Molecules: High-Quality Biodiesel Production From Buriti (Mauritia Flexuosa) Oil Soapstock
Molecules: High-Quality Biodiesel Production From Buriti (Mauritia Flexuosa) Oil Soapstock
Article
High-Quality Biodiesel Production from Buriti
(Mauritia flexuosa) Oil Soapstock
Samantha Siqueira Pantoja 1 , Vanessa Albuquerque de Mescouto 2 ,
Carlos Emmerson Ferreira da Costa 1 , José Roberto Zamian 1 , Geraldo Narciso da Rocha Filho 1
and Luís Adriano Santos do Nascimento 1,2, *
1 Laboratory of Catalysis and Oil-Chemistry, Graduate Program in Chemistry, Institute of Exact and Natural
Sciences, Federal University of Pará, Belém, Pará, CEP 66075-110, Brazil;
[email protected] (S.S.P.); [email protected] (C.E.F.d.C.); [email protected] (J.R.Z.);
[email protected] (G.N.d.R.F.)
2 Laboratory of Oils of the Amazon, Institute of Biological Sciences, Graduate Program in Biotechnology,
Federal University of Pará, Belém, Pará, CEP 66075-110, Brazil; [email protected]
* Correspondence: [email protected]; Tel.: +55-091-98171-4947
Received: 11 November 2018; Accepted: 8 December 2018; Published: 28 December 2018
Abstract: The buriti palm (Mauritia flexuosa) is a palm tree widely distributed throughout tropical
South America. The oil extracted from the fruits of this palm tree is rich in natural antioxidants.
The by-products obtained from the buriti palm have social and economic importance as well, hence
the interest in adding value to the residue left from refining this oil to obtain biofuel. The process of
methyl esters production from the buriti oil soapstock was optimized considering acidulation and
esterification. The effect of the molar ratio of sulfuric acid (H2 SO4 ) to soapstock in the range from 0.6
to 1.0 and the reaction time (30–90 min) were analyzed. The best conditions for acidulation were molar
ratio 0.8 and reaction time of 60 min. Next, the esterification of the fatty acids obtained was performed
using methanol and H2 SO4 as catalyst. The effects of the molar ratio (9:1–27:1), percentage of catalyst
(2–6%) and reaction time (1–14 h) were investigated. The best reaction conditions were: 18:1 molar
ratio, 4% catalyst and 14 h reaction time, which resulted in a yield of 92% and a conversion of 99.9%.
All the key biodiesel physicochemical characterizations were within the parameters established by
the Brazilian standard. The biodiesel obtained presented high ester content (96.6%) and oxidative
stability (16.1 h).
1. Introduction
Biodiesel is a fuel derived from vegetable oils or animal fat that is formed by mono-alkyl-esters of
long chain fatty acids. It can be used for replacing fossil diesel fuel in whole or in part in compression
ignition engines for automotive propulsion or energy generation [1]. One of the advantages of using
biodiesel is the high cetane number compared to diesel. Biodiesel has no aromatics or sulfur, and
it is composed of about 10 to 11% oxygen by weight. Consequently, the use of this fuel reduces the
emissions of carbon monoxide, unburned hydrocarbons, and particulate matter when compared to
diesel fuel. Furthermore, it is a renewable, biodegradable, alternative and nontoxic fuel [2].
There are several critical issues for biodiesel production, such as high prices and the low
availability of raw vegetable oils. In addition, the high cost of feedstocks makes biodiesel production
cost about 1.5 times more than diesel [3]. On the other hand, technological solutions have been
proposed, such as using less pure raw materials such as frying oil, soapstocks and waste oil [4].
There are approximately 4000 vegetable species around the world from which one can extract
oil [5]. In Brazil, the Amazon region is known for its biodiversity, and has several industries
that specialize in the production of vegetable oils, such as: açaí oil (Euterpe oleracea), andiroba oil
(Carapa guianensis), buriti oil (Mauritia flexuosa), Brazil nut oil (Bertholletia excelsa), and copaiba oil
(Copaífera officinalis). These oils are mainly used in the cosmetic, pharmaceutical and food industries.
Mauritia flexuosa is one of the most common palms across tropical South America. The so-called
“varzea” (floodplain) forests, in the Brazilian Amazonia, are largely dominated by Mauritia flexuosa
and other palms [6]. The fruits of buriti (Mauritia flexuosa) (Figure 1) have a red and squamous shell,
and a reddish and oily pulp with between 20–30% (wt.) of oil which has an elevated concentration of
carotenes. It is estimated that the average annual production of pulp is approximately 0.79 t ha−1 and
oil is 17.0 kg ha−1 [7].
Buriti oil is used in drugs, cosmetics, foods and polymeric materials. The search for new natural
sources of β-carotene has encouraged the development of processes for extracting oil from buriti,
which is rich in carotenoids [8,9]. Due to the presence of these natural antioxidants, this oil becomes
less susceptible to oxidation; published studies have shown that buriti oil has a much higher oxidative
stability (4155.6 min) than passion fruit oil (160.8 min) and rubber seed oil (291.6 min), measured in a
Rancimat apparatus at 100 ◦ C, suggesting that buriti oil could be useful in the food industry [10].
The chemical and physical refining processes of vegetable oils, such as degumming, neutralization,
bleaching and deodorization, have been designed to remove substances that may impart undesirable
flavor, color, or keeping quality and to obtain odorless, bland and oxidatively stable oils, which are
acceptable to consumers [11]. About 6% of soapstock is generated during the process of refining
vegetable oils. The cost of this material is around one-tenth of the price of refined oil, so it is a cheap
source of fatty acids [12].
Soapstock consists of a heavy aqueous lipid emulsion having about 50% water, phosphatides,
pigments and other minor non-polar compounds. In addition to these, it has salts of free fatty acids
and triglycerides, which can be converted to biodiesel [13].
Generally, in the industrial processing of this material, acidification is first carried out,
using sulfuric acid and steam to achieve partial acid hydrolysis and/or removal of the acyl and
phosphoacylglycerol ester bonds of the starting material. After acidulation, the spontaneous separation
into two phases occurs, an aqueous phase, and an oil layer, formed by pigments, acylglycerol-free fatty
acids, and other lipophilic materials; this is called acid oil [14].
The main contribution reported in this paper was to test the best reaction conditions of the
acidulation stages for soapstock and for esterification of acid oil in order to obtain and provide a
previously unpublished physical and chemical description of the biodiesel produced, from waste
derived from refining buriti oil, demonstrating its viability as a raw material for biofuel.
2. Results
palmitic, palmitoleic, stearic, oleic, linoleic and linolenic acids, with the largest share being oleic acid
(71.4%). Comparing the fatty acid composition of buriti oil found in the literature [7] with that of the
soapstock used in this research, it was found that the compositions were similar.
Table 1. Main characteristics of the buriti soapstock oil and buriti oil.
Effect of the Acid/Soapstock Molar Ratio and Effect of the Time on Soapstock Acidulation
For the acidulation stage of the soapstock, molar ratios for sulfuric acid/soapstock of 0.6, 0.8 and
1.0 were used and the time was kept constant at 1 h. As shown in Table 2, when the molar ratio was
increased from 0.6 to 0.8 there was an increase in conversion into fatty acids from 91.3% to 94.4%, while
at a molar ratio of 1.0 conversion was 92.5%. Increasing the percentage of catalyst raised viscosity in
the reaction slurry, and therefore slowed the mass transfer of the reagents to and from the surface
of the catalyst, decreasing the reaction rate [15]. The molar ratio of 0.8 was thus established as the
best condition.
To evaluate the influence of time on acidulation of the soapstock, reactions of 30, 60 and 90 min
were performed and the acid/soapstock molar ratio was kept constant at 0.8. As shown in Table 2,
when the reaction time was increased from 30 min to 60 min there was an increase in conversion into
fatty acids from 90.2% to 94.4%, while at 90 min of reaction, conversion was 91%. This behavior can
be explained because catalyst activity is slightly inhibited by the formation of water in the reaction
mixture [16]. The best conditions for acidulation of buriti oil soapstock were therefore established as
an acid/soapstock molar ratio 0.8 and a reaction time of 60 min.
Table 2. Effect of the acid/soapstock molar ratio a and effect of the time on soapstock acidulation b .
However, esterification is a reversible reaction, and thus requires a greater amount of alcohol for the
reaction to proceed [17]. When the molar ratio was raised from 9:1 (77.3%) to 18:1 (83.9%), there was
an increase in the ester content, but when the molar ratio 27:1 (72.4%) was used, it was found that the
ester content was reduced; therefore, a molar ratio of 18:1 showed better performance. This behavior
occurs because, when there is an excess of methanol, the reaction is slowed due to dilution of the
reaction medium [18].
Figure 2. Effect the time on esterification of acid oil. Reaction conditions: Molar ratio of methanol/acid
oil 18:1; 4% of H2 SO4 .
2.4. Physical-Chemical Characterization of the Biodiesel Obtained from Buriti Oil Soapstock
The biodiesel yield obtained from buriti oil soapstock was 92%, calculated with respect to the
initial mass of the acid oil used. Table 3 shows the results obtained with the physical-chemical
characterization of the biodiesel from buriti oil soapstock, the limits stipulated in Brazil, according
Molecules 2019, 24, 94 5 of 9
to the Resolution of the National Agency for Petroleum, Natural Gas and Biofuels (RANP 45/2014),
European standard (EN 14214) and American standard (ASTM D 6751).
Table 3. Physical-chemical characterization of the biodiesel obtained from buriti oil soapstock.
Specific mass for a biodiesel is related to its molecular structure. Specific mass is directly
proportional to the carbonic chain size of the alkyl ester and inversely proportional to the number of
double bonds [22]. The specific mass of the biodiesel derived from buriti oil soapstock was 877.3 kg/m3 ;
a value within the limits specified in RANP 45/2014, this parameter influences the efficiency of fuel
atomization [23].
The viscosity of biodiesel obtained from buriti oil soapstock was 5.22 mm2 /s; that value is within
the limits established by RANP 45/2014 and ASTM D 6751, and above that established by EN 14214.
This characteristic is important because fuels with high viscosity tend to form larger droplets upon
injection, resulting in poorer atomization and creating problems such as enhanced polymerization
reaction and more carbon deposits. Additionally, a highly viscous fuel mixes more slowly with air and
causes weak combustion, exhaust smoke and emissions, apart from problems caused by increased
viscosity in cold weather. On the other hand, a fuel with low viscosity cannot provide sufficient
lubrication for the accurate fit of fuel injection pumps, resulting in increased wear or leakage [24].
The minimum flash point required by the RANP is 100 ◦ C, ASTM D6751 is 130 ◦ C and EN 14214
is 101 ◦ C. The flash point of biodiesel obtained from buriti oil soapstock was 174 ◦ C. Flash point is a
property related to safety that is usually considered in determining handling, transportation and fuel
storage conditions. This property is defined as the minimum temperature at which the volatile fuel
flashes or ignites momentarily when in contact with a flame or spark at a pressure of 101.325 kPa [25].
Acid value indicates the presence of free fatty acids in a fuel sample. Presence of free fatty acids
in biodiesel may cause engine corrosion and the formation of deposits [26]. The acidity of biodiesel
obtained from buriti oil soapstock was 0.04 mg KOH/g, well above the maximum value allowed by
RANP norm 45/2014, ASTM D6751 and EN 14214 (0.5 mg KOH/g) indicating that this biofuel has a
small amount of free fatty acids, since there was a high conversion of those esters in the esterification
reaction. This would probably not cause problems in relation to engine corrosion.
Cold filter plugging point (CFPP) is measured using a standard device; it is the lowest temperature
(◦ C) at which the biodiesel can cross this device during a specific time [27]. Cold filter plugging
point (CFPP) of a fuel is related to performance in cold climates. With low operating temperature,
fuel consumption can diminish and reduce the performance of fuel pumps, lines and injectors [28].
The CFPP for biodiesel obtained from buriti oil soapstock was 3 ◦ C, a value below the maximum level
stipulated in RANP 45/2014 and EN 14214, indicating that this fuel can be used without problems in
cold weather regions. This value is related to the high content of esters of unsaturated acids in this
biofuel, at around 77.2%.
Corrosivity to copper is a property established for determining the potential capacity a fuel has of
causing corrosion in metal parts; high values of this property indicate that the fuel can cause corrosion
problems in the engine and tank. This property is associated with the presence of acids or sulfur
Molecules 2019, 24, 94 6 of 9
compounds [22]. Corrosivity to copper of biodiesel obtained from buriti oil soapstock was 1, which is
the threshold value stipulated by RANP 45/2014 and EN 14214. And corrosivity to copper of biodiesel
obtained from buriti oil soapstock is below the value stipulated in ASTM D 6751.
The biodiesel obtained presented a high level of esters, around 96.6%, indicating its elevated
purity and the high efficiency of the esterification reaction. This value is above the minimum value of
96.5%, stipulated by RANP 45/2014 and EN 14214. Figure 3 shows (A) Buriti oil soapstock, a heavy
emulsion and (B) Biodiesel from buriti oil soapstock, with a low viscosity.
Figure 3. (A) Buriti oil soapstock and (B) biodiesel from buriti oil soapstock.
The high oxidative stability of biodiesel from the buriti oil soapstock was 16.1 h; this value is
above the minimum stipulated by RANP 45/2014 (8 h), ASTM D 6751 (3 h) and EN 14214 (6 h). Several
researchers have studied the oxidative stability of biodiesel. During long periods of storage, this
is one of the problems that affects biodiesel. Other parameters that influence stability, such as the
presence of heat, air, light and peroxides, have been studied [29]. The high stability of this biodiesel
may be influenced by the fatty acids’ composition of the soapstock, which presented mostly oleic acid
(C18:1), around 71.4%, and palmitic acid (C16:0), around 21.1%. The relative rates of oxidation of the
methyl esters of oleic (C18:1), linoleic (C18:2) and linolenic (C18:3) acids is 1:12:25 [30]. The presence of
saturated fatty acid, which is less susceptible to oxidation, may also have contributed. Additionally,
buriti oil has tocopherols and carotenoids, which are natural antioxidants, and provide this biodiesel
with high oxidative stability [31].
3.1. Materials
The soapstock from buriti oil was kindly donated by the Beraca Ingredientes Naturais S.A.
company, located in the municipality of Ananindeua, in the State of Pará. The reagent used for
acidification was sulfuric acid (95–97%) purchased from Fmaia (Belo Horizonte, Brazil). The reagents
used in the characterization of the buriti oil soapstock, in the esterification of acid oil and in the
biodiesel characterization were as follows: sodium hydroxide was obtained from Ecibra (São Paulo,
Brazil), sulfuric acid (95–97%) was obtained from Fmaia (Fmaia, Brazil), sodium sulfate (99.9%)
was purchased from Isofar (Duque de Caxias, Brazil), methyl alcohol (99.9%) and heptane were
purchased from Dinamica (Diadema, Brazil), and analytical grade BF3 (12% in methanol) was obtained
from Acros organics (Alvorada, Brazil). Analytical standards, MSTFA (N-methyl-N-trimethylsilyl
trifluoroacetamide), methyl ester fatty acid (C4:0–C24:0) and C17:0 (methyl heptadecanoate (99.9%)
were obtained from Aldrich (São Paulo, Brazil).
Molecules 2019, 24, 94 7 of 9
where ai is the initial acidity of the soapstock and af is the final acidity, after acidulation.
4. Conclusions
The biodiesel produced was of high quality, with all of the physical-chemical properties analyzed
being within the limits established by the Brazilian, American and European standards, except for the
viscosity that was above the value stipulated in EN 14214, which demonstrates the viability of buriti
oil soapstock as a raw material for producing biofuel.
Author Contributions: S.S.P. performed synthesis, literature research and wrote the first draft of this paper.
V.A.d.M. performed synthesis and biodiesel characterization. C.E.F.d.C. helped to discuss some results and
provide oxidative stability experiment. J.R.Z. helped to discuss some results. G.N.d.R.F. provided part of the
reactants and materials, and the laboratories (LOA and LCO) where the final stage of tests was performed. He also
provided the correction of translation and helped to write about catalytic tests. L.A.S.d.N. provided the initial
concept for this work and advised MABL, ANO and MRS in this research, as well as providing reactants and
materials (for two research projects) and corrected the drafts and the final version of this paper.
Funding: This research was funded by CNPQ, grant number 432221/2018-2.
Acknowledgments: The authors would like to thank the laboratories that supported this work: The Laboratory
of Catalysis and Oil Chemistry (LCO/UFPA), the Laboratory of Research and Analysis of Fuels (LAPAC/UFPA)
and the Laboratory of Oils of the Amazon (LOA). The researchers would also like to thank CAPES and FAPESPA
for financial support.
Conflicts of Interest: The authors declare no conflict of interest.
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