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Tribology International
journal homepage: www.elsevier.com/locate/triboint
art ic l e i nf o
a b s t r a c t
Article history:
Received 17 March 2015
Received in revised form
6 July 2015
Accepted 8 July 2015
Available online 16 July 2015
Vegetable or synthetic lubricants, also called biolubricants, are less harmful to the environment. In order
to quantify their biodegradability, some tests are able to predict how long oil/lubricants will take to be
degraded in the environment. This study proposes to evaluate the biodegradability of bio-based
lubricants using a bio-kinetic model (without microorganisms), comparing their performances with
fresh vegetable oil and mineral oil. The results are presented through an Effective Composition for
Biodegradation (ECB), half-lives and biodegradation time prole. The synthesized biolubricants showed
ECB values closer to vegetable oil than mineral oil. Half-life times are approximately 12 days for fresh
vegetable oil, around 2030 days for the biolubricants, and over 200 days for the mineral oil.
& 2015 Elsevier Ltd. All rights reserved.
Keywords:
Biodegradability
Bio-based lubricant
Basestock oil
1. Introduction
Biodegradability is an important characteristic for the majority
of today's chemical industry products, and represents a way of
measuring the risk level of decomposition presented by these
products when deployed to the environment. Biodegradation is a
natural process caused by the action of microorganisms, in the
presence of oxygen, nitrogen and minerals.
In the process of formulating lubricant oils, biodegradability is
strongly dependent on the oil used. Basestock oils and nished
lubricants are products with a potential risk of being in direct
contact with the environment, which may happen in their
production, distribution, services usage or even in disposal after
their utilization. Therefore, environmental authorities have been
increasingly demanding less toxicity in these products, so they will
cause less harm to the nature [13].
The impacts on the environment caused by inappropriate
disposal of the wastes are huge. Lubricants, when in intentional
or accidental contact with the soil, make it useless for farming and
civil construction, killing the vegetation and the microorganisms
[4,5]. Brazilian Environmental National Council (CONAMA) determine that the best environmental management for used or
contaminated oils is re-rening and, for that, there are many
companies properly registered in this Council that are able to
perform this activity [6].
2. Standard methods
One of the rst methods proposed to evaluate the biodegradability of lubricant oils and fuels was the CEC L-33-T-82,
302
Table 1
Physicochemical properties of vegetable and mineral oils.
Samples
15
33
Flash
point
(1C)
TAN
(mg
KOH/g)
Viscosity (cSt)
286
162
1.120
0.001
261.3 19.6
19.9 4.8
VI
40 1C 100 1C
84
174
303
checked for purity by GC/FID (495 wt%). Physicochemical properties of these samples are reported in Table 2.
3.3. Biodegradability method
The method described by Rhee (2005) [10] was performed to
estimate the biodegradability of lubricants, without using microorganisms. This procedure uses a bio-kinetic model, which was
already validated as a very accurate method when compared to
the standard results obtained using the ASTM D5864-11 [12]
method (which evaluates the biodegradation of lubricants using
aerobic microorganisms) to quickly estimate the biodegradability
of lubricants. This method uses glass chromatographic columns
packed with silica gel and bauxite activated under nitrogen gas
ow, as shown in Fig. 3.
The experiments were performed using initially 2 g of the
samples dissolved in 10 mL of n-pentane. According to the
Table 2
Bio-based lubricants physicochemical properties.
Samples Specic gravity Pour
at 20 1C (g/cm) point
(1C)
BL1
BL2
0.9033
0.9138
42
36
Flash
point
(1C)
TAN
(mg
KOH/g)
Viscosity (cSt)
264
258
0.021
0.025
17.6
18.3
VI
40 1C 100 1C
4.31
4.33
159
152
304
4. Calculations
According to Rhee (2005) [10] the Effective Composition for
Biodegradation (ECB) is calculated based on the quantity of nonaromatics and esters fractions, associated with the ECB coefcient
(), as shown in Eq. 1.
ECB U F 1 F 3 =100
Table 3
Coefcients for the ECB calculation (Rhee, 2005
[10]).
Lubricants base
ECB Coef. ()
Mineral
Poly-alpha-olen 2a
Poly-alpha-olen 4a
Poly-alpha-olen 6 or superiora
Natural Esters
Polyol Esters
0.3
0.8
0.6
0.4
1.0
0.8
0:49 lnt
lnt 1=2
305
5.2. Biodegradability
The biolubricants biodegradability was estimated using the
bio-kinetic model. Before carrying out the tests with the biolubricants, biodegradability analysis of samples from vegetable
castor oil was performed to assess the results of a typical
biodegradable product. The results from this method are the
Effective Composition for Biodegradation (ECB), the half-life and
the estimation of the percentage of biodegradation as a function of
time. The values found for three runs with the same sample of
pure castor oil are shown in Table 4. The results indicate that
vegetable oil shows values of ECB and half-life close to those
reported by Rhee (2005) [10] for canola oil (t 9 days).
For the bio-based lubricant samples evaluated, it was observed
that BL1 and BL2 showed half-lives of about 26 and 20 days,
respectively. In Figs. 4 and 5, cumulative biodegradation estimates
as a function of time are presented for three experimental runs for
BL1 and BL2, respectively, showing average ECB of 0.57 for BL1 and
0.64 for BL2.
The estimated cumulative biodegradation for the naphthenic
mineral oil samples is shown in Fig. 6. Good reproducibility for
three replicates can be observed as previously seen for the other
samples. According to Rhee (2005) [10], for mineral lubricants, ECB
values range from 0.22 to 0.36 and half-lives from 114 to 231 days.
The ECB values and half-lives obtained for the samples of mineral
oil evaluated in this study are thus within the range reported above.
It may be observed that the biodegradability of the mineral
naphthenic oil is lower than what was observed for the biolubricant samples (average ECB of 0.23 and half-life of 225 days). For
mineral base oils, several authors have reported biodegradability
studies relating their results with chemical and physical properties
[28,29] or their chemical composition [17]. In general, the biodegradability of basestock mineral oils is strongly related to the
presence of aromatic and naphthenic compounds in their composition (the higher the content of these compounds the lower the
biodegradability). The bio-based lubricants in this study, obtained
from castor oil, would be likely to present higher biodegradability
than mineral basestock oils.
A comparison between the biodegradation proles for the
biolubricant samples with those for castor vegetable oil and for
the mineral oil samples is presented in Fig. 7. As mentioned before,
the biodegradability of the biolubricant samples are clearly higher
when compared to mineral oil. On the other hand, some loss in
biodegradability is observed for the biolubricant samples when
compared to the fresh castor vegetable oil, which was expected
Table 4
Effective composition of biodegradation (ECB) and halflife (t) for three runs with pure castor oil.
Run
ECB
1
2
3
0.774
0.802
0.780
12 days
Fig. 6. Estimated biodegradation proles for the mineral basestock oil. () Exp. 1;
( ) Exp. 2; and () Exp. 3.
Biodegradation (%)
306
100
90
80
70
60
50
40
30
20
10
0
0
20
40
60
Fig. 7. Estimated biodegradation proles for castor oil (), BL1 ( ), BL2 ( ) and
mineral oil (). Half-life times are 12, 26, 20 and 225 days, respectively.
6. Conclusions
This study estimates the biodegradability of different oils
(vegetable, synthesized and mineral), using experiments without
microorganisms. Two different synthesized biolubricants (BL1 and
BL2) were evaluated along with a mineral and a vegetable oil
(castor oil), using this method as a form of comparison. As
expected, the castor oil presented the highest ECB value (0.78)
whilst the mineral oil showed the lowest (0.23), which means a
very high half-life for the mineral oil and the opposite for the
vegetable oil. Nonetheless, the vegetable oil is not the best choice
to be used as a direct lubricant especially because of its limitations
in thermal and oxidative stability. In the other hand, the synthesized biolubricants have high viscosity index and low pour point,
which makes them an appropriate lubricant option, especially
because of the good half-lives they presented, around 26 days for
BL1 and 20 days for BL2. Very little difference may be identied
when comparing the half-lives of BL1 and BL2, meaning there is no
considerable change in using 2-ethylhexyl or octyl ricinoleates as a
bio-based lubricant. Furthermore, a huge difference can be spotted
when comparing the biodegradation as a function of time of the
synthesized lubricants with that of the mineral oil.
Acknowledgments
The authors wish to thank nancial and logistic support
provided by PETROBRAS (Petrleo Brasileiro S.A.) and CNPq (Conselho Nacional de Pesquisa e Desenvolvimento Cientco).
References
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challenge to base material producers and formulators. J Synth Lubr 2003;20:
5368.