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Fuel 155 (2015) 1–6

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Fuel
j o u r n a l h o m e p a g e : w w w. e l s e v i e r. c o m / l o c a t e / f u e l

Purification adsorbents of biodiesel by dry washing, employing starch


and cellulose as natural

Michelle Garcia Gomes a,1, Douglas Queiroz Santos b,2, Luís Carlos de Morais c,3, Daniel Pasquini a,
a
Federal University of Uberlândia, Chemistry Institute, Av. João Naves de Ávila, 2121, Bloco 1D, Campus Santa Mônica, Uberlândia, Minas Gerais 38400-902, Brazil
b
Federal University of Uberlândia, Technical School of Health, Av. Prof. José Inácio de Souza, s/n , Bloco 6X, 1 andar, Campus, Uberlândia, Minas Gerais 38400-902, Brazil
c
Federal University of Triângulo Mineiro, Institute of Exact Sciences, Natural and Education, Av. Dr. Randolfo Borges, 1400, Univerdecidade, Uberaba, Minas Gerais 38064-200, Brazil

h i g h l i g h t s

Biodiesel from sunflower oil was successfully purified with natural adsorbents.
Starch from different sources and cellulose fibers were used as adsorbents.
Dry washing has removed more impurities than the wet washing.
Was reduced the acidity index, alkalinity, free glycerine and turbidity of biodiesel.

a r t i c l e i n f o a b s t r a c t
Article history: This work describes a study of the purification of biodiesel produced from sunflower oil by dry cold
Received 12 January 2015
washing using natural adsorbents as cellulose and starch from different sources (corn, potato, cassava
Received in revised form 31 March 2015
Accepted 3 April 2015 and rice), and the comparison with dry cold washing with a commercial adsorbent Select 450 and with
Available online 13 April 2015 the conventional wet washing with hot water. The purification by dry washing was carried out by varying
the amount of adsorbents in 1%, 2%, 5% and 10% (w/v) at 25 C for 10 min. For the purification by wet
Keywords:
washing, the biodiesel was successively washed with acidified water and pure water at 85 C until
Sunflower oil neutralisation. The efficiency of the processes for the removal of biodiesel impurities was evaluated by
Biodiesel determining the acidity index, combined alkalinity, free glycerine and turbidity of the biodiesel. All
Purification adsor- bents studied presented good efficiency in the removal of the impurities and showed similar
Natural adsorbents behaviour independent of the kind or amount of adsorbent employed. The use of natural adsorbents for
the purifi- cation of biodiesel have been shown to be a promissory process to be applied as an industrial
stage of the
purification of biodiesel during their production.
2015 Elsevier Ltd. All rights reserved.

1. Introduction Additionally, depending on oil origin (ester) used, it is possible to


obtain biodiesel with physicochemical characteristics similar to
The most common way to produce biodiesel is by transesteri- diesel. The resulting products of this reaction are divided into two
fication. Transesterification is the general term used to describe a phases, the first one composed mainly of esters (biodiesel), fatty
class of important organic reactions in which an ester is trans- acids and certain amounts of glycerides, and the second phase,
formed into another by the exchange of alkoxide groups. Among the denser, constituted mainly by glycerol and residues of
all of the alternatives, the transesterification can be considered transesterified triglycerides. Phase separation is by settling and/or
the best choice because this process is relatively simple [1]. centrifugation [2]. After the removal of glycerine, biodiesel may
present traces of alcohol, catalyst, free fatty acids, glycerine, water,
⇑ Corresponding author at: Federal University of Uberlândia, Chemistry Institute, etc. However, it is essential to use the purification and drying pro-
Av. João Naves de Ávila, 2121, Bloco 1D, Campus Santa Mônica, Uberlândia, Minas cesses so that biodiesel becomes acceptable in the market; i.e., it
Gerais 38400-902, Brazil. Tel.: +55 34 32394143; fax: +55 34 32394208. is essential that certain specifications are complied with to ensure
E-mail addresses: pasquini@iqufu.ufu.br, danielpasquini2013@gmail.com the quality of biodiesel. In this way, it is necessary to establish
(D. Pasquini). quality standards, aiming to set limits for the levels of
1
Tel.: +55 34 32394143.
2 contaminants that will not harm the quality of emissions from
Tel.: +55 34 32182773.
3 burning, as well as per- formance, integrity and security of the
Tel.: +55 34 96890357.
engine [2–4].

http://dx.doi.org/10.1016/j.fuel.2015.04.012
0016-2361/ 2015 Elsevier Ltd. All rights reserved.
2 M.G. Gomes et al. / Fuel 155 (2015) 1–6
M.G. Gomes
The reduction of impurities in the biodiesel can be achieved byet al. / Fuel 155 (2015) 1–6 3
2. Materials and methods
applying further purification steps, subsequent to decantation.
Traditionally, the most widely used method is wet scrubbing 2.1. Biodiesel preparation
(wet washing), which consists of using hot water due to the high
solubility of these contaminants in water, coupled with the low The biodiesel employed in this study was obtained from com-
cost, simplicity, efficiency and abundance. The disadvantage of mercial sunflower oil (LIZA) by alkaline transesterification via the
the method, besides the formation of the emulsion, preventing methyl route. In the method employed for obtaining biodiesel from
the separation of esters and allow the formation of free fatty acids sunflower, 20% methanol (v/v) and 0.6% NaOH (w/v) were
and soap, is the large volume of wastewater generated. In this last employed as catalysts, with respect to the sunflower oil. Initially,
case, it can be circumvented by applying dry purification methods sodium methoxide was obtained by mixing methanol and sodium
which do not use water to wash the biodiesel. hydroxide under constant agitation until complete homogenisa-
The technique of dry washing is promising for removing the tion. Then, the sodium methoxide was added to the sunflower
contaminants present in the biodiesel because of its low cost, sim- oil, and the mixture was kept under constant stirring for 30 min,
plicity of design and operation, and because of the selectivity of at a temperature of 60 C. At the end of the reaction, the mixture
some adsorbents [2–5]. Adsorption is a physical–chemical phe- was transferred to a separatory funnel in order to separate the
nomenon of great importance due to the multiple applications in phases. After resting, we observed two distinct phases: one con-
industry. The liquid phase adsorption is one of the most well used taining esters, which was less dense and lighter, and the other rich
and effective methods for the removal of impurities. The process of in glycerine, which was denser and darker. After standing for 24 h,
solid–liquid adsorption exploits the ability which certain solids glycerine was removed and the resulting biodiesel was employed
have in attracting substances present in the liquid phase to their in the different purification processes studied here [11,12,15].
surface. Thus, the components of the liquid phase can be
separated.
2.2. Purification processes
Several studies in the literature report different adsorbents hav-
ing been used for biodiesel purification. Faccini used commercial
2.2.1. Wet washing
adsorbents such as Magnesol , Amberlite BD10 DRY , Purolite PD
The purification process of biodiesel with water was performed
206 and silica [6]. Manique carried out the purification process in the separatory funnel, with successive washes with acidified
using agroindustrial residue (ash from rice hulls) and compared water (HCl 1 N – 1: 4, 85 C) and distilled water (85 C), until neu-
this with the acidic aqueous washing and Magnesol [7]. Manuale tralisation. Then, the biodiesel was dried in an oven at 105 C by
and co-workers elected a commercial silica, Trysil 3000, as a 1 h. After this, the resulting sample was stored for later analyses
good adsorbent material for biodiesel purification [8]. Berrios [4,7].
and Skelton shown purification using magnesium silicate [1].
Cavallari evaluated the biodiesel purification processes for dry
2.2.2. Dry washing
cleaning, including adsorption methods in different materials and
The purification process of biodiesel via dry washing was car-
filtration membranes, making a comparative critical analysis of
ried out employing different natural adsorbents (potato starch
purification processes studied and tested by several authors,
(YOKI), corn starch (CARGILL), cassava starch (AMAFIL), rice starch
using, as a basis, published articles and dissertations [5]. Silva and
(MAIZENA) and eucalyptus bleached Kraft cellulose) and a com-
co-workers tested the removal of free glycerol into biodiesel
mercial adsorbent Select 450 . The process was carried out by add-
using smectite clay, diatomaceous earth, amorphous silica and
ing 1%, 2%, 5% and 10% (w/v) of adsorbents with respect to the
specific commercial resin for biodiesel purification in order to
biodiesel, and the mixture remained under constant stirring for
have a pattern for adsorp- tion tests [9]. Leeruang and Pengprecha
10 min at 25 C and 150 rpm. Then, the samples were filtered in
studied the biodiesel puri- fication with silica from natural
a simple funnel with filter paper to remove the adsorbents and
bentonite [10]. Atadashi and co- workers conducted a study
the purified biodiesel was stored for later analyses.
related to biodiesel refining technolo- gies and also made a
critical review of the latest research findings
related to biodiesel refining technologies, both conventional purifi-
cation as the latest technology with membranes [11,12]. Costa car- Select 450 is a selective adsorbent developed from Oil-Dri
ried out the study with three alternative adsorbents: bentonite Company. Select 450 is prepared from natural aluminium silicate
clay,
diatomite A and B; the commercial resin Purolite PD206 was used Biofuels (ANP) standards.
as a standard [13]. Paula and co-workers evaluated the effective-
ness of treating biodiesel prepared from discarded frying soybean
oil, using the techniques of washing with distilled water,
distillation and adsorption with bauxite, bentonite and attapulgite
[14].
In short, there are many biodiesel purification studies with
adsorbents via dry washing, but no work was found concerning
the studies employing starch and cellulose as adsorbents. The cel-
lulose and starch are cheap materials, abundant, from renewable
sources, biodegradable, non-toxic, biocompatible and have great
potential to be employed as natural adsorbents in the purification
of biodiesel.
In this way, this study aims to perform the study of the adsorp-
tion of biodiesel contaminants after the production process of
biodiesel from sunflower oil, using natural adsorbents, such as
potato starch, corn starch, rice starch, cassava starch, eucalyptus
bleached kraft cellulose, along with an industrial adsorbent,
Select 450, and to compare this with the use of water in the pur-
ification of biodiesel, using techniques and analysis methodologies
established by the National Agency of Petroleum, Natural Gas and
and
4 magnesium, which is modified through a special process for
M.G. Gomes et al. / Fuel 155 (2015) 1–6
producing an adsorbent with affinity to soaps, metals and
phospholipids.

2.3. Biodiesel characterisation

The samples of biodiesel before and after the dry and wet pur-
ification processes were characterised with respect to the acidity
index (EN 14104), combined alkalinity (AOCS method Cc 17-19),
free glycerine and turbidity. The efficiency of the different pro-
cesses was assessed by analysis of variance (ANOVA) double factor
without repetition, and those considered significant were those
which presented p 6 0.05 [16,17].

2.3.1. Acidity index


The method used in this work follows the standard EN 14104,
using an alcoholic solution of KOH as the titrant and phenolph-
thalein as indicator. The acidity index, based on standard EN
14104, is given by mass of sodium hydroxide required to
neutralise free fatty acids contained in one gram of sample. Acidity
is the per- centage of free fatty acids in a fat or oil. According to
the proposed
regulations RANP 14/2012, the value cannot exceed 0.50 mg 2.4. Characterisation of adsorbents by scanning electron microscopy
KOH/g (SEM)
[7,18].
The process consists of neutralisation by means of a 0.1 mol L 1 The morphology of the adsorbents (potato starch, corn starch,
solution of KOH, with the free fatty acids existing in a sample of 5 cassava starch, rice starch, eucalyptus bleached Kraft cellulose
g of biodiesel dissolved in a solvent consisting of a neutralised
and Select 450 ) were analysed by SEM. The SEM analyses were
solu- tion of 10 ml of ethyl alcohol. The titration is performed carried out in a CARL ZEISS microscope Mod. EVO MA10, operating
until the turning point of phenolphthalein solution (3 drops), i.e.,
at 20 kV range. The samples were placed on a metallic support and
until the detection of a permanent pink colour of the sample. previously coated with a layer of gold. From the obtained images,
The acidity index is determined from Eq. (1) and the result is
the particle sizes of the adsorbents were estimated.
expressed as mg KOH per gram of sample.
Acidity index ¼ ðV C Fc 56:11Þ=m ð1Þ 2.5. Determination of the surface area and pore size of adsorbents
where: V = volume of KOH solution spent on titration;
C = concentration of KOH solution; Fc = correction factor of KOH N2 adsorption–desorption experiments were conducted at 77 K
solution; m = mass of the biodiesel sample. using a Micrometrics Surface and Pore Size Analyzer, model ASAP
2020. Prior to the experiment the sample was degassed at 573 K
for 18 h. The surface area was obtained using the BET model. The
2.3.2. Combined alkalinity
pore size distribution was evaluated from the desorption branches
The procedure used was based on the AOCS method Cc 17-19,
of the isotherms using the Barrett–Joyner–Halenda (BJH) method.
which uses titration with 0.01 N HCl solution [6].
Into a 250 mL Erlenmeyer, approximately 5 g of the sample, if it
was not washed biodiesel, or 100 g, if the sample was washed bio- 3. Results and discussions
diesel, was weighed. Then, it was added to the 1 ml sample of bro-
mophenol blue solution (0.4% in water). The sample was titrated The yield of biodiesel, obtained in the transesterification pro-
with 0.01 N HCl solution until the blue colour turned yellow. The cess employed in this study, was 87% (calculated in relation to
combined alkalinity, which can be reported as ‘‘ppm Na/g of sam- the initial mass of oil and the final mass of biodiesel fraction).
ple’’ is given by Eq. (2). This value is in agreement with the values found in the literature
Combined alkalinity ¼ ðVa N 22:99 1000Þ=m ð2Þ [4,7,11,12,15]. Fig. 1 shows the SEM images of the adsorbents
employed in the purification processes carried out in this work.
where: N = concentration of HCl solution, Va = volume of HCl spent It is possible to verify the different morphologies and sizes of the
in the titration; m = mass of the biodiesel sample. samples. The corn starch, rice starch and Select 450 are polyhe-
dral, the potato starch is ellipsoidal, the cassava starch is semi-
2.3.3. Free glycerine spherical, and the cellulose is in tape format. The sizes of the
The strategy employed to determine the free glycerine content adsor- bent particles estimated from the SEM images are
in biodiesel was the oxidation of free glycerine with periodic acid, presented in Table 1. Both the morphologies and sizes of the
resulting in formic acid and formaldehyde. The concentration of samples are in agreement with the values reported in the
free glycerine is calculated based on the result of the titration of literature [20]. These differences in size and shapes can reflect,
formic acid [3]. In Brazil, as in Europe and the United States, the mainly, the sizes of the surface areas of the particles, and hence
maximum permitted free glycerine in biodiesel is 0.02 wt.% [3]. can perform different roles in the processes of adsorption of
In a 250 mL separatory funnel, 3 g of biodiesel sample, 20 ml of impurities from the biodiesel. Although was observed differences
distilled water and 0.5 ml of aqueous sulphuric acid solution (acid of the particle sizes from SEM images, it is possible see from Table
to water ratio 1:4, v/v) was added. The mixture was stirred to 1, that the values of the surface area and pore sizes were not
homogenise the solution and allowed to stand until separation of significantly different for the starch and cellulose samples.
the two phases. The dense phase (lighter) was removed from the Additionally, it was observed that the sur-
separatory funnel and placed in a 250 ml Erlenmeyer flask. The free face area and pore size for Select 450 is very higher than that
glycerine was determined from this solution withdrawn from observed for cellulose and starch samples.
the separatory funnel. To this solution, 50 ml of sodium periodate The results of the characterisations of the biodiesel samples,
solu- tion, at a concentration of 5.5 g L 1, was added and the obtained before and after the different processes of purification,
mixture was allowed to stand for 10 min. Then, 4.0 g sodium employing 1%, 2%, 5% and 10% of adsorbents, are presented in
bicarbonate and 1.5 g of potassium iodide was added with stirring Table 2.
to homoge- nise. This solution was titrated with 0.1 N sodium The acidity index indicates the amount of fatty acids existing
arsenite until the colour of the mixture remained clear. Then, 3 in biodiesel. It is an important factor to be determined, since free
drops of aqueous starch solution (1% w/v) were added and the fatty acids favour the process of fuel degradation and
titration was contin- ued until the turn, i.e. when the solution compromises the life of the motor causing corrosion, deposit
became colourless [19]. The free glycerine content is obtained formation and fouling. The acidity cannot be regarded as a
from Eq. (3). constant or characteristic, because it originates from the partial
hydrolysis of triglycerides and thereby joins the degree of
Free glycerine ¼ ½ðVb VsÞ 0:1 =m ð3Þ degradation, quality and storage of the raw material [4,21]. It is
possible to verify from the data pre- sented in Table 2 and by the
where: Vb is the volume (ml) of arsenite solution consumed in the
graph in Fig. 2, that the acidity index showed good results for all
blank titration, Vs is the volume (ml) of arsenite solution consumed
samples within the limit established by the ANP standards, i.e.,
in the titration of the sample, is the title of the sodium arsenite
below 0.50 mg KOH/g of biodiesel. It is important to highlight
solution, and m is mass (g) of the sample of biodiesel. that all adsorbents tested presented a better performance than the
purification by wet washing with water. The only exception was
2.3.4. Turbidity the purification performed with 1% of Select
The turbidity of the biodiesel before and after the different 450 . Additionally, the amount and kind of adsorbents did not sig-
pur- ification processes were analysed on a portable nificantly influence the resulting acidity index, showing no specific
turbidimeter, model 2100P, HACH brand. selectivity of the kind of adsorbent employed.
Fig. 1. SEM images of the different adsorbents: (a) potato starch – magnification 1500 ; (b) corn starch – magnification 1500 ; (c) cassava starch – magnification 1500 ; (d)
rice starch – magnification 1500 ; (e) Select 450 – magnification 1500 ; (f) cellulose – magnification 1400 .

Table 1
Average diameters of the adsorbent samples estimated from the SEM images, surface area determined by BET model, total specific pore volume and average pore diameter
calculated by the BJH method.

Average diameter range (lm)


2 3
Sample Surface area (m /g) Total specific pore volume (cm /g) Average pore diameter (nm)

Potato starch 27.5–59.5 1.0449 + 0.5402 0.003504 7.0037


Corn starch 8.4–21.8 0.9641 + 0.2795 0.004124 7.0758
Cassava starch 9.6–24.3 0.3270 + 0.0589 0.004045 7.6795
Rice starch 38.5–67.6 1.8587 + 0.2274 0.003989 7.2950
Cellulose 3.7–13.0 3.1415 + 1.2758 0.015881 7.0601
Select 450 28.8–40.0 163.9332 + 1.0553 0.347068 10.2971
The combined alkalinity is substantially removing the
an indirect measure of the entire glycerine
amount of sodium in the concentration, independently
biodiesel. The sodium of the amount of adsorbent
contamination is caused by employed. It is possible to
the use of catalysts in the highlight the good
biodiesel production process performance in the case of
in the form of NaOH. This the use of potato starch (5%),
sodium in the form of ions cassava starch (1–2%), rice
causes the formation of starch (1% and 5%) and cel-
insoluble soaps which lulose (10%). In contrast, the
generate engine deposits and, use of corn starch (1% and
in addition, can catalyse 5%), cellu- lose (1% and 5%),
polymerisation reactions [4]. Select 450 (5%) and for the
From Table 2 and Fig. 3, it wet washing process, all
is possible to verify that the surpassed the required by
combined alkalinity tests standards – 0.02%.
yielded good results, but the The turbidity is a
best result was obtained measure that gives
employing potato starch – AB information about the visual
(5% and over), corn starch – aspect of the biodiesel which
AM (10%), cassava starch – can be related to the presence
AK (up to 5%) and Select 450 of impurities. The presence of
– Sel (2% and over). In the glycerine, water and some
latter case, the explanation is sediment is highly
in the fact that the Select detrimental to biodiesel
450 is a product because it accelerates its
commercially developed for dete- rioration and damages
the control of soap in the pro- its combustion, as well as
cess, and so it was expected accelerating the saturation of
this good performance shown. the filters and causing
In gen- eral, the best values damage to the fuel system
were found when more than [22]. It is possible to verify
5% of adsorbents was from the data presented in
employed, and, additionally, Table 2 and from the graph in
increasing the amount of Fig. 5 that the purification
adsor- bents decreases the processes carried via dry
combined alkalinity. It is washing with the different
important to high- light that adsorbents were very
for combined alkalinity, there effective in the removal of
is no maximum and/or turbidity of the biodiesel. On
minimum stipulated by the contrary, for purification
standards. via wet washing with water,
The glycerine an increase in the turbid- ity
concentration is an important was verified. In general, the
quality parameter of increased amount of
biodiesel. The free glycerine adsorbents decreased the
in biodiesel associated with turbidity. The best results
the presence of tri-, di- and were reported for potato
monoacylglycerols is starch – AB (5% and 10%),
responsible for the formation cassava starch – AK (1% and
of carbon deposits in the 2%) and Select 450 – Sel (1%,
engine due to its incomplete 5% and 10%).
combustion. Furthermore, Due to the similar
according to the temperature behaviour observed for the
and stor- age time, the different adsor- bents studied
glycoside present in the here, and in order to evaluate
biodiesel tends to precipitate the effect of each dif- ferent
[2,4]. From Table 2 and Fig. 4, adsorbent on the removal of
it is possible to verify that for contaminants, and to verify
all dry washing purifications whether they have
employing different significantly different
adsorbents, they pre- sented behaviour between them, the
a similar effect on the statistical treatment was
removal of free glycerine, carried out using the
analysis of
Table 2 160
Results of the characterisations of biodiesel samples, before and after the
purification processes. 140

Biodiesel Bio
Acidity index Combined Free Turbidity 120
sample (mg KOH/g) alkalinity glycerine (%) (NTU) w
(ppm Na/g) 100
AB
Bio 0.172 ± 0.027 87.9 ± 8.0 0.129 ± 0.001 52.8 ± 8.0
80 AM
W 0.136 ± 0.024 57.5 ± 7.0 0.058 ± 0.002 341.5 ± 5.0 AK
60
AB 1% 0.111 ± 0.003 27.9 ± 3.0 0.006 ± 0.003 17.5 ± 1.0 AA
AB 2% 0.114 ± 0.001 44.4 ± 1.0 0.006 ± 0.003 3.1 ± 1.0
40 Cel
AB 5% 0.106 ± 0.004 0.0 ± 0.5 0.000 ± 0.001 0.9 ± 1.0
AB 10% 0.100 ± 0.009 0.0 ± 0.5 0.023 ± 0.001 0.8 ± 1.0 20 Sel

AM 1% 0.120 ± 0.008 94.8 ± 1.0 0.052 ± 0.001 29.8 ± 1.0


0
AM 2% 0.106 ± 0.008 91.9 ± 1.0 0.007 ± 0.002 7.0 ± 1.0
AM 5% 0.129 ± 0.001 58.8 ± 3.0 0.030 ± 0.001 3.3 ± 1.0 1% 2% 5% 10%

AM 10% 0.104 ± 0.008 0.0 ± 1.0 0.006 ± 0.003 1.6 ± 2.0


Fig. 3. Graph for the comparison of the combined alkalinity obtained for all the
AK 1% 0.099 ± 0.001 0.0 ± 0.5 0.000 ± 0.001 0.6 ± 2.0 biodiesel samples before and after purification with different processes (wet and
AK 2% 0.098 ± 0.002 0.0 ± 0.5 0.000 ± 0.001 0.6 ± 2.0 dry) and with different amounts of adsorbents.
AK 5% 0.099 ± 0.001 0.2 ± 0.3 0.007 ± 0.002 1.1 ± 1.0
AK 10% 0.099 ± 0.001 22.6 ± 3.0 0.022 ± 0.001 1.4 ± 1.0

AA 1% 0.100 ± 0.001 54.7 ± 2.0 0.000 ± 0.001 14.7 ± 1.0


AA 2% 0.097 ± 0.002 26.7 ± 4.0 0.007 ± 0.002 12.1 ± 1.0 0.14
AA 5% 0.100 ± 0.001 65.9 ± 1.0 0.000 ± 0.001 8.8 ± 3.0
AA 10% 0.098 ± 0.002 36.8 ± 5.0 0.007 ± 0.002 2.3 ± 3.0 0.12
Bio
Cel 1% 0.097 ± 0.002 95.5 ± 1.0 0.029 ± 0.001 5.2 ± 1.0
0.1
Cel 2% 0.099 ± 0.001 140.1 ± 1.0 0.015 ± 0.001 5.8 ± 1.0 W
Cel 5% 0.099 ± 0.001 42.9 ± 3.0 0.068 ± 0.001 4.9 ± 2.0 AB
0.08
Cel 10% 0.099 ± 0.001 50.1 ± 2.0 0.000 ± 0.001 2.8 ± 3.0 AM
Sel 1% 0.198 ± 0.001 79.6 ± 1.0 _ 0.4 ± 2.0 0.06 AK
Sel 2% 0.101 ± 0.001 27.3 ± 4.0 0.008 ± 0.002 1.5 ± 1.0 AA
Sel 5% 0.093 ± 0.005 9.1 ± 3.0 0.047 ± 0.001 0.4 ± 2.0 0.04
Cel
Sel 10% 0.099 ± 0.002 8.9 ± 3.0 0.008 ± 0.002 0.5 ± 2.0
0.02 Sel
Limit 0.50 _ 0.02 _
ANP 0

Where: Bio = pure biodiesel, without purification; W = biodiesel washed with water 1% 2% 5% 10%
and dried (wet washing); AB = biodiesel purified via dry washing with potato
starch; AM = biodiesel purified via dry washing with corn starch; AK = biodiesel Fig. 4. Graph for the comparison of the free glycerine obtained for all the biodiesel
purified via dry washing with cassava starch; AA = biodiesel purified via dry samples before and after purification with different processes (wet and dry) and
washing with rice starch; Cel = biodiesel purified via dry washing with cellulose; with different amounts of adsorbents.
Sel = biodiesel purified via dry washing with Select 450 .

adsorbents employed in this study are effective in the removal of


impurities of the biodiesel.
0.25
In summary, the use of natural and biodegradable adsorbents
(cellulose and starch), is very interesting for application in the
0.2 industrial process of biodiesel preparation, due to the effectiveness
Bio
of the removal of contaminants and mainly due the fact that this
W
purification step can be carried out at room temperature avoiding
0.15 AB
heating the biodiesel and preventing the generation of sub-prod-
AM ucts by the thermal degradation of biodiesel.
0.1 AK
AA
Cel
0.05
Sel

0
1% 2% 5% 10%

Fig. 2. Graph for the comparison of the acidity index obtained for all the biodiesel
samples before and after purification with different processes (wet and dry) and
with different amounts of adsorbents.

variance (ANOVA). The results of this treatment are presented in


Table 3.
From the data in Table 3, we can conclude that the type of
adsorbent employed only affects the combined alkalinity
parame- ter, and the amount of adsorbent used affect only the
Fig. 5. Graph for comparison of the turbidity obtained for all the biodiesel samples
turbidity. For all other parameters, the kind and amount of before and after purification with different processes (wet and dry) and with
adsorbent employed did not affect the results. In general, we can different amounts of adsorbents.
conclude that all of the
T use of adsorbents for the [4] Manique MC, Faccini CS, to the study of thermal stability
a Onorevoli B, Benvenutti EV, of micro–
b purification of biodiesel via Caramão EB. Rice husk ash as nano silica epoxy composites.
l dry cold washing has the Chem Intell Lab Syst
an adsorbent for purifying
e 2011;105:114–24.
advantage of drastically biodiesel from waste frying
[18] National Agency of Petroleum.
oil. Fuel
reducing wastewater, making Natural Gas and Biofuels–
3 2011;92:56–61.
Results obtained from ANOVA test the process environmentally [5] Cavallari PI. Avaliação dos ANP. Technical Bulletin January
2014; 2014.
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