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Journal of Cleaner Production 135 (2016) 679e688

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Journal of Cleaner Production


journal homepage: www.elsevier.com/locate/jclepro

Biodiesel production from waste cooking oil for use as fuel in artisanal
fishing boats: Integrating environmental, economic and social aspects
Elisa Helena Siegel Moecke a, b, *, Rafael Feller a, He
lia Alice dos Santos c,
Marina de Medeiros Machado a, Anelise Leal Vieira Cubas d, Ana Regina de Aguiar Dutra e,
Lucas Leonardo Vieira Santos f, Sebastia ~o Roberto Soares f
a
Environmental Engineering, University of Southern Santa Catarina e UNISUL, CEP 88279900, Palhoça, Santa Catarina, Brazil
b polis, SC, Brazil
Federal University of Santa Catarina e UFSC, Department of Food Science and Technology, Itacorubi, 88034-001, Floriano
c
City College of Palhoça e FMP, Department of Pedagogy, CEP 88130-470, Palhoça, Santa Catarina, Brazil
d
UNA - PCA, Articulation Academic Unit of Production, Construction and Agribusiness, Environmental Engineering, University of Southern Santa
Catarina e UNISUL, CEP 88279900, Palhoça, Santa Catarina, Brazil
e
Production Engineering, University of Southern Santa Catarina e UNISUL, CEP 80137-270, Palhoça, Santa Catarina, Brazil
f
Life Cycle Assessment Research Group (CICLOG) e Environmental Engineering Postgraduate Program (PPGEA) e Federal University of Santa
Catarina - UFSC, Technological Center e University Campus, Trindade, Mailbox 476, CEP 88040-970, Florianopolis, Santa Catarina, Brazil

a r t i c l e i n f o a b s t r a c t

Article history: Concern in relation to creating environmental protection policies is increasing, particularly with regard
Received 12 July 2015 to the reuse of waste for power generation. In this context, biodiesel production from waste cooking oils
Received in revised form could play an important role. Biodiesel is a biofuel that can be produced from saturated fatty raw ma-
25 May 2016
terial discarded by restaurants, such as oils and fats used for cooking processes. This paper describes a
Accepted 26 May 2016
biodiesel production plant installed at Pinheira Beach in the State of Santa Catarina, southern Brazil and
Available online 11 June 2016
aims to discuss the environmental, social and economic impacts by analyzing the biodiesel production by
life cycle assessment (LCA), relationship with the emission of greenhouse gases. The plant is run by an
Keywords:
Waste cooking oil
association and is aimed at promoting the recycling of waste cooking oil from restaurants and residences
Biodiesel in the area and, at the same time, enables the continuity of artisanal fisheries in the region. The trans-
Transesterification esterification production process was used to convert waste cooking oils into biodiesel using basic
Methyl esters catalysis in the presence of methanol. A batch system with the capacity to produce 200 L of biodiesel per
Life cycle assessment day was adopted. The data obtained for the biodiesel produced at the plant were 879.2 kg m3 density,
Carbon footprint 495.74 mg kg1 water content, 94.38% ester content, and 1.5 mg.kg1 sodium plus potassium. Related to
the Life Cycle Assessment the results demonstrate that the category that most contributes to the
emissions generated in biodiesel production process is the collection stage with 92.10% contribution,
presenting a significant difference to the productions stage which contributed 7.9%. The plant provides
environmental, social and economic gains for the community, for instance, increased income for the
associates and fishermen, environmental education in schools, and cooking oil recycling opportunities.
© 2016 Elsevier Ltd. All rights reserved.

1. Introduction the search for alternatives that do not harm the environment and
the use of clean renewable energy and reverse logistics are of great
1.1. General discussion of biofuels importance (Nikolaou et al., 2013). The clean production of energy
addresses environmental aspects by optimizing processes, whereas
In order to achieve the sustainability of production processes in reverse logistics the recycling and reuse of materials, which meet
the requirements of environmental protection and social aspects,
are priority issues (Yam and Mak, 2014). The use of waste cooking
* Corresponding author. University of Southern Santa Catarina e UNISUL, Pedra
oils to produce biodiesel fits these concepts, given that this initia-
Branca Unit, Avenue Pedra Branca, 25, Pedra Branca, CEP 88137-270, Palhoça, SC, tive avoids the inappropriate disposal of wastes and promotes the
Brazil. use of a sustainable fuel (Giraçol et al., 2011), reducing the costs of
E-mail address: smoecke@gmail.com (E.H.S. Moecke).

http://dx.doi.org/10.1016/j.jclepro.2016.05.167
0959-6526/© 2016 Elsevier Ltd. All rights reserved.
680 E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688

production and associated activities (Skarlis et al., 2012). transesterification of waste cooking oil to methyl esters using
One of the best ways to use waste oils in an efficient and cost- Agglomerated Zr-SBA-15/bentonite as active and stable catalyst.
effective way is to produce biofuel. Math et al. (2010) address The process displays high potential for the conversion of low grade
that transesterified vegetable oil (biodiesel) has attracted attention feedstock. Mohammadshirazi et al. (2014) conducted an energetic
all over the world as an alternative fuel for diesel engines because of and economical evaluation of the biodiesel production process
its reusability. from cooking oil waste using the conventional transesterification
Biodiesel can be obtained through different processes, trans- method. According to the results of this economical analysis, the
esterification being the most widely used method due to its tech- cost benefit relation was of 2.081 $, where the avarege liquid return
nical simplicity and efficiency (Morais et al., 2010). The and productivity were of 1.298 $ L1 e 0.946 $ kg1, respectively.
transesterification reaction can be carried out using alkali, acid or Utlu and Koçak (2008) developed a study which the objective
enzyme catalysts, depending on the undesirable compounds was to perform experimentally parametric tests of a turbocharged
(especially water) and free fatty acids present (Nair et al., 2012). In diesel injection engine fueled with biodiesel obtained from waste
general, the reaction proceeds more rapidly with alkali catalysts as cooking oil at several steady state operating conditions. The pro-
compared to the use of acids (Yaakob et al., 2014). The alkali- duction process was based on the transesterification method that
catalyzed transesterification of waste cooking oil is somewhat required 200 ml methyl alcohol, 6.5e8.5 g NaOH that is determined
limited in the presence of high concentrations of free fatty acids with titration, and 1e2 g acetic acid. In the first stage, test applied
and water, given that it favors the saponification reaction (Ullab the transesterification reaction is realized in the reactor tank at
et al., 2015). Despite this drawback, the alkali-catalyzed trans- 65  C temperature during 1 h. The second stage is composed of
esterification of waste cooking oil is still widely used (Yaakob et al., product rest and raw biodiesel separation from glycerin, then,
2013). washing process of obtained raw biodiesel is done by using the
After being subjected to successive heating to high temperature same volume of pure water, and second washing process follows
(around 190  C), waste cooking oils show chemical and physical and this washing process is carried out to increase the pellucidity of
changes arising from thermal, oxidative and hydrolytic reactions, biodiesel by using bubble method. They could conclude that
with the formation of various harmful and undesirable compounds cooking oil methyl ester as alternative diesel engine fuel can be
(Yaakob et al., 2013). Diya uddeen et al. (2012) report about the used successfully to operate a turbocharged direct injection diesel
injurious effect of frying oil in food preparation formulations for engine without modifications to engine or injection system.
feeding domestic animals, which resulted in a ban from 2002 in the Phan and Phan (2008) produced biodiesel from waste cooking
EU. Because this may return to the human food chain through meat oil that were collected from restaurants and shops within Ho Chi
consumption (Issariyakul et al., 2007). Thus, waste cooking oils Minh City, Vietnam. The transesterification was carried out in a
must be disposed of safely to avoid harm to human health and the 500 ml three-neck glass flask connecting with a reflux condenser
environment (Kulkarni and Dalai, 2006). using tap water to condense methanol vapour and a thermocouple
Although biodiesel comes from a renewable source, it should be probe. KOH pellets were dissolved in methanol before being poured
produced in an efficient and economic process in which the impacts in the reactor containing about 200 g of waste cooking oil (WCO)
and emissions are minimized or eliminated according to the pre- heated up to a desired temperature, which was 30  C, 50  C or 70  C.
cepts of clean production (Bonilla et al., 2010). In order to corrob- The reaction was kept at a desired temperature for 20 min, 40 min,
orate to the Bonilla et al. assertion, the authors Chang et al. (2014) 60 min, 90 min or 120 min. The results showed that the highest
and Sheinbaum-Pardo et al. (2013) emphasize that biodiesel is a yield of biodiesel was obtained at the ratio of methanol/WCO of
biodegradable fuel derived from renewable sources and its com- 7:1e8:1 during 80e90 min at temperatures ranging 30e50  C in
bustion has less harmful effects on human health compared to the presence of 0.75 wt% KOH.
petroleum diesel, with lower emissions of pollutants, such as car- Vasudevan and Briggs (2008) performed-state-of-the-art
bon monoxide and fine particulate matter, due to a more complete research that examined different biodiesel sources (edible and
combustion process Sheinbaum-Pardo et al., 2013). Furthermore, nonedible), virgin oil versus waste oil, algae-based biodiesel that is
there is no sulfur in its composition (Chang et al., 2014). gaining increasing importance, the role of different catalysts
Avhad and Marchetti (2015) presents some advantages of bio- including enzyme catalysts, and the current state-of-the-art in
diesel include: domestic origin, reducing the dependency on im- biodiesel production.
ported petroleum, biodegradability, high flash point and inherent
lubricity in the neat form. Tan et al.(2015) also mentions that bio- 1.2. Biofuels in the Brazil context
diesel has low toxicity.
Currently, the cost of biodiesel is high as compared to conven- National Petroleum Agency (ANP) and the Brazilian Association
tional diesel oil because most of the biodiesel is produced from of Vegetable Oil Industries (ABIOVE) data, referring to October,
pure vegetable oil (Sheinbaum-Pardo et al., 2013). However, the 2014, show that in this year, about 20,609 m3 of cooking oil were
cost of biodiesel can be reduced by using low cost feedstock such as allocated to biodiesel production, surpassing the year 2012, with
animal fat and used cooking oil (Chang et al., 2014). The fact that the 17,827 m3 (ABIOVE, 2014). In Brazil, about 80% of the produced
cost of biodiesel is high compared to diesel or other fuels biodiesel is derived from soybean oil, according to the Ministry of
(Enweremadu and Mbarawa, 2009), but it can be minimized when Agrarian Development (MDA), soy is considered one of the biggest
produced from a residue is reinforced by the previously mentioned culture in Brazil, soy production is almost half his acreage in grains,
authors Bonilla et al. (2010). In contrast, Enweremadu and Mbarawa especially in the Midwest and South. Technological advances are
(2009) point out that the increasing awareness of the depletion of the main reasons for this increase over the years (MAPA, 2015), but
fossil fuel resources and the environmental benefits of biodiesel the oil content in soybeans is not the highest, and, according to
fuel has made it more attractive in recent times. Paulillo et al. (2006), the oil content is approximately 18% and
The next paragraphs discuss about biodiesel production from 0.2e0.4 tons.ha1.
waste cooking oils. These studies were conducted in different In 2012e2013 Brazil's soybean crop occupies an area of 27.7
countries and reported here by different authors, reinforcing the million hectares, totaling 81.5 tons (EMBRAPA SOJA, 2015), in the
importance of reuse of cooking oil for the biodiesel production. As 2013e2014 season, for the National Supply Company (Conab), there
an example, Melero et al. (2014) carried out to investigate was increase of 6.2% in soybean cultivation area and productivity
E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688 681

reached about 3.07 kg.ha1 (CONAB, 2014). The supply chain that dimensions. To support this fact, is quoted the report Garcez and
involves culture, such as biodiesel, generates $US 980 M/y. Until Vianna (2009) that analyze the Brazilian Biodiesel Policy does
October 2014, it was 2,056,118 m3 of soybean oil for biodiesel possess the laudable objectives of promoting social inclusion and
production (ABIOVE, 2014). regional development. However, it has been found that a lack of
One of the major concern in biodiesel production is economic incentives, training, and strong Policy mechanisms have resulted in
viability. The raw material for biodiesel is considered the most the following: soybean as the dominating feedstock; the majority of
important variable cost of biodiesel in the global market. In Brazil, authorized biodiesel production capacity being installed in the
most biodiesel plants use refined vegetable oils as main raw ma- Central-West of the country; and the role of family farmers being
terial. Therefore, the cost of the refined vegetable oils contributed limited to that of producers of grains. The Policy also overlooks
about 80% of the total biodiesel production (Lam et al., 2009). The some important aspects of environmental sustainability, such as
use of the waste cooking oil as raw material for production of consumption patterns and the promotion of agricultural practices
biodiesel can reduce the cost of the final product, and is environ- that are less intensive on local ecosystems. The authors of the
mentally friendly. Currently in production of Brazilian biodiesel, article hope that the issues previously highlighted may contribute
only 0.61% is from the WCO (ANP, 2016a,b). to the national and international debate regarding biodiesel policy.
The price estimates for biodiesel can vary greatly. According to In this context, this paper describes a study on a small-scale
estimates by the International Energy Agency - IEA (IEA, 2010), the biodiesel production plant, where waste cooking oil from restau-
scale can affect 25% the final cost of biodiesel, whereas the price of rants and residences was turned into fuel for use in artisanal fishing
raw materials might represent differences of up to 50% of the final boats and the vehicles that make the selective waste collections in
cost. According to Parente (2003) a major proportion of the cost of the region. Furthermore, aims to discuss the environmental, social
biodiesel is attributed to the cost of raw material, which is around and economic impacts by analyzing the biodiesel production with
2/3 of the total production costs. The remaining portions of the life cycle assessment (LCA), relationship with the emission of
costs (such as transesterification reagents) can be partially absor- greenhouse gases.
bed by credits from the sale of glycerin. The author shows that for a
cost of raw materials of US$ 400/ton the cost of biodiesel produc- 2. Materials and methods
tion would be about US$ 0.36/L. Considering a profit margin and
freight about 25% of the final price, the biodiesel sales price would 2.1. Case study
be US$ 0.45/L, which might be considered competitive with respect
to diesel oil. 2.1.1. Study area characteristics
Alnuami et al. (2014) shows in their article that the cost of raw The biodiesel production plant, the object of this case study, is
materials in the biodiesel production is amount to about 80% of the located in a protected area named Environmental Protection Area
total operating cost, and explain that this fact is related to the high Surrounding the Coast of Serra do Tabuleiro State Park. The Serra do
cost of the feedstock oils. This high cost of feedstock oils is in turn Tabuleiro State Park is located between the geographical co-
attributed to the unavailability of sufficient agricultural land for the ordinates 2740 20900 to 28º0704200 South latitude and 48º340 0900 to
cultivation of the oil seeds for biodiesel production as the food 48º570 1300 West longitude, and covers an area of 84.130 ha, in the
materials for food production. State of Santa Catarina, Brazil (FATMA, 2009). According to infor-
At present the S10-diesel commercialization is around US$ 0.81/ mation provided by the Environmental Foundation of the State of
L1 (ANP, 2016a,b). As for biodiesel, data from the National Agency of Santa Catarina (FATMA), the park notably encompasses five of the
Petroleum (ANP) show that, in March 2015, in Brazil, the price of six phytogeographic regions of the state: mangroves, sandbanks,
the S-10 diesel (with lower sulfur content) to the refinery was US$ dense tropical rainforest, mixed tropical rainforest, and high-
0.53/L,2 3.3% higher than the average price paid to biodiesel plants, altitude grasslands (Klein, 1981). Pinheira Beach, which is charac-
which stayed at $ 0.51/L3 (ANP, 2015). terized by artisanal fishing and tourism, lies within the coastal re-
It is known that the total value of commercialization of biofuels, gion of Serra do Tabuleiro State Park.
80% refer to the cost of the raw material (US$ 0.41/L4) (Alnuami The plant is operated by an association named Pro-CREP (Create,
et al., 2014). Thus, with the use of waste vegetable oils to bio- Recycle, Educate and Preserve) comprised of Pinheira Beach resi-
diesel production, the cost concerning the raw material is zero, as it dents, which also carries out the collection and sorting of recyclable
is a residue which would be discarded, representing a saving of solid wastes.
about 21.6%, demonstrating the economic viability of biofuels Pinheira Beach was colonized by Azoreans and until the 1970s it
production from saturated vegetable oils. was still characterized as a fishing community. It has a colony of
Thus, for Brazil, according to Lucena (2008), biodiesel proposal fishermen with 30 boats registered. Severo (2008) found that the
is associated with import substitution, generating reducing main cost component of the fishing activity is the fuel (oil) used by
external vulnerability, increased national energy independence, the boats.
foreign exchange savings and consequently reduction of country Artisanal fishing is an important activity in the State of Santa
risk. Furthermore, in Brazil, as in other countries, as expressed Catarina, with around 30,000 artisanal fishermen who account for
before, interest in biodiesel is not limited to the economic dimen- approximately 30% of the state fish production. However, there are
sion, but also search results in the social and environmental problems associated with this activity, such as difficulties in rela-
tion to maintaining the fishing colonies, competition from indus-
trial fishing and pollution.
1
Considering the actual conversion price of real (R$) to US dollars (US$) on In addition to artisanal fishing, tourism drives the economy of
March 4th, 2016 in the amount of R$ 3.86 (price in Real - R$ 3.14/L e Bovespa, the region and increases the users of local services, especially res-
2016). taurants, which generate large amounts of waste cooking oil that
2
Considering the actual conversion price of real (R$) to US dollars (US$) on are often discarded improperly.
March 4th, 2016 in the amount of R$ 3.86 (price in Real - R$ 2.04/L - Bovespa, 2016).
3
Based on these concepts, the biodiesel production plant at
Considering the actual conversion price of real (R$) to US dollars (US$) on
March 4th, 2016 in the amount of R$ 3.86 (price in Real - R$ 1.98/L - Bovespa, 2016).
Pinheira Beach has the characteristics of a sustainable activity,
4
Considering the actual conversion price of real (R$) to US dollars (US$) on meeting the requirements of clean production and reverse logistics,
March 4th, 2016 in the amount of R$ 3.86 (price in Real - R$ 1.58/L - Bovespa, 2016). based on the following principles:
682 E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688

 Environmental conservation, through proper disposal of waste environment, waste and cooking oil separation. The perception of
cooking oils; the problems, the implemented strategies and other elements that
 Waste recycling by reusing waste cooking oils to produce make up their way of life, such as relations with the community and
biodiesel; knowledge of the natural environment were also addressed. In-
 Reuse of residues by utilizing the byproduct of the trans- terviews were scanned on a data sheet for carrying out the
esterification reaction (glycerol) and high acidity oil to produce assessments.
soap; After the data collection, activities related to the implementa-
 Reduction of production costs by using scrap materials for tion of the biodiesel plant in Pinheira Beach next to the waste
manufacturing reactors and solar panels for water heating in the sorting center (Pro-CREP) were initiated to satisfy the needs of
biodiesel purification process; fishermen and restaurants owners. To establish the type of trans-
 Environmental education and campaigns to involve the local formation to be adopted the following steps were carried out:
community in the collection of waste cooking oils; optimization of the production process on a laboratory scale,
 Social inclusion, with the participation of residents in the bio- equipment manufacturing, plant construction, and biodiesel pro-
diesel production process and the integration of artisanal fish- duction and evaluation.
ermen, aimed at encouraging them to remain living in the same During the project implementation, talks were given to
neighborhood and to continue the activity of artisanal fishing in disseminate the concepts within the community and provide
the region. environmental education in primary and secondary schools, in
addition to meetings with artisanal fishermen.
In order to reinforce the requirements of cleaner production and
reverse logistics, adopted by the biodiesel production plant at 2.1.3. Biodiesel production plant
Pinheira Beach is discussed here the LCA methodology, which aims Once the amount of waste cooking oil available per month had
at continuous improvement of processes and products, minimizing been quantified, was established architecture of the biodiesel
or eliminating waste. LCA is considered a methodology that seeks production plant and the optimization of reaction conditions of
continuous improvement of processes, aimed at quantifying, biodiesel production on a laboratory scale, the reactors and other
managing and further reduction of impacts, defined as a method- equipment were designed.
ology that evaluates and quantifies the potential impacts associated Scrap stainless steel material was primarily used to manufacture
with a product's life cycle, process or service (Guinee et al., 2011). the equipment. The transesterification reactor was designed for a
According to Lo € fgren et al. (2011), the LCA is seen as the most capacity of 80 L with mechanical stirring using a three-phase
important methodology in environmental management today. electric motor (WEG, W22 tri-phase motor, 220 V, 0.75 HP). The
According to Johnson (2008), the carbon footprint is the total reactor for the catalytic mixture was designed for a capacity of 15 L
greenhouse gases (GHG) emitted directly or indirectly by a person, with fins to dissipate the heat generated during the dissolution of
organization or product throughout its life cycle. One approach of KOH in methanol. A three-phase electric motor (WEG, W22 three-
LCA, known as Carbon Footprint, allows the analysis of direct and phase motor, 220 V, 0.5 HP) was coupled to this reactor to stir the
indirect emissions of greenhouse gases produced during the life mixture in order to facilitate the KOH dissolution.
cycle of an activity. As the International Standard ISO 14067, the The decanter for glycerol separation was designed for a capacity
calculation of product carbon footprint is based on the Life Cycle of 150 L. The washer and the desiccator were designed for a ca-
Assessment methodology, established in ISO 14040 and 14044 pacity of 200 L each. The washer was equipped with mechanical
standards. stirring using the same type and model installed in the trans-
esterification reactor. The distiller for methanol recovery (from
2.1.2. Survey of economic, social and environmental impacts on both glycerin and biodiesel) was designed for a capacity of 60 L. The
Pinheira beach four tanks for waste cooking oil storage and decanting were made
Open interviews were conducted with key local stakeholder of PVC material, with a capacity of 1000 L each.
(especially artisanal fishermen and restaurant owners) focusing on The next step was the construction of the physical space of the
issues related to: 1) activities in the area such as fishing and tourism plant (84 m2) to receive the reactors and other equipment. Con-
(main sources of income); 2) environment as the selective collec- structed wetlands with horizontal sub-surface flow have been
tion of cooking oil and aspects related to preserving the environ- deployed to wastewater treatment of the biodiesel production
ment and its importance for the continuation of fishing and process. For this system plants were used macrophyte species
tourism. In order to allow the understanding of the influence of the Typha latifolia and Scirpus sp. The reactors and other equipment
changes (social, economic, political, technical and environmental) were placed at key locations around the plant according to the
on the changes experienced directly by them and by other mem- production flow, as shown in the flowchart of Fig. 1.
bers of the community over time. The waste cooking oil was collected from restaurants in 50 L
The next step consists of interviews with semi-structured canisters and taken to the plant where samples were taken for
questionnaires given to residents of Pinheira beach. At this stage, acidity and moisture determination. When the levels of free fatty
fishermen interviews were conducted (15), restaurant owners (34), acids were very high (>2%) and water content was high
teachers (16) and students (170) of primary and secondary (>700 mg kg1), the oil was considered inappropriate (approxi-
education. mately 3% of the total volume collected per month) for catalysis-
In the interviews with fishermen, issues were discussed relating based biodiesel production because the free fatty acids react with
to fisheries and its importance for the region, artisanal fishing costs the base catalyst to form soap. The soap formed during the reaction
and health problems. The issues raised with the restaurant owners impairs the separation of glycerol, which reduces the ester pro-
were referring to the cooking oil quantitative generated per month, duction yield (Nurfriti et al., 2013; Enweremadú and Mbarawa,
the destination of the oil, and if they would like to donate the oil to 2009; Phan and Phan, 2008).
produce biodiesel to be used by fishermen that provide fish for The oils considered as suitable for biodiesel production were
restaurants. filtered for the removal of food waste, which was disposed of in
In the school environment questions have been raised about the landfills, and then transferred to a sequence of three decanters,
parent activity, environmental issues related to protecting the where they were separated from water and small particulates were
E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688 683

Fig. 1. Flowchart of raw material processing.

separated out. For the transesterification, the water and particulate moderate when the IP is between 5.0 and 10.0 mEq O2 kg1 oil; and
free oil was placed in a reactor, equipped with mechanical stirring, high when the IP is greater than 10 mEq O2 kg1 oil (Canesin et al.,
heated up to 50  C, and a catalytic mixture (KOH and methanol) was 2014).
added. After the transesterification reaction, methyl esters (bio- The acid number, as well as the peroxide value, reflects the
diesel) were separated from glycerol by decantation. Free-glycerol amount of free fatty acids (FFA) in the oil. Free fatty acids are
esters were rinsed with water heated to a temperature of formed under different conditions, such as high temperatures and
45 ± 3  C and dried with anhydrous sodium sulfate (Na2SO4). Low oxidation, which can occur in the presence of peroxides or light
cost water heating solar panels were installed at the plant. Meth- (Canakci, 2007). The WCO samples used in the production of bio-
anol recovered by distillation was returned to the production pro- diesel showed high values for peroxide and FFA. When the acidity
cess. The crude glycerin obtained from the biodiesel production values are greater than 2.0%, the saponification reaction can reduce
process and the waste cooking oil with free fatty acids content the transesterification reaction efficiency. Felizardo et al. (2006)
above 2% were used for soap production. have studied the influence of the oil acid value on the production
of biodiesel, six experiments were conducted using WCO with acid
values of 0.42 and 2.07. In all experiments, the biodiesel produced
2.1.4. Physicochemical characterization of waste cooking oils from the WCO with the lower acid value had a purity higher than
It is important to assess the quality of the raw material by the one obtained from the more acidic cooking oil, by as much as
providing a physicochemical characterization of the cooking oil, 14%. It was also observed that those methyl ester layers could be
given that oil degradation can lead to a decrease in ester yield. The more easily separated from the glycerol rich phases than the ones
presence of hydroperoxides caused by the exposure of oil to high produced using the more acidic WCO.
temperatures can aid the oil degradation. Table 1 shows the The saponification index (IS), which consists of the complete
physical and chemical parameters of the waste cooking oil collected hydrolysis of triacylglycerols in alkaline solutions, leads to the
from the restaurants and residences and used for the production of formation of fatty acid salts and can be used for the rapid assess-
biodiesel. ment of the potential formation of esters by determining the
The refined soybean oil oxidation level is considered low when theoretical percentage of esters according to Equation (1), as shown
the peroxide index (PI) is between 1.0 and 5.0 mEq O2 kg1 oil;
684 E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688

Table 1
Physicochemical parameters of waste cooking oils used in biodiesel synthesis.

Characteristics Units Valuea Methods

Acid value (IA) (mg KOH g1) 1.93 (±0.48) AOAC n. 940.28 (2005)
Water content (mg kg1) 655.75 (±87.24) ISO 12937 (2000)
Saponification value (IS) (mg KOH g1) 174.89 (±6.07) AOAC n.920.16 (2005)
Iodine value (IP) (g I2 100 g1) 111.64 (±8.31) AOAC n. 993.20 (2005)
Peroxide index (IP) (mEq O2 kg1) 12.02 (±2.91) AOAC n.965.33 (2005)
a
Average values of nine samples analyzed.

by Canesim (2014): reaction.


After the transesterification involving glycerol separation and
Ester content ð%Þ ¼ 100 ðIS  IAÞ=IS (1) decanting is completed, the crude biodiesel purification stage be-
Thus, the theoretical percentage of esters that can be obtained gins for the removal of the catalyst (KOH) used in the reaction and
from waste cooking oil will be 98.90%. NaCl from the food cooking process. The purification of the bio-
The fatty acids composition of the waste cooking oil showed diesel was more efficient using water heated to 40  C (±3  C) at a
small differences in comparison with soybean oil and larger dif- ratio of 70:30 (v/v) biodiesel/water.
ferences in relation to oleic acid (C18:1) and linoleic acid (C18:2). A low-cost water heating system based on solar panels was
This indicates that the waste cooking oil is a blend of vegetable oils suitable for maintaining the water at a temperature of 15  C (±3  C)
of different origins and also reflects the influence of the oxidation above room temperature without the use of electricity, throughout
process during the heating (Çetinkaya and Karaosmanog lu, 2004). the year, which allowed a saving of approximately 55.44 kWh/
The predominant fatty acids found in vegetable oils are divided month. Drying by adsorption with anhydrous sodium sulfate
into saturated (Cn:0), with no double bonds in the carbon chain, (Na2SO4), which is the last step in the biodiesel production process,
and unsaturated, with double bonds in the carbon chain. The un- was necessary to reduce the water content.
saturated fatty acids are divided into monounsaturated (Cn:1) and
polyunsaturated (Cn:2,3) as described by Ramos et al. (2009). The
2.1.6. Life cycle assessment settings
percentages of these compounds are shown in Table 2.
The carbon footprint of the biodiesel manufacturing process
The unsaturation parameters were calculated from the compo-
from cooking oil (raw material) was evaluated and is considered in
sition of monounsaturated and polyunsaturated fatty acids (wt%)
the study as zero impact because it is a residue. Thus, an LCA was
present in the oil using the empirical equation shown in Eq. (2)
conducted based on the survey data provided by the primary bio-
(Ramos et al., 2009).
diesel plant and shaped into specialized software for the global
warming impact category. Fig. 2 shows the inputs and outputs of
DU ðwt%Þ ¼ monounsaturated ðCn : 1Þ
the product system to be studied. The functional unit (FU) of the
þ 2 X polyunsaturated ðCn : 2; 3Þ (2) present study was set to 2028 kg of biodiesel (cradle to gate).
The Life Cycle Inventory (LCI), focused on specific environmental
The waste cooking oil used by Ramos et al. (2009) showed a
issues in this case - the emission of greenhouse gases (GHG)eis
degree of unsaturation similar to that of the oil used at the plant in
presented with one of the major steps in this study. The GHG
this study; however, the oil used by Ramos contained a higher
emission factor (tCO2e.kg1) provided by the Intergovernmental
concentration of monounsaturated fatty acids and lower levels of
Panel on Climate Change (IPCC) and the GHG Protocol, using the
saturated and polyunsaturated fatty acids.
methodology of Life Cycle Assessment for its determination. The
method used to collect the data necessary for modeling was by
2.1.5. Biodiesel production system completing the ICV by the head of the plant for which data were the
The biodiesel production capacity per day adopted at the plant most accurate and reliable.
was a batch of 200 L. The first process stage is filtration, aimed at In the Life Cycle Impact Assessment, to estimate emissions for
separating out the solid impurities, followed by decantation to each of the elementary input and output streams considered in
remove the fine solids and water. At this stage, 8e15% of the total product supply (Fig. 2), we used the SimaPro 8.0.2 software. The
volume was discarded, in the form of solid wastes and water, and impact assessment method chosen was the IPCC (2007) GWP 100a,
disposed of in a sanitary landfill facility. The conditions during the developed by IPCC. All GHG emissions accounted for were
optimization process (molar ratio - 1:6 oil/methanol, temperature expressed as tons of equivalent carbon dioxide (CO2e), following
50  C, KOH - 0.75% in relation to the oil mass, and reaction time 2 h standard accepted by the world scientific community, stipulated by
under mechanical stirring) were applied in the transesterification IPCC, the scientific body for matters of UN climate change.

Table 2
Compositions (wt%) of saturated, monounsaturated and polyunsaturated fatty acids, and degree of unsaturation of waste cooking oil and vegetable oils.

Chain Composition (wt%)

Waste cooking oila Waste cooking oil from Madridb Soybeanc Sunflowerc Cornc

Saturated 18.86 14.61 15.3 11.1 8.0


Monounsaturated 37.60 45.45 25.6 25.6 66.4
Polyunsaturated 43.54 39.94 59.1 63.3 25.3
Degree of unsaturation 124.68 125.33 143.8 152.2 117
a
Waste cooking oil used in this study.
b
Bautista et al., 2009.
c
Ramos et al., 2009.
E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688 685

Fig. 2. Inputs e outputs of the product system.

3. Results and discussion (Enweremadú and Mbarawa, 2009; Demirbas, 2009; Thanh et al.,
2010; Yaakob et al., 2013). Brazilian regulations do not specify a
The data collection revealed that the amount of WCO in the threshold value for the iodine index, but the European biodiesel
Pinheira Beach area was seasonal, reaching 5000 L per month in the standard EN 14214:2012 establishes a limit of 120 g I2 100 g1.
summer season due to the increased flow of tourists at that time of The iodine value is a measure of total unsaturation of a fatty
the year. Around 30 restaurants and a number of residents partic- material, the more unsaturation is present in the oil, the higher the
ipated in the project by storing waste cooking oil in 50-L canisters. index iodine (Lin et al., 2006; Ramos et al., 2009). The conversion of
A utility vehicle (Fiat Ducato), running on biofuel (B50) produced at FFA of WCO into methyl esters in this work was 94.38% (±3.54),
the plant, was used to collect the donated WCO. while the work performed by Phan and Phan (2008) also using
WCO alkali catalyst and the conversion was 90e92%. The oil is
converted into methyl esters related to the content of FFA, the free
3.1. Characterization of the waste cooking oil-based biodiesel FFA with the catalyst to form soap (Leung et al., 2010) and water
and the lower conversation (Wang et al., 2007).
In addition to the sodium and potassium measurements, the
specific mass, water content, methyl ester content and esterified
fatty acids profile were determined. 3.2. Biodiesel use
Table 3 shows the results obtained for the biodiesel produced
from waste cooking oil at the Pinheira Beach plant and the speci- Currently, the biodiesel produced at the biodiesel plant is used
fications established by the Brazilian National Petroleum Agency - to supply two vehicles, one that collects the solid waste (Ford truck,
ANP (Brazil, 2014). model 816) and a utility vehicle (Ducato, Fiat) that collects the
The water content of the biodiesel was twice the limit estab- waste cooking oil, both using B70, and three fishing boats, using
lished by the Brazilian National Petroleum Agency (ANP). However, B50. The vehicles did not shown any wear on the motor or any other
this value adheres to the EN 14214:2012 European specifications problem caused by the biodiesel after one year of use. The marine
(500 mg kg1). The density of the biodiesel is acceptable according engines (MWM Sprint and Yanmar) used in the boats showed
to standards required by ANP. The density is directly linked to the regular wear after 4 years of B50 biodiesel use, which leads us to
carbon chain length of the alkyl ester. The longer the carbon chain conclude that biodiesel is a safe fuel for use in boat engines.
the higher the density of the biodiesel will be, but this value de- All WCO is donated either by restaurants like the homes, and the
creases with the degree of unsaturation of the molecule (Vie ^gas distance to the oil collection is near the plant (an axis of 50 km),
et al., 2015). The peroxide value and the iodine index were typical reducing the costs of transporting the WCO, and in this way you can
of biodiesels obtained from waste cooking oil and basic catalysis provide biodiesel a lower value (15%) than diesel for fishermen.

Table 3
Quality parameters for biodiesel produced at the Pinheira Beach plant.

Quality parameters Unit ANP 4 - Brazil specificationa EN 14214:212 specificationb Biodieselc


 3 
Density at 20 C kg m 850e900 (860e900 at 15 C) 879.2 (±2.21)
Water content, max. mg kg1 200 500 495.74 (±141.1)
Methyl esters content, min. % mass 96.5 96.5 94.38 (±3.54)
Sodium þ potassium, max. mg/kg 5 5 1.5 (±0.13)
Acid value Mg KOH g1 0.5 0.5 0.48 (±0.18)
Peroxide value mEqO2 kg1 e e 3.82 (±1.33)
Iodine index, max. g I2100 g1 note 120 115.38 (±6.51)
a
Brazilian National Petroleum Agency (ANP) - Technical Regulation No. 3/2014 of the ANP Resolution No. 45, as of 8.25.2014.
b
EN 14214:2012 is a European Standard from 2012.
c
Mean values and standard deviation of 8 biodiesel samples.
686 E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688

Table 4 3.4. Gains for the community


Inventory Lifecycle of the CS and PS inflows.

Inputs Amount Unit Since the beginning of implementation of the plant today are
Cooking Oil 2500 kg
performed movements in the community as the “Ecovida” next to
KOH 17,3 kg Pro-CREP Association to disseminate the importance of protecting
Methanol 364.46 kg nature, because the community benefits from it to make their living
Water 2775 kg (and tourism artisanal fisheries). In this event the schools bring
NaSO4 Anhydrous 38.45 kg
their students to experience to work in the biodiesel plant and
Electricity 158.73 kWh
sorting and even learn how they separate the oil that is processed
into biofuel. The truck “Science Mobile” developed by the Univer-
sity of Southern Santa Catarina (Brazil), offers workshops, focused
Table 5
Carbon Equivalent for categories of emissions. on the environment, where students have the opportunity to
develop new knowledge. With this, the community begins to un-
Carbon equivalent (tCO2e) using petroleum (100%)
derstand how the waste properly disposed of, in addition to envi-
Collection stage (CS) Production stage (PS) Total emissions (TE) ronmental gains can help implement income of associates and for
4.17 0.36 4.53 fishermen.
Based on data from interviews, questionnaires can be said that
the Biodiesel Plant in Pinheira Beach provided the residents and the
3.3. Life cycle inventory and impact assessment rest of the community with the following benefits:

Through the development of ICV, data from elementary streams  More than 1800 residents were involved in environmental ed-
of biodiesel production input were obtained, considering the ucation events, encompassing 1300 primary school students,
collection stage (CS) and the production stage (PS), noted in Table 4. 400 secondary school students, 60 teachers, 80 community
The collection stage refers to the route by the Association leaders, and 14 community agents;
vehicle of the collection points of the raw material (waste cooking  110 people, including associates, fishermen and their families,
oil) for biodiesel production. The collection points are the com- benefited directly from the project;
mercial establishments, which are the project partners, and are  Monthly income increased by around 100% for the associate
located in different places, totaling about 30 points. members;
The production stage refers to all processes defined by the  The cost of fueling the artisanal fishing boats was reduced (in
system boundary in the biodiesel production from the cooking oil. 2014, biodiesel was sold at BRL 1.50 per liter, whereas as fossil
At this stage the raw material is already in the plant for use in the diesel cost approximately BRL 2.89 in the region);
production process.  The project enabled the empowerment of a 50-people team,
Considering the collection stage (CS), equivalent to 4.17 tons of including 39 undergraduates and 1 PhD holder, 1 environmental
CO2 were emitted. As for the Production Phase (PS) gave 0.36 tons engineer, and 9 mature program participants (Programa da
of CO2 equivalent pointing to a carbon footprint of 4.53 tons of CO2 Maturidade), related to socio-educational knowledge;
equivalent (Table 5).  The plant became a learning environment for undergraduate
However, it is noteworthy that the vehicle used in the collection engineering students.
of waste cooking oil used fuel B50, and even if the same vehicle is
used for the collection of recyclable materials in the region, In the economic field can be mention the acquisition of biodiesel
reducing 25% of emissions CO2 from the collection stage, decreasing by artisanal fishermen at a lower price than diesel that was used
to 3.13 tCO2e emissions at the Collection Stage (Table 6). previously. The association that manages the plant increased the
In the Graph 1 shows that the category that most contributes to gains (100%).
the emissions generated in biodiesel production process is the CS
with 92.10% contribution, presenting a significant difference to the
4. Conclusions
PS which contributed 7.9%.
Although, according to Dermibas (2007), combustion of bio-
The biodiesel production process at the plant located at Pinheira
diesel alone provides over a 90% reduction in total unburned hy-
Beach has contributed to the development of the local community,
drocarbons (HC), and a 75e90% reduction in polycyclic aromatic
providing environmental benefits, such as the appropriate disposal
hydrocarbons (PAHs). Biodiesel further provides significant re-
of waste cooking oil, use of biodiesel on fishing boats, social gains
ductions in particulates and carbon monoxide than petroleum
through environmental education programs, and increased income
diesel fuel.
associated with biodiesel sales.
One of the factors that most influence so that the CS is the main
The use of stainless steel scrap materials in the manufacturing of
source of impact is linked to the fact that the means of transport
equipment (reactors, distillers and washers) and the plant con-
fuels that carries out the collection of the raw material used to
struction was found to be a good strategy. In addition to reducing
produce biodiesel be non-renewable sources (diesel) and generate
costs, by avoiding spending associated with new materials in the
large amounts of CO2, but also considers the vehicle consumption
production chain, it was efficient.
and the consumption of used road.
The results related to Life Cycle Assessment e Carbon Footprint e

Table 6
Comparison of the CO2e emission in the Collection and Production stages using petroleum and biodiesel.

Carbon equivalent production stage Collection stage (CS) Production stage (PS) Total emissions (TE)

Carbon equivalent using petroleum (100%) (tCO2e) 4.17 0.36 4.53


Carbon equivalent using B50 (Biodiesel 50%) (tCO2e) 3.13 0.36 3.49
E.H.S. Moecke et al. / Journal of Cleaner Production 135 (2016) 679e688 687

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