-hamburg.de

Contents
1. Introduction ............................................................................................................... 2
2. Theory and theoretical basics ................................................................................... 3
3. Rapeseed Oils Chemical and Physical properties. ................................................... 4
4. Experiment ................................................................................................................ 5
4.1.

Experimental set up. ........................................................................................... 5

4.2.

Reagents ............................................................................................................ 5

4.3.

Process steps. .................................................................................................... 5

4.3.1

Transesterification. ....................................................................................... 5

4.3.2

Neutralization ............................................................................................... 8

4.3.3

Distillation..................................................................................................... 9

4.3.4

Separation.................................................................................................. 10

4.3.5

Density measurement ................................................................................ 11

5. Results .................................................................................................................... 12
6. Discussion ............................................................................................................... 14
7. Summary................................................................................................................. 14
8. References .............................................................................................................. 15

1. Introduction
Nowadays vegetable oils are used as a biomass source alternative to the normal diesel
fossil fuel. The resulting product named as Biodiesel is obtained by the transesterification
process, which involves a reaction of vegetable oils with methanol, although animal
oil/fats, tallow and waste cooking oil could be used as well. Raw oil obtained directly from
the vegetables is not being produced in large scale. The main reason for this fact is that
it is too costly, that is why most of the biodiesel obtained at the present comes from the
waste vegetable oil sourced from restaurants and industrial food producers (Wha14).
The interest in biodiesel as a renewable energy resource, arise when considering its
advantages: high flash point, good lubricity, high cetane number (above 100 compared to
40 for normal diesel fuel), less pollutants emissions mainly CO2 and sulfur dioxide (Bio14).
As an example in 2003 the European community decided to replace nearly 6% of the
annual consumed fossil fuels with biofuels, by the year 2010. The decision accelerated
the biodiesel production and it shows a growing trend, for instance in 2008 the annual
biodiesel production in the world was 7.75 million metric tons (Masato Kouzu, 2012).
Rapeseed oil has the greatest potential for biodiesel production; hence it will be used in
our practice. In experiment biodiesel I, the crude rapeseed oil was obtained from the seeds
by cold pressing (extrusion), in the following practice biodiesel II the transesterification
process was applied to refine the crude oil gathered previously.

Figure 1. Transesterification of triglyceride with methanol. (J.M. ENCINAR, 2010)

Transesterification consist of a reversible reaction of a triglyceride with an alcohol, the


products formed are esters and glycerol as shown in figure 1. The glycerine molecule of
a triglyceride has three fatty acids chains attached. During esterification process, the
triglyceride reacts with alcohol, and a catalyst is used as well, usually a strong alkaline.
From this reaction the products are mono-alkyl ester or biodiesel (FAME) and glycerol
(Wha14).

In the practice the alcohol used was methanol (which produces methyl esters) and the
catalyst potassium hydroxide (KOH), as products Rape Methyl Ester (from raw rapeseed
oil) and glycerine were obtained. Some methanol could be added in excess to drive the
reaction towards the right and ensure a complete conversion.
The experiment was executed in the laboratory N.2.36 of the Hamburg University of
Applied Sciences (HAW campus Bergedorf), which provided the equipment, chemicals
and feedstock required for transesterification. The crude oil used was obtained previously
by the Biodiesel I experiment by cold pressing rapeseed. In this report, the procedure
followed will be explained, the mass balances and oil conversion rate will be calculated
and compared to the values expected from similar experiments found in the literature.

2. Theory and theoretical basics


For the large scale industrial production of biodiesel, the alcohol (methanol) and the
catalyst (KOH or NaOH) are added in a stepwise manner to achieve a high yield of
biodiesel. After that, the glycerol (glycerine) is removed at the end of each step. Most of
the manufacturing plants make use of batch reactors.
The glycerol produced after the reaction is extracted in a settling tank or using a centrifuge,
it is possible because the glycerol has a very low solubility in the esters. The dissolved
methanol is separated from the methyl esters. The unreacted excess methanol could be
then recovered and used for further transesterifications (Selahattin Umdu, 2008).

Figure 2. Rapeseed oil Transesterification flow chart. (Van Gerpen, 2005)

The percentage of oil conversion, defined as the ratio of refined oil (FAME) to the crude
oil depends on the processing parameters, such as the molar ratio of methanol to oil, the
catalyst concentration, the time for the reaction, the type of alkaline catalyst and the
reaction temperature. Depending on the mentioned parameters, the oil conversion could
be found between the ranges of 85% to 98% (Jeong, et al., 2004). Different authors have
studied the influence of the catalyst concentration and found after transesterification, that
the oil conversion percentage range between 90% and 98% (J.M. ENCINAR, 2010)
(Masato Kouzu, 2012).

3. Rapeseed Oils Chemical and Physical properties.


The chemical and physical properties of the rapeseed oil are majorly dependent on the
quality of the original rapeseed and the processing technology (Gis, et al., 2011). For this
experiment, the Rapeseed oil used was obtained from rapeseed with a 5% of moisture
content. The technology used was a Screw extruder P500R from Anton Fries Corporation
getting from the feedstock around 30% of oil. Literature values for the rapeseed oil
properties are shown in the table 1.
Table 1. Properties of rapeseed oil and sub products.

RME
Rapeseed
oil
Methanol
Glycerin

Density [g/l]@
20C
886,00-900,001

Viscosity
[mm/s]@ 20C
6,00-9,002

Higher Heating
Value [J/g]
40370,003

Lower Heating
Value [J/g]
37458,004

914,505
794,009
1260,0013

74,196
0,73710
741,0014

40200,007
22900,0011
19000,0015

37620,008
20100,0012
16000,0016

(Gis, et al., 2011)


(Gis, et al., 2011)
3
(Delucchi, et al., 2003)
4
(Delucchi, et al., 2003)
5
(Temperature dependence of density and viscosity of vegetable oils., 2012)
6
(Temperature dependence of density and viscosity of vegetable oils., 2012)
7
(Parrilla, et al.)
8
(Parrilla, et al.)
9
(Olah, 2011)
10
(Viscosities of vegetable oils and fatty acids., 1992)
11
(Olah, 2011)
12
(Olah, 2011)
13
(Emissions and Temperature Measurements in Glycerol Flames, April 2224, 2012 )
14
(Emissions and Temperature Measurements in Glycerol Flames, April 2224, 2012 )
15
(Yaar, 2012)
16
(Emissions and Temperature Measurements in Glycerol Flames, April 2224, 2012 )
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4. Experiment
4.1. Experimental set up.
The following instruments and tools were used for the practice:
- Rotary evaporator Heidolph Laborota 4003.
- Centrifuge Hettlich Universal 30 F
- Density meter Heraeus
- Digital weighing scales.
- Vessels
- Magnetic stirrer.

4.2. Reagents
In order to achieve the processes of the experiment, the next reagents were used and
provided by the HAW laboratory staff.

Methanol.
Potassium Hydroxide (KOH) pellets.
Hydrochloric acid (HCL).

4.3. Process steps.


For the process of obtaining refined rapeseed oil RME (Rapeseed Methyl Esther) several
chemical separation steps are defined.
4.3.1 Transesterification.
For this step, the water bed of the rotary evaporator was preheated to 60 C. A fixed
feedstock weight (Rapeseed oil) of 120g was prepared into the flask, as shown in figure
3 and figure 4.

Figure 3. Weighting of the input rapeseed oil.

Figure 4. Preheating the rapeseed oil

While the oil was being heated, the Potassium Hydroxide and the Methanol needed were
weighted. The amounts were calculated according to the next stoichiometric relations
(Kaltschmitt, et al., 2009):

Where = 880 ; = 32 ; = 4 (Kaltschmitt, et al., 2009).


The rapeseed oil weight was stablished from the beginning of the experiment as 120g.
= 17.45

Figure 5. Weighting the HCL needed

A similar procedure is used to calculate the catalyst (KOH) weight, based in literature
values (Kaltschmitt, et al., 2009)

Where = 880 ; = 56 ; = 1/12 (Kaltschmitt, et al., 2009).


The rapeseed oil weight was stablished from the beginning of the experiment as 120g.

= 0.63

The catalyst and the methanol are mixed in the little flask shown in figure 5, and after 10
minutes the mixture was introduced in the rapeseed oil flask. This process was pictured
in the figure 6.

Figure 6. Mixing the reagents with the crude rapeseed oil.

After the reagents where mixed, the flask was installed in the rotary evaporator and the
machine was set at 100 rpm during 60 min.

4.3.2 Neutralization
After the transesterification process, a neutralization process took place in the experiment.
The reagent used to neutralize the catalyst in order to reduce the amount of soap
produced in the separation process. The mass of the neutralizer (Hydrochloric acid) was
calculated with the next equation (Kaltschmitt, et al., 2009), and the value was weighted
and registered in figure 5.

Where = 0.63; = 84 %; = 1; = 56 ; = 36.4 ; =


10 %; = 1; (Kaltschmitt, et al., 2009).

= 3.87

The neutralizer was added to the transesterified oil and the mixture was stirred to ensure
the mixing. The pH of the mixture was measured and as an additional measurement, the

pH of the crude oil was taken and registered at the beginning. The results of this
measurements are shown in the figure 7.

Figure 7. pH measurements crude oil (left) and oil Transesterified (right)

4.3.3 Distillation.
After the measurement of pH, the mixture was distilled in the rotary evaporator. In the
evaporator the settings were re-defined for this process (figure 8):

= 2
= 80

Figure 8. New set of parameters in the evaporator for the distillation process

During this process, water and methanol where separated from the mixture by evaporation
and pumping.

4.3.4 Separation
After the distillation, the oil need to be separated from the remaining glycerin content. To
achieve this, the whole mixture was introduced in centrifuge tubes and processed in the
centrifuge machine as shown in figure 9. This device (Hettich Universal 30F) was set up
to 11000 RPM for 15 min (figure 10).

Figure 9. Transesterified oil neutralized.

Figure 10. Settings in the centrifuge machine.

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After the separation process, the glycerine was separated from the oil as shown in the
figure 11.

Figure 11. RME and glycerin separated.

4.3.5 Density measurement


As parameters to check the process, the densities of the different sub-products from the
original rapeseed oil were measured. This step is performed with the Density meter
Heraeus. Due to the fact that this device receive substance flow as an input, acetone was
used to clean the conducts and to achieve more accurate results. The density of Methanol,
Rapeseed oil, Rapeseed methyl ester (RME) oil and water was expected to be measured.

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5. Results
-

Densities: As a result of the process, the measured densities of the subproducts (methanol, rapeseed oil, transesterification distillates and Rapeseed
methyl ester oil) are shown in the table 2. From the chemical reactions are
expected the two distillates in the transesterification process to be water and
methanol.

Table 2. Measured density values.

Density @ 21.07 C [g/l]

RME
Rapeseed
Oil
Methanol
Distillate 1
Distillate 2

Value 1

Value 2

Value 3

Mean Value

904,7

903

900,7

902,80

907,3
769
857,7
815,5

905,9
773,9
854,6
816,5

909,8
790,1
857
816,2

907,67
777,67
856,43
816,07

Acidity: The pH registered for the rapeseed oil was between 4 and 5, and it is
clearly observed that the oil after neutralization had a higher acidity (pH 6) as
can be seen in the figure 7.
Mass balance: A balance of mass for the process can be computed according
to the next formula:

+ + + = + +

Where is the mass loss in the process (RME stuck to the flasks, etc.) and the distillates.
From this balance, the items of right side of the equation were weighted (figure 12).

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Figure 12. Weight of the final RME oil obtained.

= 111.16
3.31
+ + + = 120 + 0.71 + 17.50 + 3.87 [] = 142.08

= 142.08 111.16 3.31 = 27.61

RME oil yield: Due to the fact that the oil was taken through several steps, the
RME oil yield is expected to be proportionally low according to the process
efficiency. An oil yield and an oil yield percentage can be computed as follows:

% =

111.16
120

= 92.63%

An additional oil yield can be computed from the whole process mass balance,
showing a lower yield (worst efficiency).

% =

111.16
=
= 78.23%
142.08

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6. Discussion
As it could be seen from the section 5, the oil percentage conversion of crude rapeseed
oil to RME was about 92.63%. This yield is consistent to the conversion range of 85% to
98% found in the literature (Jeong, et al., 2004) (J.M. ENCINAR, 2010). Although a higher
percentage of oil conversion could be expected, this value is dependent on the processing
parameters. For instance increasing the catalyst concentration (KOH) or the molar ratio
of methanol to oil up to a given value, could give a better oil percentage conversion. It is
necessary to consider some losses of oil remaining in the flasks, centrifuge containers
and pipets used for carrying out the practice.
Regarding the densities of the feedstock and products, it could be deduced from table 2
that the product RME had a lower density (902.80 g/l) than the rapeseed crude oil (907.67
g/l) as it is expected after a transesterification. The methanols density before the
experiment (777.67 g/l) was nearly the literature value of 794 g/l. There are some
inconsistencies with the densities values for distillates 1 and 2. These educts are expected
to be water and methanol according to the practice guide (Kaltschmitt, et al., 2009). The
density values were 856,43 g/l and 816,07 g/l, neither of them matched with the literature
values for water and methanol density at the given temperature. It seems that the
distillates are not pure substances, but a mixture. Therefore a more detailed analysis
about the distillates is required.

7. Summary
Fatty acids Methyl ester oil is becoming extensively applied for industrial and transport
applications. It is an important additive for biodiesel (7% in content), hence a refining
process by means of transesterification is required for lowering its kinematic viscosity. The
scope of the practice was to compare the literature values for density and refined oil yield
with the experimental results. The experiment was successfully performed, the amount of
refined oil obtained matched the theoretical expected values (around 93%). From the
practice and theory it could be expected that the oil conversion percentage depends on
the balance of the reagents and educts as well as the catalyst concentration.

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8. References
Biodiesel. [Online] Cyberlipid.[Cited: April 09, 2014.] http://www.cyberlipid.org/glycer/biodiesel.htm.
Delucchi, Mark A. and Lipman, Timothy . 2003. ENERGY USE AND EMISSIONS FROM THE LIFECYCLE OF
DIESEL-LIKE FUELS DERIVED FROM BIOMASS. Berkeley : Institute of Transportation Studies, 2003.
Emissions and Temperature Measurements in Glycerol Flames. Jiang, Lulin, Taylor, Robert and Agrawal ,
Ajay. April 2224, 2012 . Tuscaloosa : Central States Section of the Combustion Institute , April 2224,
2012 . Spring Technical Meeting.
Gis, Wojciech, Zoltowski, Andrzej and Bochenska, Anna. 2011. PROPERTIES OF THE RAPESEED OIL
METHYL ESTERS AND COMPARING THEM WITH THE DIESEL OIL PROPERTIES. 2011. p. 3.
J.M. ENCINAR, J.F. GONZLEZ,A. PARDAL,G. MARTNEZ. 2010. Transesterification of Rapeseed Oil with
Methanol in the Presence of Various Co-Solvers. Third International Symposium on Energy from Biomass
and Waste, Venice Italy. 2010.
Jeong, G. T., et al. 2004. Production of Biodiesel Fuel by Transesterification of Rapeseed oil. Applied
Biochemistry and Biotechnology. Humana Press Inc., 2004, Vols. 113-116.
Kaltschmitt, Martin, Hartmann, Hans and Hofbauer, Hermann. 2009. Energie aus Biomasse.
Grundlagen, Techniken und Verfahren. s.l. : Springer, 2009.
Masato Kouzu, Jyu-suke Hidaka. 2012. Transesterification of vegetable oil into biodiesel catalyzed by
CaO: A review. Fuel:The Science and Technology of Fuel and Energy . 2012, Vol. 93, 1-12.
Olah, George Andrew. 2011. Methanol economy. Aarhus : Danish Methanol Association, 2011.
Parrilla, J. and Corts, C. Modelling of droplet burning for rapeseed oil as liquid fuel. Zaragoza : University
of Zaragoza.
Selahattin Umdu, Emin. 2008. Methyl Ester Production From Vegetable Oils On Heterogeneous Basic
Catalysts. Izmir : Graduate School of Engineering and Sciences of Izmir Institute of Technology, 2008.
Temperature dependence of density and viscosity of vegetable oils. Esteban, Bernat, et al. 2012. 2012,
Biomass and Bioenergy, pp. 164-171.
Van Gerpen, J. 2005. Biodiesel Processing and Production. Fuel Processing Technology. 2005, Vol. 86,
1097-1107.
Viscosities of vegetable oils and fatty acids. Noureddini, Hossein, Teoh, B. and Clements, Davis. 1992.
s.l. : University of Nebraska-Lincoln, 1992, Papers in biomedical, pp. 1189-1191.
What is Biodiesel? [Online] [Cited: April 09, 2014.] http://www.esru.strath.ac.uk/EandE/Web_sites/0203/biofuels/what_biodiesel.htm.
Yaar, Demirel. 2012. Energy and Energy Types. Energy, Production, Conversion, Storage, Conservation,
and Coupling. s.l. : Springer, 2012, p. 39.

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