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Accepted Manuscript

Biodiesel production from waste cooking oil for use as fuel in artisanal fishing boats:
Integrating environmental, economic and social aspects

Elisa Helena Siegel Moecke, Rafael Feller, Hélia Alice dos Santos, Marina de
Medeiros Machado, Anelise Leal Vieira Cubas, Ana Regina de Aguiar Dutra, Lucas
Leonardo Vieira Santos, Sebastião Roberto Soares
PII: S0959-6526(16)30646-1
DOI: 10.1016/j.jclepro.2016.05.167
Reference: JCLP 7349

To appear in: Journal of Cleaner Production

Received Date: 12 July 2015


Revised Date: 25 May 2016
Accepted Date: 26 May 2016

Please cite this article as: Moecke EHS, Feller R, Santos HAd, Machado MdM, Cubas ALV, Dutra
ARdA, Santos LLV, Soares SR, Biodiesel production from waste cooking oil for use as fuel in artisanal
fishing boats: Integrating environmental, economic and social aspects, Journal of Cleaner Production
(2016), doi: 10.1016/j.jclepro.2016.05.167.

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BIODIESEL PRODUCTION FROM WASTE COOKING OIL FOR USE AS


FUEL IN ARTISANAL FISHING BOATS: INTEGRATING
ENVIRONMENTAL, ECONOMIC AND SOCIAL ASPECTS

MOECKE, Elisa Helena Siegela,b*; FELLER, Rafaela; SANTOSc, Hélia Alice dos;
MACHADO, Marina de Medeirosa; CUBAS, Anelise Leal Vieirad; DUTRAe, Ana
Regina de Aguiar, SANTOS, Lucas Leonardo Vieiraf, SOARES, Sebastião Robertof.

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a
Environmental Engineering, University of Southern Santa Catarina – UNISUL, CEP
88279900, Palhoça – Santa Catarina, Brazil.

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b
Federal University of Santa Catarina – UFSC, Department of Food Science and
Technology, Itacorubi, 88034-001, Florianópolis – SC, Brazil.
c

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City College of Palhoça – FMP, Department of Pedagogy, CEP 88130-470, Palhoça –
Santa Catarina, Brazil.
d
UNA - PCA, Articulation Academic Unit of Production, Construction and

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Agribusiness, Environmental Engineering, University of Southern Santa Catarina –
UNISUL, CEP 88279900, Palhoça – Santa Catarina, Brazil.
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e
Production Engineering. University of Southern Santa Catarina – UNISUL, CEP
80137-270, Palhoça – Santa Catarina, Brazil.
f
Life Cycle Assessment Research Group (CICLOG) – Environmental Engineering
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Postgraduate Program (PPGEA) – Federal University of Santa Catarina - UFSC,


Technological Center – University Campus, Trindade, Mailbox 476, CEP 88040-970,
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Florianópolis, Santa Catarina, Brazil.


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*Corresponding author: Elisa Helena Siegel Moecke


Address: University of Southern Santa Catarina – UNISUL
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Pedra Branca Unit (Avenue Pedra Branca, 25, Pedra Branca, CEP 88137-270, Palhoça,
SC, Brasil)
CEP 80137-270
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Tel.: +55 48 32791014


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E-mail: smoecke@gmail.com

ABSTRACT

Concern in relation to creating environmental protection policies is increasing,


particularly with regard to the reuse of waste for power generation. In this context,
biodiesel production from waste cooking oils could play an important role. Biodiesel is
a biofuel that can be produced from saturated fatty raw material discarded by
restaurants, such as oils and fats used for cooking processes. This paper describes a
biodiesel production plant installed at Pinheira Beach in the State of Santa Catarina,
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southern Brazil and 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 association and is aimed at
promoting the recycling of waste cooking oil from restaurants and residences in the area
and, at the same time, enables the continuity of artisanal fisheries in the region. The
transesterification production process was used to convert waste cooking oils into
biodiesel using basic catalysis in the presence of methanol. A batch system with the

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capacity to produce 200 L of biodiesel per day was adopted. The data obtained for the
biodiesel produced at the plant were 879.2 kg m-³ density, 495.74 mg kg-1 water content,
94.38% ester content, and 1.5 mg.kg-1 sodium plus potassium. Related to the Life Cycle

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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

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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.

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Keywords: Waste cooking oil. Biodiesel. Transesterification. Methyl esters. Life Cycle
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Assessment. Carbon Footprint.
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1. INTRODUCTION
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1.1. General discussion of biofuels


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In order to achieve the sustainability of production processes the search for


alternatives that do not harm the environment and the use of clean renewable energy and
reverse logistics are of great importance (Nikolaou et al., 2013). The clean production of
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energy addresses environmental aspects by optimizing processes, whereas in reverse


logistics the recycling and reuse of materials, which meet the requirements of
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environmental protection and social aspects, are priority issues (Yam and Mak, 2014).
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The use of waste cooking oils to produce biodiesel fits these concepts, given that this
initiative avoids the inappropriate disposal of wastes and promotes the use of a
sustainable fuel (Giraçol et al., 2011), reducing the costs of production and associated
activities (Skarlis et al., 2012).
One of the best ways to use waste oils in an efficient and cost-effective way is to
produce biofuel. Math et al. (2010) address that transesterified vegetable oil (biodiesel)
has attracted attention all over the world as an alternative fuel for diesel engines because
of its reusability.
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Biodiesel can be obtained through different processes, transesterification being the


most widely used method due to its technical simplicity and efficiency (Morais et al.,
2010). The transesterification reaction can be carried out using alkali, acid or enzyme
catalysts, depending on the undesirable compounds (especially water) and free fatty
acids present (Nair et al., 2012). In general, the reaction proceeds more rapidly with
alkali catalysts as compared to the use of acids (Yaakob et al, 2014). The alkali-

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catalyzed transesterification of waste cooking oil is somewhat limited in the presence of
high concentrations of free fatty acids and water, given that it favors the saponification

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reaction (Ullab et al, 2015). Despite this drawback, the alkali-catalyzed
transesterification of waste cooking oil is still widely used (Yaakob et al, 2013).

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After being subjected to successive heating to high temperature (around 190 °C),
waste cooking oils show chemical and physical changes arising from thermal, oxidative

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and hydrolytic reactions, with the formation of various harmful and undesirable
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compounds (Yaakob et al., 2013). Diya'uddeen et al. (2012) report about the injurious
effect of frying oil in food preparation formulations for feeding domestic animals,
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which resulted in a ban from 2002 in the EU. Because this may return to the human
food chain through meat consumption (Issariyakul et al., 2007). Thus, waste cooking
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oils must be disposed of safely to avoid harm to human health and the environment
(Kulkarni and Dalai, 2006).
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Although biodiesel comes from a renewable source, it should be produced in an


efficient and economic process in which the impacts and emissions are minimized or
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eliminated according to the precepts of clean production (Bonilla et al., 2010). In order
to corroborate to the Bonilla et al. assertion, the authors Chang et al. (2014) and
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Sheinbaum-Pardo et al. (2013) emphasize that biodiesel is a biodegradable fuel derived


from renewable sources and its combustion has less harmful effects on human health
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compared to petroleum diesel, with lower emissions of pollutants, such as carbon


monoxide and fine particulate matter, due to a more complete combustion process
Sheinbaum-Pardo et al., 2013). Furthermore, there is no sulfur in its composition
(Chang et al., 2014).
Avhad and Marchetti (2015) presents some advantages of biodiesel include:
domestic origin, reducing the dependency on imported petroleum, biodegradability,
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high flash point and inherent lubricity in the neat form. Tan et al.(2015) also mentions
that biodiesel has low toxicity.
Currently, the cost of biodiesel is high as compared to conventional diesel oil
because most of the biodiesel is produced from pure vegetable oil (Sheinbaum-Pardo et
al, 2013). However, the cost of biodiesel can be reduced by using low cost feedstock
such as animal fat and used cooking oil (Chang et al., 2014). The fact that the cost of

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biodiesel is high compared to diesel or other fuels (Enweremadu and Mbarawa, 2009),
but it can be minimized when produced from a residue is reinforced by the previously

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mentioned authors Bonilla et al. (2010). In contrast, Enweremadu and Mbarawa (2009)
point out that the increasing awareness of the depletion of fossil fuel resources and the

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environmental benefits of biodiesel fuel has made it more attractive in recent times.
The next paragraphs discuss about biodiesel production from waste cooking oils.

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These studies were conducted in different countries and reported here by different
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authors, reinforcing the importance of reuse of cooking oil for the biodiesel production.
As an example, Melero et al. (2014) carried out to investigate transesterification of
waste cooking oil to methyl esters using Agglomerated Zr-SBA-15/bentonite as active
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and stable catalyst. The process displays high potential for the conversion of low grade
feedstock. Mohammadshirazi et al. (2012) conducted an energetic and economical
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evaluation of the biodiesel production process from cooking oil waste using the
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conventional transesterification method. According to the results of this economical


analysis, the cost benefit relation was of 2.081 $, where the avarege liquid return and
productivity were of 1.298 $ L-1 e 0,946 $ kg-1, respectivally.
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Utlu and Koçak (2008) developed a study which the objective was to perform
experimentally parametric tests of a turbocharged diesel injection engine fueled with
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biodiesel obtained from waste cooking oil at several steady state operating conditions.
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The production process was based on the transesterification method that required 200
ml methyl alcohol, 6.5–8.5 g NaOH that is determined with titration, and 1–2 g acetic
acid. In the first stage, test applied the transesterification reaction is realized in the
reactor tank at 65°C temperature during 1 h. The second stage is composed of product
rest and raw biodiesel separation from glycerin, then, washing process of obtained raw
biodiesel is done by using the same volume of pure water, and second washing process
follows and this washing process is carried out to increase the pellucidity of biodiesel
by using bubble method. They could conclude that cooking oil methyl ester as
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alternative diesel engine fuel can be used successfully to operate a turbocharged direct
injection diesel engine without modifications to engine or injection system.
Phan and Phan (2008) produced biodiesel from waste cooking oil that were
collected from restaurants and shops within Ho Chi Minh City, Vietnam. The
transesterification was carried out in a 500 ml three-neck glass flask connecting with a
reflux condenser using tap water to condense methanol vapour and a thermocouple

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probe. KOH pellets were dissolved in methanol before being poured in the reactor
containing about 200 g of waste cooking oil (WCO) heated up to a desired temperature,

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which was 30°C, 50°C or 70°C. The reaction was kept at a desired temperature for 20
min, 40 min, 60 min, 90 min or 120 min. The results showed that the highest yield of

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biodiesel was obtained at the ratio of methanol/WCO of 7:1– 8:1 during 80–90 min at
temperatures ranging 30–50°C in the presence of 0.75 wt% KOH.

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Vasudevan and Briggs (2008) performed-state-of-the-art research that examined
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different biodiesel sources (edible and nonedible), virgin oil versus waste oil, algae-
based biodiesel that is gaining increasing importance, the role of different catalysts
including enzyme catalysts, and the current state-of-the-art in biodiesel production.
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1.2. Biofuels in the Brazil context


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National Petroleum Agency (ANP) and the Brazilian Association of Vegetable Oil
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Industries (ABIOVE) data, referring to October, 2014, show that in this year, about
20,609 m3 of cooking oil were allocated to biodiesel production, surpassing the year
2012, with 17,827 m3 (ABIOVE, 2014). In Brazil, about 80% of the produced biodiesel
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is derived from soybean oil, according to the Ministry of Agrarian Development


(MDA), soy is considered one of the biggest culture in Brazil, soy production is almost
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half his acreage in grains, especially in the Midwest and South. Technological advances
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are the main reasons for this increase over the years (MAPA, 2015), but the oil content
in soybeans is not the highest, and, according to Paulillo (2006), the oil content is
approximately 18% and 0.2 - 0.4 tons.ha-1.
In 2012-2013 Brazil’s soybean crop occupies an area of 27.7 million hectares,
totaling 81.5 tons (EMBRAPA SOJA, 2015), in the 2013-2014 season, for the National
Supply Company (Conab), there was increase of 6.2% in soybean cultivation area and
productivity reached about 3.07 kg.ha-1 (CONAB, 2014). The supply chain that involves
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culture, such as biodiesel, generates $US 980 M/y. Until October 2014, it was 2,056,118
m3 of soybean oil for biodiesel production (ABIOVE, 2014).
One of the major concern in biodiesel production is economic viability. The raw
material for biodiesel is considered the most important variable cost of biodiesel in the
global market. In Brazil, most biodiesel plants use refined vegetable oils as main raw
material. Therefore, the cost of the refined vegetable oils contributed about 80% of the

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total biodiesel production (Lam et al., 2009). The use of the waste cooking oil as raw
material for production of biodiesel can reduce the cost of the final product, and is

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environmentally friendly. Currently in production of Brazilian biodiesel, only 0.61% is
from the WCO (ANP, 2016).

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The price estimates for biodiesel can vary greatly. According to estimates by the
International Energy Agency - IEA (IEA, 2010), the scale can affect 25% the final cost

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of biodiesel, whereas the price of raw materials might represent differences of up to
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50% of the final cost. According to Parente (2003) a major proportion of the cost of
biodiesel is attributed to the cost of raw material, which is around 2/3 of the total
production costs. The remaining portions of the costs (such as transesterification
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reagents) can be partially absorbed 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 production
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would be about US$ 0.36/L. Considering a profit margin and freight about 25% of the
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final price, the biodiesel sales price would be US$ 0.45/L, which might be considered
competitive with respect to diesel oil.
Alnuami et al. (2014) shows in their article that the cost of raw materials in the
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biodiesel production is amount to about 80% of the total operating cost, and explain that
this fact is related to the high cost of the feedstock oils. This high cost of feedstock oils
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is in turn attributed to the unavailability of sufficient agricultural land for the cultivation
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of the oil seeds for biodiesel production as the food materials for food production.
At present the S10-diesel commercialization is around US$ 0.81/L1 (ANP, 2016).
As for biodiesel, data from the National Agency of Petroleum (ANP) show that, in
March 2015, in Brazil, the price of the S-10 diesel (with lower sulfur content) to the

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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$ 3.14/L – Bovespa, 2016).
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refinery was US$ 0.53/L2, 3.3% higher than the average price paid to biodiesel plants,
which stayed at $ 0.51 / L3 (ANP 2015).
It is known that the total value of commercialization of biofuels, 80% refer to the
cost of the raw material (US$ 0.41/L4) (Alnuami et al., 2014). Thus, with the use of
waste vegetable oils to biodiesel production, the cost concerning the raw material is
zero, as it is a residue which would be discarded, representing a saving of about 21.6%,

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demonstrating the economic viability of biofuels production from saturated vegetable
oils.

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Thus, for Brazil, according to Lucena (2008), biodiesel proposal is associated with
import substitution, generating reducing external vulnerability, increased national

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energy independence, foreign exchange savings and consequently reduction of country
risk. Furthermore, in Brazil, as in other countries, as expressed before, interest in

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biodiesel is not limited to the economic dimension, but also search results in the social
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and environmental dimensions. To support this fact, is quoted the report Garcez and
Vianna (2009) that analyze the Brazilian Biodiesel Policy does possess the laudable
objectives of promoting social inclusion and regional development. However, it has
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been found that a lack of incentives, training, and strong Policy mechanisms have
resulted in the following: soybean as the dominating feedstock; the majority of
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authorized biodiesel production capacity being installed in the Central-West of the


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country; and the role of family farmers being limited to that of producers of grains. The
Policy also overlooks some important aspects of environmental sustainability, such as
consumption patterns and the promotion of agricultural practices that are less intensive
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on local ecosystems. The authors of the article hope that the issues previously
highlighted may contribute to the national and international debate regarding biodiesel
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policy.
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In this context, this paper describes a study on a small-scale biodiesel production


plant, where waste cooking oil from restaurants and residences was turned into fuel for
use in artisanal fishing boats and the vehicles that make the selective waste collections
in the region. Furthermore, aims to discuss the environmental, social and economic

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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$ 2.04/L - Bovespa, 2016).
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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).
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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$ 1.58/L - Bovespa, 2016).
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impacts by analyzing the biodiesel production with life cycle assessment (LCA),
relationship with the emission of greenhouse gases.

2 MATERIALS AND METHODS

2.1 Case Study

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2.2.1 Study area characteristics

The biodiesel production plant, the object of this case study, is located in a

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protected area named Environmental Protection Area Surrounding the Coast of Serra do
Tabuleiro State Park. The Serra do Tabuleiro State Park is located between the

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geographical coordinates 27°4'209" to 28º07'42" South latitude and 48º34'09" to
48º57'13" West longitude, and covers an area of 84.130 hectares, in the State of Santa

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Catarina, Brazil (FATMA, 2009). According to information provided by the
Environmental Foundation of the State of Santa Catarina (FATMA), the park notably
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encompasses five of the six phytogeographic regions of the state: mangroves,
sandbanks, dense tropical rainforest, mixed tropical rainforest, and high-altitude
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grasslands (Klein, 1981). Pinheira Beach, which is characterized by artisanal fishing and
tourism, lies within the coastal region of Serra do Tabuleiro State Park.
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The plant is operated by an association named Pro-CREP (Create, Recycle, Educate


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and Preserve) comprised of Pinheira Beach residents, which also carries out the
collection and sorting of recyclable solid wastes.
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Pinheira Beach was colonized by Azoreans and until the 1970s it was still
characterized as a fishing community. It has a colony of fishermen with 30 boats
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registered. Severo (2008) found that the main cost component of the fishing activity is
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the fuel (oil) used by the boats.


Artisanal fishing is an important activity in the State of Santa Catarina, with around
30,000 artisanal fishermen who account for approximately 30% of the state fish
production. However, there are problems associated with this activity, such as
difficulties in relation to maintaining the fishing colonies, competition from industrial
fishing and pollution.
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In addition to artisanal fishing, tourism drives the economy of the region and
increases the users of local services, especially restaurants, which generate large
amounts of waste cooking oil that are often discarded improperly.
Based on these concepts, the biodiesel production plant at Pinheira Beach has the
characteristics of a sustainable activity, meeting the requirements of clean production
and reverse logistics, based on the following principles:

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• Environmental conservation, through proper disposal of waste cooking oils;
• Waste recycling by reusing waste cooking oils to produce biodiesel;

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• Reuse of residues by utilizing the byproduct of the transesterification reaction

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(glycerol) and high acidity oil to produce soap;
• Reduction of production costs by using scrap materials for manufacturing
reactors and solar panels for water heating in the biodiesel purification process;

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• Environmental education and campaigns to involve the local community in the
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collection of waste cooking oils;
• Social inclusion, with the participation of residents in the biodiesel production
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process and the integration of artisanal fishermen, aimed at encouraging them to


remain living in the same neighborhood and to continue the activity of artisanal
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fishing in the region.


In order to reinforce the requirements of cleaner production and reverse logistics,
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adopted by the biodiesel production plant at Pinheira Beach is discussed here the LCA
methodology, which aims at continuous improvement of processes and products,
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minimizing or eliminating waste. LCA is considered a methodology that seeks


continuous improvement of processes, aimed at quantifying, managing and further
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reduction of impacts, defined as a methodology that evaluates and quantifies the


potential impacts associated with a product's life cycle, process or service (Guinée et al.,
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2011). According to Löfgren, Tillman, and Rinde (2011), the LCA is seen as the most
important methodology in environmental management today. According to Johnson
(2008), the carbon footprint is the total greenhouse gases (GHG) emitted directly or
indirectly by a person, organization or product throughout its life cycle. One approach
of LCA, known as Carbon Footprint, allows the analysis of direct and indirect emissions
of greenhouse gases produced during the life cycle of an activity. As the International
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Standard ISO 14067, the calculation of product carbon footprint is based on the Life
Cycle Assessment methodology, established in ISO 14040 and 14044 standards.

2.2.2 Survey of economic, social and environmental impacts on Pinheira beach


Open interviews were conducted with key local stakeholder (especially artisanal
fishermen and restaurant owners) focusing on issues related to: 1) activities in the area

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such as fishing and tourism (main sources of income); 2) environment as the selective
collection of cooking oil and aspects related to preserving the environment and its

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importance for the continuation of fishing and tourism. In order to allow the
understanding of the influence of the changes (social, economic, political, technical and

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environmental) on the changes experienced directly by them and by other members of
the community over time.

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The next step consists of interviews with semi-structured questionnaires given to
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residents of Pinheira beach. At this stage, fishermen interviews were conducted (15),
restaurant owners (34), teachers (16) and students (170) of primary and secondary
education.
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In the interviews with fishermen, issues were discussed relating to fisheries and its
importance for the region, artisanal fishing costs and health problems. The issues raised
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with the restaurant owners were referring to the cooking oil quantitative generated per
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month, the destination of the oil, and if they would like to donate the oil to produce
biodiesel to be used by fishermen that provide fish for restaurants.
In the school environment questions have been raised about the parent activity,
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environmental issues related to protecting the environment, waste and cooking oil
separation. The perception of the problems, the implemented strategies and other
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elements that make up their way of life, such as relations with the community and
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knowledge of the natural environment were also addressed. Interviews were scanned on
a data sheet for carrying out the assessments.
After the data collection, activities related to the implementation of the biodiesel
plant in Pinheira Beach next to the waste sorting center (Pro-CREP) were initiated to
satisfy the needs of fishermen and restaurants owners. To establish the type of
transformation to be adopted the following steps were carried out: optimization of the
production process on a laboratory scale, equipment manufacturing, plant construction,
and biodiesel production and evaluation.
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During the project implementation, talks were given to disseminate the concepts
within the community and provide environmental education in primary and secondary
schools, in addition to meetings with artisanal fishermen.

2.2.3 Biodiesel production plant


Once the amount of waste cooking oil available per month had been quantified, was

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established architecture of the biodiesel production plant and the optimization of
reaction conditions of biodiesel production on a laboratory scale, the reactors and other

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equipment were designed.
Scrap stainless steel material was primarily used to manufacture the equipment. The

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transesterification reactor was designed for a capacity of 80 L with mechanical stirring
using a three-phase electric motor (WEG, W22 tri-phase motor, 220 V, 0.75 HP). The

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reactor for the catalytic mixture was designed for a capacity of 15 L with fins to
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dissipate the heat generated during the dissolution of KOH in methanol. A three-phase
electric motor (WEG, W22 three-phase motor, 220 V, 0.5 HP) was coupled to this
reactor to stir the mixture in order to facilitate the KOH dissolution.
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The decanter for glycerol separation was designed for a capacity of 150 L. The
washer and the desiccator were designed for a capacity of 200 L each. The washer was
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equipped with mechanical stirring using the same type and model installed in the
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transesterification reactor. The distiller for methanol recovery (from both glycerin and
biodiesel) was designed for a capacity of 60 L. The four tanks for waste cooking oil
storage and decanting were made of PVC material, with a capacity of 1,000 L each.
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The next step was the construction of the physical space of the plant (84 m2) to
receive the reactors and other equipment. Constructed wetlands with horizontal sub-
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surface flow have been deployed to wastewater treatment of the biodiesel production
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process. For this system plants were used macrophyte species Typha latifolia and
Scirpus sp. The reactors and other equipment were placed at key locations around the
plant according to the production flow, as shown in the flowchart of Figure 1.
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Figure 1. Flowchart of raw material processing.

The waste cooking oil was collected from restaurants in 50 L canisters and taken
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to the plant where samples were taken for acidity and moisture determination. When the
levels of free fatty acids were very high (> 2%) and water content was high (> 700 mg
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kg-1), the oil was considered inappropriate (approximately 3% of the total volume
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collected per month) for catalysis-based biodiesel production because the free fatty
acids react with the base catalyst to form soap. The soap formed during the reaction
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impairs the separation of glycerol, which reduces the ester production yield (Nurfriti et
al., 2013; Enweremadu and Mbarawa, 2009; Phan and Phan, 2008).
The oils considered as suitable for biodiesel production were filtered for the
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removal of food waste, which was disposed of in landfills, and then transferred to a
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sequence of three decanters, where they were separated from water and small
particulates were separated out. For the transesterification, the water and particulate free
oil was placed in a reactor, equipped with mechanical stirring, heated up to 50 °C, and a
catalytic mixture (KOH and methanol) was added. After the transesterification reaction,
methyl esters (biodiesel) were separated from glycerol by decantation. Free-glycerol
esters were rinsed with water heated to a temperature of 45 ± 3°C and dried with
anhydrous sodium sulfate (Na2SO4). Low cost water heating solar panels were installed
at the plant. Methanol recovered by distillation was returned to the production process.
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The crude glycerin obtained from the biodiesel production process and the waste
cooking oil with free fatty acids content above 2% were used for soap production.

2.2.4 Physicochemical characterization of waste cooking oils


It is important to assess the quality of the raw material by providing a
physicochemical characterization of the cooking oil, given that oil degradation can lead

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to a decrease in ester yield. The presence of hydroperoxides caused by the exposure of
oil to high temperatures can aid the oil degradation. Table 1 shows the physical and

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chemical parameters of the waste cooking oil collected from the restaurants and
residences and used for the production of biodiesel.

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

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Characteristics Units Value(*) Methods
Acid value (IA) (mg KOH g-1) 1.93 (± 0.48) AOAC n. 940.28
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(2005)
Water content (mg kg-1) 655.75 (± 87.24) ISO 12937 (2000)
Saponification value (IS) (mg KOH g-1) 174.89 (± 6.07) AOAC n.920.16
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(2005)
Iodine value (IP) (g I2 100 g-1) 111.64 (± 8.31) AOAC n. 993.20
(2005)
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Peroxide index (IP) (mEq O2 kg-1) 12.02 (± 2.91) AOAC n.965.33


(2005)
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* Average values of nine samples analyzed.

The refined soybean oil oxidation level is considered low when the peroxide index
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(PI) is between 1.0 and 5.0 mEq O2 kg-1 oil; moderate when the IP is between 5.0 and
10.0 mEq O2 kg-1 oil; and high when the IP is greater than 10 mEq O2 kg-1 oil (Canesim
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et al., 2014).
The acid number, as well as the peroxide value, reflects the amount of free fatty
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acids (FFA) in the oil. Free fatty acids are formed under different conditions, such as
high temperatures and oxidation, which can occur in the presence of peroxides or light
(Canakci, 2007). The WCO samples used in the production of biodiesel showed high
values for peroxide and FFA. When the acidity values are greater than 2.0%, the
saponification reaction can reduce the transesterification reaction efficiency. Felizardo
et al. (2006) 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
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2.07. In all experiments, the biodiesel produced from the WCO with the lower acid
value had a purity higher than the one obtained from the more acidic cooking oil, by as
much as 14%. It was also observed that those methyl ester layers could be more easily
separated from the glycerol rich phases than the ones produced using the more acidic
WCO.
The saponification index (IS), which consists of the complete hydrolysis of

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triacylglycerols in alkaline solutions, leads to the formation of fatty acid salts and can be
used for the rapid assessment of the potential formation of esters by determining the

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theoretical percentage of esters according to Equation 1, as shown by Canesim (2014):
Ester content (%) = 100 (IS – IA)/IS (1)

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Thus, the theoretical percentage of esters that can be obtained from waste cooking
oil will be 98.90%.

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The fatty acids composition of the waste cooking oil showed small differences in
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comparison with soybean oil and larger differences in relation to oleic acid (C18:1) and
linoleic acid (C18:2). This indicates that the waste cooking oil is a blend of vegetable
oils of different origins and also reflects the influence of the oxidation process during
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the heating (Çetinkaya and Karaosmanoğlu, 2004).


The predominant fatty acids found in vegetable oils are divided into saturated
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(Cn:0), with no double bonds in the carbon chain, and unsaturated, with double bonds in
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the carbon chain. The unsaturated fatty acids are divided into monounsaturated (Cn:1)
and polyunsaturated (Cn:2,3) as described by Ramos et al. (2009). The percentages of
these compounds are shown in Table 2.
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Table 2. Compositions (wt%) of saturated, monounsaturated and polyunsaturated fatty


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acids, and degree of unsaturation of waste cooking oil and vegetable oils.
Composition (wt%)
AC

Waste
Chain Waste
cooking oil
cooking Soybeanc Sunflowerc Cornc
from
oila
Madridb
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 124.68 125.33 143.8 152.2 117
unsaturation
a
Waste cooking oil used in this study; bBautista et al., 2009; cRamos et al., 2009.
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The unsaturation parameters were calculated from the composition of


monounsaturated and polyunsaturated fatty acids (wt%) present in the oil using the
empirical equation shown in Eq. 2 (Ramos et al., 2009).
DU (wt%) = monounsaturated (Cn:1) + 2 X polyunsaturated (Cn:2; 3) (2)

The waste cooking oil used by Ramos et al. (2009) showed a degree of unsaturation

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similar to that of the oil used at the plant in this study; however, the oil used by Ramos
contained a higher concentration of monounsaturated fatty acids and lower levels of

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saturated and polyunsaturated fatty acids.

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2.2.5 Biodiesel production system
The biodiesel production capacity per day adopted at the plant was a batch of 200

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L. The first process stage is filtration, aimed at separating out the solid impurities,
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followed by decantation to remove the fine solids and water. At this stage, 8-15% of the
total volume was discarded, in the form of solid wastes and water, and disposed of in a
sanitary landfill facility. The conditions during the optimization process (molar ratio -
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1:6 oil/methanol, temperature 50 °C, KOH - 0.75% in relation to the oil mass, and
reaction time 2 h under mechanical stirring) were applied in the transesterification
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reaction.
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After the transesterification involving glycerol separation and decanting is


completed, the crude biodiesel purification stage begins for the removal of the catalyst
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(KOH) used in the reaction and NaCl from the food cooking process. The purification
of the biodiesel was more efficient using water heated to 40 °C (± 3 °C) at a ratio of
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70:30 (v/v) biodiesel/water.


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A low-cost water heating system based on solar panels was suitable for maintaining
the water at a temperature of 15 °C (± 3 °C) above room temperature without the use of
electricity, throughout the year, which allowed a saving of approximately 55.44
kWh/month. Drying by adsorption with anhydrous sodium sulfate (Na2SO4), which is
the last step in the biodiesel production process, was necessary to reduce the water
content.
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2.2.6 Life Cycle Assessment settings


The carbon footprint of the biodiesel manufacturing process from cooking oil (raw
material) was evaluated and is considered in the study as zero impact because it is a
residue. Thus, an LCA was conducted based on the survey data provided by the primary
biodiesel plant and shaped into specialized software for the global warming impact
category. Figure 2 shows the inputs and outputs of the product system to be studied. The

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functional unit (FU) of the present study was set to 2028 kg of biodiesel (cradle to gate).

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Figure 2. Inputs e outputs of the product system.


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The Life Cycle Inventory (LCI), focused on specific environmental issues in this
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case - the emission of greenhouse gases (GHG) - is presented with one of the major
steps in this study. The GHG emission factor (tCO2e.kg-1) provided by the
Intergovernmental Panel on Climate Change (IPCC) and the GHG Protocol, using the
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methodology of Life Cycle Assessment for its determination. The method used to
collect the data necessary for modeling was by completing the ICV by the head of the
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plant for which data were the most accurate and reliable.
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In the Life Cycle Impact Assessment, to estimate emissions for each of the
elementary input and output streams considered in product supply (Figure 2), we used
the SimaPro 8.0.2 software. The impact assessment method chosen was the IPCC
(2007) GWP 100a, developed by IPCC. All GHG emissions accounted for were
expressed as tons of equivalent carbon dioxide (CO2e), following standard accepted by
the world scientific community, stipulated by IPCC, the scientific body for matters of
UN climate change.
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3. RESULTS AND DISCUSSION


The data collection revealed that the amount of WCO in the Pinheira Beach area
was seasonal, reaching 5,000 L per month in the summer season due to the increased
flow of tourists at that time of the year. Around 30 restaurants and a number of residents
participated in the project by storing waste cooking oil in 50-L canisters. A utility
vehicle (Fiat Ducato), running on biofuel (B50) produced at the plant, was used to

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collect the donated WCO.

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3.1 Characterization of the waste cooking oil-based biodiesel
In addition to the sodium and potassium measurements, the specific mass, water

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content, methyl ester content and esterified fatty acids profile were determined.

Table 3 shows the results obtained for the biodiesel produced from waste cooking

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oil at the Pinheira Beach plant and the specifications established by the Brazilian
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National Petroleum Agency - ANP (Brazil, 2014).

Table 3. Quality parameters for biodiesel produced at the Pinheira Beach plant.
ANP 4 - EN
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BRAZIL 14214:212
Quality parameters Unit Biodiesel (c)
Specification Specification
(a) (b)
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Density at 20 ° C kg m-3 850 - 900 (860 – 900 879.2 (± 2.21)


at 15 ºC)
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Water content, max. mg kg-1 200 500 495.74 (± 141.1)


Methyl esters % mass 96.5 96.5 94.38 (± 3.54)
content, min.
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Sodium + potassium, mg/kg 5 5 1.5 (± 0.13)


max.
Acid value Mg KOH g- 0.5 0,5 0.48 (± 0.18)
1
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Peroxide value mEqO2kg-1 -- -- 3.82 (± 1.33)


Iodine index, max. g I2100g-1 note 120 115.38 (± 6.51)
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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.

The water content of the biodiesel was twice the limit established by the Brazilian
National Petroleum Agency (ANP). However, this value adheres to the EN 14214:2012
European specifications (500 mg kg-1). The density of the biodiesel is acceptable
according to standards required by ANP. The density is directly linked to the carbon
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chain length of the alkyl ester. The longer the carbon chain the higher the density of the
biodiesel will be, but this value decreases with the degree of unsaturation of the
molecule (Viêgas et al., 2015). The peroxide value and the iodine index were typical of
biodiesels obtained from waste cooking oil and basic catalysis (Enweremadú, Mbarawa,
2009; Demirbas, 2009; Thanh et al., 2010; Yaakob, 2013). Brazilian regulations do not
specify a threshold value for the iodine index, but the European biodiesel standard EN

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14214:2012 establishes a limit of 120 g I2 100 g-1.
The iodine value is a measure of total unsaturation of a fatty material, the more

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unsaturation is present in the oil, the higher the index iodine (Lin et al., 2006; Ramos et
al., 2009). The conversion of FFA of WCO into methyl esters in this work was 94.38 %

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(± 3.54), while the work performed by Phan and Phan (2008) also using WCO alkali
catalyst and the conversion was 90 - 92%. The oil is converted into methyl esters related

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to the content of FFA, the free FFA with the catalyst to form soap (Leung et al., 2010)
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and water and the lower conversation (Wang et al., 2007).

3.2 Biodiesel use


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Currently, the biodiesel produced at the biodiesel plant is used to supply two
vehicles, one that collects the solid waste (Ford truck, model 816) and a utility vehicle
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(Ducato, Fiat) that collects the waste cooking oil, both using B70, and three fishing
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boats, using B50. The vehicles did not shown any wear on the motor or any other
problem caused by the biodiesel after one year of use. The marine engines (MWM
Sprint and Yanmar) used in the boats showed regular wear after 4 years of B50
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biodiesel use, which leads us to conclude that biodiesel is a safe fuel for use in boat
engines.
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All WCO is donated either by restaurants like the homes, and the distance to the oil
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collection is near the plant (an axis of 50 km), reducing the costs of transporting the
WCO, and in this way you can provide biodiesel a lower value (15%) than diesel for
fishermen.

3.3 Life Cycle Inventory and Impact Assessment


Through the development of ICV, data from elementary streams of biodiesel
production input were obtained, considering the collection stage (CS) and the
production stage (PS), noted in Table 4.
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The collection stage refers to the route by the Association vehicle of the collection
points of the raw material (waste cooking oil) for biodiesel production. The collection
points are the commercial establishments, which are the project partners, and are located
in different places, totaling about 30 points.
The production stage refers to all processes defined by the system boundary in the
biodiesel production from the cooking oil. At this stage the raw material is already in

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the plant for use in the production process.

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Table 4. Inventory Lifecycle of the CS and PS inflows.
Imputs Amount Unit

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Cooking Oil 2500 kg
KOH 17,3 kg
Methanol 364,46 kg

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Water 2775 kg
NaSO4 Anhydrous 38,45 kg
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Electricity 158,73 kWh

Considering the collection stage (CS), equivalent to 4.17 tons of CO2 were emitted.
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As for the Production Phase (PS) gave 0.36 tons of CO2 equivalent pointing to a carbon
footprint of 4.53 tons of CO2 equivalent (Table 5).
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Table 5. Carbon Equivalent for categories of emissions.


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Carbon Equivalent (tCO2e) using Petroleum (100%)


Collection Stage Production Stage Total Emissions
(CS) (PS) (TE)
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4,17 0,36 4,53

However, it is noteworthy that the vehicle used in the collection of waste cooking
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oil used fuel B50, and even if the same vehicle is used for the collection of recyclable
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materials in the region, reducing 25% of emissions CO2 from the collection stage,
decreasing to 3.13 tCO2e emissions at the Collection Stage (Table 6).

Table 6. Comparison of the CO2e emission in the Collection and Production stages
using petroleum and biodiesel.
Carbon Equivalent Collection Stage Production Stage Total Emissions
Production Stage (CS) (PS) (TE)
Carbon Equivalent
using Petroleum (100%) 4,17 0,36 4,53
(tCO2e)
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Carbon Equivalent
using B50 (Biodiesel 50%) 3,13 0,36 3,49
(tCO2e)

In the Graph 1 shows that the category that most contributes to the emissions
generated in biodiesel production process is the CS with 92.10% contribution,
presenting a significant difference to the PS which contributed 7.9%.

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Graph 1. CO2 emissions equivalent by category as a percentage.

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Although, according to Dermibas (2007), combustion of biodiesel alone provides


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over a 90% reduction in total unburned hydrocarbons (HC), and a 75–90% reduction in
polycyclic aromatic hydrocarbons (PAHs). Biodiesel further provides significant
reductions in particulates and carbon monoxide than petroleum diesel fuel.
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One of the factors that most influence so that the CS is the main source of impact is
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linked to the fact that the means of transport fuels that carries out the collection of the
raw material used to produce biodiesel be non-renewable sources (diesel) and generate
large amounts of CO2, but also considers the vehicle consumption and the consumption
of used road.
3.4 Gains for the community
Since the beginning of implementation of the plant today are performed movements
in the community as the "Ecovida" next to Pro-CREP Association to disseminate the
importance of protecting nature, because the community benefits from it to make their
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living (and tourism artisanal fisheries). In this event the schools bring their students to
experience to work in the biodiesel plant and sorting and even learn how they separate
the oil that is processed into biofuel. The truck "Science Mobile" developed by the
University of Southern Santa Catarina (Brazil), offers workshops, focused on the
environment, where students have the opportunity to develop new knowledge. With
this, the community begins to understand how the waste properly disposed of, in

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addition to environmental gains can help implement income of associates and for
fishermen.

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Based on data from interviews, questionnaires can be said that the Biodiesel Plant
in Pinheira Beach provided the residents and the rest of the community with the

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following benefits:
• More than 1,800 residents were involved in environmental education events,

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encompassing 1,300 primary school students, 400 secondary school
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students, 60 teachers, 80 community leaders, and 14 community agents;
• 110 people, including associates, fishermen and their families, benefited
directly from the project;
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• Monthly income increased by around 100% for the associate members;


• The cost of fueling the artisanal fishing boats was reduced (in 2014,
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biodiesel was sold at BRL 1.50 per liter, whereas as fossil diesel cost
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approximately BRL 2.89 in the region);


• The project enabled the empowerment of a 50-people team, including 39
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undergraduates and 1 PhD holder, 1 environmental engineer, and 9 mature


program participants (Programa da Maturidade), related to socio-
educational knowledge;
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• The plant became a learning environment for undergraduate engineering


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students.
In the economic field can be mention the acquisition of biodiesel by artisanal
fishermen at a lower price than diesel that was used previously. The association that
manages the plant increased the gains (100%).
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4. CONCLUSIONS

The biodiesel production process at the plant located at Pinheira Beach has
contributed to the development of the local community, providing environmental
benefits, such as the appropriate disposal of waste cooking oil, use of biodiesel on
fishing boats, social gains through environmental education programs, and increased

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income associated with biodiesel sales.
The use of stainless steel scrap materials in the manufacturing of equipment
(reactors, distillers and washers) and the plant construction was found to be a good

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strategy. In addition to reducing costs, by avoiding spending associated with new

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materials in the production chain, it was efficient.
The results related to Life Cycle Assessment – Carbon Footprint – demonstrate that
the category that most contributes to the emissions generated in biodiesel production

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process is the collection stage with 92.10% contribution, presenting a significant
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difference to the productions stage which contributed 7.9%. However, considering the
fact that the vehicle collection also operates the collection of recyclable materials from
the region, the related CO2e value related to collection stage is reduced by 25% (3,13
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CO2e).
These results demonstrate that the biodiesel produced at the local plant can be used
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in the activities of fishing and selective collection without causing damage to the
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engines. Furthermore, it should be emphasized that student participation in the project


played a major role, turning the plant into a teaching and learning environment.
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ACKNOWLEDGEMENTS
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This study was supported by the National Council of Scientific and Technological
Development (CNPq) of the Brazilian Ministry of Science, Technology and Innovation
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(Project N° 560444/2008-7), and the Santander University Solidarity Award.

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ACCEPTED MANUSCRIPT
HIGHLIGHTS

 Promotion the recycling of waste cooking oil and continuity of artisanal fisheries.

 The biodiesel can be used in the fishing activities with no damage to the engines.

 Physicochemical quality biodiesel parameters was in accordance with Brazilian


laws.

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 It was developed an Life Cycle Assessment in the biodiesel production;

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 The CO2e more significant was related to the collection stage (transport).

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