Renewable and Sustainable Energy Reviews 102 (2019) 83–95

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Renewable and Sustainable Energy Reviews

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

Critical insights into the effects of bio-based additives on biodiesels T

properties
Ibrahim Lawana,b, Weiming Zhoua, Zaharaddeen Nasiru Garbaa,c, Mingxin Zhanga,
Zhanhui Yuana, , Lihui Chena,
⁎ ⁎

a
College of Materials Engineering, Fujian Agriculture and Forestry University, China
b
Department of Agricultural and Environmental Engineering, Bayero University Kano, Nigeria
c
Department of Chemistry, Ahmadu Bello University Zaria, Nigeria

ARTICLE INFO ABSTRACT

Keywords: Over the years, efforts have been made by researchers to come up with sustainable, non-toxic, cheap and bio-
Biodiesel degradable biodiesel additives in order to address the fuel quality challenges faced when using biodiesels.
Fuel properties Substantial achievements have been recorded on improving the oxidation stability and cold flow properties
Bio- additive (cloud point, pour point and cold filter plugging point) of the biodiesel with respect to the standard specifica-
Plant extracts
tions, with the bio-based additives in most cases performing similar to the synthetic additives. Herein, a critical
Bio-oil
review of the status quo has been made and some intriguing issues are raised for further investigations.
Maximum induction period of up to 23.99 h and maximum reduction of 4–5 °C in cold flow properties have been
documented. Some of the bio-based additives were found to negatively affect other fuel properties of biodiesels,
although the values were still within the acceptable limits. Also, of all the reported additives, Pongamia pinnata
leaves extract was found to significantly increase the brake thermal efficiency (BTE), brake specific fuel con-
sumption (BSFC), carbon monoxide (CO) emission and hydrocarbon (HC) emission and remarkably decreased
oxides of nitrogen (NOX). Generally, this review summarizes and highlights some basic information for hopeful
synthesis of effective biodiesel additives that will ensure cheap, non-toxic and sustainable solution to biodiesel
fuel challenges. Strikingly, bio-oils from non-edible sources and ethyl levulinate appear as the most suitable
additives for improving the oxidative stability and low temperature properties of biodiesels respectively.

1. Introduction deterioration. Oxidation of biodiesel occurs due to removal of hydrogen

The major issues that motivate the current interest in bio-energy are
energy security, energy independence, economic development [1,2]
and the concern about the environment [3–6]. Countries like China
have been promoting bio-fuel commercialization in their various ways
including establishing national standard, providing financial incentives,
initiating demonstration programs and framing national strategy [7].
Among bio-fuels, biodiesel is considered as the best substitute for petro
diesel [8]. This is possibly due to its high flash point, low toxicity, good
lubricity, negligible sulphur content, biodegradability, lower overall
exhaust emissions and possible derivation from renewable feedstock
[6,9–11]. Despite these highlighted advantages, however, its adopt-
ability and widespread are still hindered by some technical challenges,
one of which is the fuel quality [12].
Oxidation, poor low temperature tolerance and microbial degrada-
tion of biodiesels are well-established challenges resulting in fuel
from a carbon atom [13] and/or reaction of biodiesels with ambient
oxygen [14–16] to produce hydro-peroxide, peroxides and carboxylic
acids [17,18]. It negatively affects the biodiesel fuel quality and engine
performance [19]. It has been established that the oxidation reaction
usually involves the unsaturated fatty acid composition of the methyl
ester and it is accelerated by air, heat and light [13,14,20,21]. Poor low
temperature tolerance of biodiesels occurs as a result of crystallization
of saturated fatty acid contents of the biodiesels during winters, causing
clogs in the fuel lines and filters [22–24]. It has been established that
higher amounts of saturated esters in biodiesels increase the cloud
point, pour point and cold filter plugging point of the biodiesel [24].
Microbial activities have also been found to cause biodiesel deteriora-
tion [25–29]. Beker et al. [30] established that microbial degradation of
biodiesels causes increase in viscosity, acid number and water content
of the biodiesel to values outside the standard specifications.
To tackle the aforesaid challenges facing the biodiesel quality and

⁎
Corresponding authors.
E-mail addresses: zhanhuiyuan@fafu.edu.cn (Z. Yuan), lihuichen@fafu.edu.cn (L. Chen).

https://doi.org/10.1016/j.rser.2018.12.008
Received 31 May 2018; Received in revised form 19 November 2018; Accepted 6 December 2018
1364-0321/ © 2018 Elsevier Ltd. All rights reserved.
I. Lawan et al. Renewable and Sustainable Energy Reviews 102 (2019) 83–95

Nomenclature EL Ethyl levulinate

EAA Ethyl acetoacetate
Abbreviation Description EVAC Ethylene-vinyl acetate co-polymer
CP Cloud point
BHA 2-tert-butyl-4-methoxyphenol PP Pour point
TBHQ 2-tert-butylbenzene-1,4-diol CFPP Cold filter plugging point
DBPC 2,6-ditertbutyl-4-methylphenol PGE Polyglycerol esters
DDA Duralt diesel additive MSBO Metathesized soybean oil
SDS Sodium dodecylsulfate MTO Metathesized triolein
BHT Butyl hydroxyl toluene SFO Ozonated sunflower oil
TPC Total phenolic content TAG Tri-acetyl glycerol
CDNP Dethyl phosphate TBGs Tert-butylated glycerol
CDN-S Diethyl phosphothioate AGs Glycerol esters
CDN-Ph Phynyldiphenyl phosphate BC-FAME Branched-chain fatty acid methyl esters
Te Onset temperature Me iso-C18:1 Methyl isooleate
To Offset temperature Me iso-C18:0 Methyl iso-stearate isomers
Tmax Maximum degradation temperature SBO Soybean oil
IPDT Internal procedure degradation temperature LPSBO Low-palmitate soybean oil
CNSL Cashew nut shell liquid BTE Brake thermal efficiency
GC-MS Gas chromatography couple to mass spectrometry CO Carbon monoxide
NMR Nuclear magnetic resonance HC Hydrocarbon
IONOL Tri-tertbutyl phenol (NOX) Oxides of nitrogen

stability, the use of synthetic chemical additives has been found to be
very effective. For example, additives such as2-tert-butyl-4-methox-
yphenol (BHA), 2-tert-butylbenzene-1,4-diol (TBHQ) and 2,6-di-tert-
butyl-4-methylphenol (DBPC) have been employed in minimizing fuel
deterioration due to oxidation [31]. Again, the sugar esters S270 and
S1570, polyglycerol ester LOP-120DP, silicon oil TSA 750, duralt diesel
additive (DDA), sodium dodecyl sulfate (SDS) and magnesium sulfate
are effective in preventing fuel crystallization due to low temperatures
[23]. Microbial activities could be inhibited by some, but not all, syn-
thetic additives, thereby preventing microbial degradation of biodiesel
[30].
Synthetic additives are however expensive and this triggers the need
for intensive research to develop cheaper, non-toxic, biodegradable and
renewable additives with satisfactory efficacy. Substantial achieve-
ments have been recorded in recent years; but there have been little or
no comprehensive reviews of these crucial reports. Herein, we critically
summarize some of the related articles and establish the state-of-the-art.
Moreover some hypotheses and recommendations are raised for further
studies.
2. Effects of Bio-based additives on biodiesel fuel properties
2.1. Effects of Bio-based additives on oxidative stability of biodiesel
2.1.1. Effects of plants extract on oxidative stability
In an effort to enhance the oxidation induction period of biodiesel,
the use of plant extracts has been reported from a number of literatures.
Ramalingam et al. [32] studied the effects of pongamia pinnata leaf
extract on the oxidative stability of biodiesel blends. They revealed
significant increase in the induction period with increase in the additive
(leaf extract) dosage. The authors reported an induction period of up to
14 h which represents 180% increase as compared to the neat sample.
The activity of the additive appears to be largely attributed to the
presence of carotenoid and chlorophyll II among the eight components
of the extracts established. In another development, Fernandes et al.
[33] studied the effects of ethanol extract of moringa oliefra leaves as a
potential antioxidant for biodiesel. The investigation established that
extracts from 98% ethanol exhibited greater antioxidant effects than
those from 70% ethanol, with maximum induction period of 19.3 h.
This was attributed to the presence of phenolic compounds and less
polar solvent present in the 98% ethanol. Consistently, Rocha et al. [34]
also used moringa leaves extract as an additive to enhance biodiesel
oxidation stability. Increase in dosage of the extract was observed as
being directly proportional to the induction period of the doped bio-
diesel where maximum induction period of 8.75 h was recorded from
the highest dosage used (4000 ppm) which represents an improvement
of about 74% compared to the neat biodiesel sample. However, the
activity of this extract was inferior when compared with that of butyl
hydroxyl toluene (BHT), a synthetic additive.
The last two independent studies demonstrated a variation in total
phenolic content (TPC) from the extracts (Table 1), likely owing to the
differences in the species of moringa used by the groups, leaves condi-
tions prior to extraction and the extraction methodology adopted. Both
groups have attributed the performance of the extract to the presence of
phenolic compounds, which is in line with some previous reports
[35–40]. On the other hand, the significant differences observed in the
oxidation induction periods obtained by the two groups could be ex-
plained from the observed variations in the concentration of the ethanol
used, the type of biodiesel and the dosage used as well as the variation
in TPC (Table 1). Moringa extract could therefore serve as an effective
additive for the improvement of oxidation stability of biodiesel. How-
ever, the economic values of this plant as a source of food and feedstock
as a result of its nutritive and/or medicinal values [41–45]could limit
its possible adoption and commercialization as bio-additive.
The antioxidant activity of curcumin, a plant belonging to the
ginger family which contains β-carotene and their mixtures, on bio-
diesel has been previously investigated [35]. The study established that
curcumin exhibits striking antioxidant activity. Induction period of 9.11
and 6.35 h were achieved using 1500 and 500 ppm dosages, respec-
tively. In another similar independent study, ginger extract showed
higher miscibility with biodiesel largely due to the lower water content
and higher proportion of non-polar compounds in the extract [46]. The
study generated an induction period as high as 23.99 h using a max-
imum dosage of 2000 ppm. Moreover, even with the minimum dosage
of 250 ppm used in the study, the doped sample was within the ac-
cepted standard limit. The activity of this additive on the biodiesel was
due to the presence of high amount of phenolic compounds in the
ethanolic ginger extract. Some previous studies also reported the effi-
cacy of ginger as antioxidant [47,48]; and some bio-active compounds
present in ginger have been found to be effective as natural anti-
microbial agents [49–51], which could also be exploited for inhibition
of microbial degradation of biodiesel.

84
 Table 1
Summary on the Effects of Bio-based Additives on the Oxidation Stability of Biodiesel.
Additive(s) Amount(s) Solvent(s) Biodiesel(s) Findings Ref.
I. Lawan et al.

Pongamiapinnata leaves extract 0.5–1.5% (vol/vol.) Ethanol (80%) + AC (20%) B20-Calophyllum biodiesel • Miscibility of the additive with the biodiesel was achieved with ethanol/additive ratio of [32]
1:50
• Increase in oxidation stability with increase in additive dosage from 0.5% to 1.5% vol/vol
• Induction period increased from 5 hrs to 14 hrs representing 180% increase
Moringaoleifera leaves extract 100–1000 μg/g Ethanol (98% &70%) B100-Moringa oil biodiesel • Higher amount of phenolic compounds were obtained with 70% ethanol than 98% ethanol [33]
• TPC of 57.0 ± 3.1 mg GAE/g & 39.8 ± 0.7 mg GAE/g for the 70 & 98% ethanol extracts
respectively
• Higher efficient concentration of 76.7 ± 0.4 μg/mL with 98% ethanol
• The additive increase the induction period from3.8 to10.3 h with 98% ethanol extract
• The extract exhibit superior activity over TBHQ additive
Moringaoleifera leaves extract 1000–4000 ppm Ethanol B100-Commercial biodiesel blends • TPC of 24.89 ± 1.00 mg GAE/g was obtained from the extracts [34]
• Increase in oxidation stability with increase in additive dosage from 1000 to 4000 ppm
• Induction period of 8.75 hrs was achieved at 4000 ppm
• The doped biodiesel remained stable up to 90 days at room temperature
Curcumin and β-carotene 500–1500 ppm – B100-Soybean oil biodiesel • Curcumin was found to have superior antioxidant activity [35]
• The activity of curcumin extract has outperformed TBHQ
• Induction period of 6.35 h was recorded using 500 ppm and 9.11 h was recorded with
1500 ppm
• Biodiesel doped with curcumin extracts was found to be stable up to 180 days
Ginger extract 250–2000 ppm Ethanol (100%) B100-Pongamia pinnata biodiesel • Lower water content and higher proportion of non-polar compounds results to higher [46]
miscibility of the extracts with the biodiesel
• Maximum induction period of 23.99 h was recorded with the highest dosage
• Minimum dosage of 250 ppm was enough to meet the ASTM D6751 and EN 14112
standards
Rosemary, oregano and basil extracts 0.7% (vol/vol.) Ethanol (99.5%) B100-Soybean oil biodiesel of 17.662, 16.306 and 1.939 mg GAE/g were obtained for the herbs respectively [52]

85
• TPC oxidation stability of the doped biodiesel was found to be endothermic and not
• The
spontaneous
• The ethnolic extracts of rosemary, oregano and basil were found to be effective in
inhibiting oxidation stability
Rosemary, oregano and basil extracts 0.8% (vol/vol.) Ethanol (99.5%) B100-Soybean oil biodiesel • Positive correlation between total phenolic content of the extracts and oxidation stability [53]
of biodiesel was established
• Positive correlation between relative factor and induction period was established
• Maximum induction period of 10.18 h was achieved with 1:1 rosemary and oregano mix
extracts
Rosemary, oregano and basil extracts 0.8% (vol/vol.) Ethanol (99.5%) B100-Soybean oil biodiesel • The mix-extracts were found to be better than mix-synthetic additives [56]
• Mix proposion of 50,12.50% and 37.50% rosemary, oregano and basil were found to be
the best
• Mix-extracts exhibits induction period of 10.18 h while the mix-synthetic exhibit 70.69 h
Pinewood bio-oil 1–8% (wt.) AC, CH, TO, IPP,2HE, DE, MA, EA, B100-Sunflower oil biodiesel • Biodiesel was found to be miscible with the additive for all the organic solvents used [57]
ISPPA, nBA • Increase in oxidation stability with increase in additive dosage
• Some variation in oxidation stability was observed with solvents used
• Induction period of 8.8 hrs was achieved with 8% wt. dosage additive using the isopropyl
acetate solvents
Pinewood bio-oil < 2% wt. H2O, H2O/BT, H2O/EA, H2O/ B100-Sunflower oil biodiesel < 2% wt of the additive was found to be miscible with the biodiesel [58]
ISPPA
• The crude bio-oil achieved improvement of oxidation stability by 135%
• Hydrothermal treated bio-oil (at 300 °C and 8.5 MPa) achieved improvement of oxidation
• stability by 400%
Pine pellets/chips oil – – B100-Poultry fat biodiesel • Addition of bio-oil resulted to drastic increase in DSC onset temperature [59]
• Addition of bio-oil resulted to increase in oxidation temperature from 155 °C to 225 °C
• The finding is attributed to the phenolic compounds present in the bio-oil
Pine wood oil – B100-Soybean oil biodiesel • Phenolic compounds obtained is 10% of the bio-oil [60]
• The bio-oil was moderately active
• Bi-functional phenolic compounds were responsible for the activity
• Mono-functional phenolic compounds were inactive
(continued on next page)
Renewable and Sustainable Energy Reviews 102 (2019) 83–95
I. Lawan et al. Renewable and Sustainable Energy Reviews 102 (2019) 83–95

B100: 100% biodiesel, B20: 20% biodiesel, TPC: Total phenolic compounds, AC: Acetone, CH: Cyclohexane, TO: Toluene, IPP: Isopropanol, 2EH: 2-ethyl-1-hexanol, DE: Diethyl ether, MA: Methyl acetate, EA: Ethyl
Spacino et al. [52]studied the effects of ethanol extracts of some

[61]

[72]

[73]

[75]

[76]
Ref.
herbs (rosemary, oregano, basil and their mixed formulation) as natural
antioxidants on B100 soybean biodiesel oxidation process. The findings

biodiesel doped with technical CNSL met the minimum standard for the oxidation
reveal that the oxidation reaction of the doped biodiesel became en-

of CNSL by electrochemical method signicantly reduced cardonol content

the bio-oil with 50% ethyl acetate improves miscibility of up to 50% bio-oil

hydrogenated cardanol achieved higher oxidation stability compared to the neat

activity of the technical CNSL was found to be less than that of TBHQ and BHT
the bio-oils obtained were found to have limited miscibility with the biodiesel

dothermic and not spontaneous, indicating that the herbs were effec-
period of 28.1 and 26.0 h were achieved for pine and malle wood oils

tive. Of all these additives (extracts), a mixed formulation of 50% ro-

Te, To and Tm were found to increase with the addition of the additive
semary, 25% oregano and 25% basil extracts was the most effective. In
another similar investigation, a biodiesel doped with 1:1 mixed for-

acetate, ISPPA: Isopropyl acetate, nBA: n-butyl acetate, BT: Butanol, Te: Onset temperature of degradation, To: off-set temperature of degradation, Tm: Maximum temperature of degradation.
mulation of rosemary and oregano extracts revealed a maximum in-
duction period of 10.18 h where a positive correlation exists between
the induction period and the relative protection factor of the biodiesel
[53]. Based on these two independent studies, it could be concluded
highest activity was obtained with 1000 ppm dosage

that the rosemary and oregano extracts could provide substantial an-
modified CNSL exhibits better oxidation stability
activity of the additive was comparable to BHT

tioxidation effects on the biodiesel due to the presence of phenolic

period of 7.31 ± 0.20 h was achieved

compounds in them. The antioxidation activity of rosemary has also

been reported by other research groups [54,55]. Interestingly, the in-
duction periods of samples doped with rosemary, oregano and basil
cardanol and heat treated biodiesel

extracts were shown by Gabriela et al. [56] to be higher than those

doped with the synthetic antioxidants TBHQ, BHA and BHT (Fig. 1).

2.1.2. Effects of bio-oils on oxidative stability

While the aforementioned studies investigated the use of alcoholic
plant extracts as additives for biodiesel, some research groups focused
on the possible use of various bio-oils obtained from some plant bio-
respectively

• Modifiation

mass for the same purpose. Garcia et al. [57] extracted bio-oil from
• Induction

• Induction

additives
• Blending

stability

pinewood and examined their efficiency on bio-oil extraction and

Findings

• Both

• The
• The
• The
• The
• The
• The
• The

miscibility with biodiesel (Table 1). They established an enhanced

miscibility of the bio-oil with the biodiesel, with a clear trend of in-
crease in the induction period with increasing additive dosage (Fig. 2),
with maximum induction period achieved using isopropyl acetate
(8.8 h). The antioxidation effects are largely due to the presence of
B100—Commercial biodiesel

B100-Soybean oil biodiesel

B100-Beef tallow biodiesel

B100-Canola oil biodiesel

B100-Cotton oil biodiesel

phenolic compounds.
Similarly, Gil-Lalaguna et al. [58] studied the activity of bio-oil from
pinewood as biodiesel additive for the improvement of its oxidation
stability. The bio-oil was hydrothermally treated using different solvent
Biodiesel(s)

media (Table 1) under different operating conditions (temperature:

250, 290 and 3000C and pressure: 4, 4.5, 5.0, 5.2, 5.3, 8.5, 8.7, 10.2,
10.8 and 11.5 MPa). The doped biodiesel sample showed improved
oxidation stability by 135% with the crude bio-oil and 400% with the
bio-oil hydrothermally treated with water solvent at 3000C and
8.5 MPa. Also, it is established that the doped sample remained stable
for almost four months largely due to the presence of phenolic com-
pounds and subsequent increase in the concentration of catechol after
the hydrothermal treatment of the bio-oil. The impact of various bio-oil
Methanol (99.8%)

and mix-ratios on the oxidation stability of biodiesel has been dissected

Hexane/EA

previously [59]. The bio-oil used was obtained from semi-continuous

Solvent(s)

auger pyrolysis of pine pellets and batch pyrolysis of pine chips. It was
used to dope biodiesel using varying dosages (Table 1). Good mis-
–

cibility of the bio-oil with the biodiesel and an increase in the oxidation
induction temperature from 155 to 225 °C was noted which shows
improvement on the oxidation stability of the doped biodiesel.
500–2000 ppm
10–50% (wt.)

5000 mg/kg

The activity of bio-oil as antioxidant on soybean biodiesel has been

Amount(s)

5000 ppm
800 ppm

found to be moderate, though still below that of the synthetic anti-

oxidant, BHT [60]. This investigation demonstrated that bi-functional
phenolic compounds containing catechol or guaiacol group are re-
sponsible for the antioxidation activity. The effects of oils obtained
Malle and pine wood fast pyrolysis

from malle and pine woods on biodiesel has been studied previously
[61]. The authors reported that only less than 20% wt. of both of the
bio-oils was miscible with the biodiesel. However, mixing the bio-oils
Cashew nut shell liquid

Cashew nut shell liquid

Cashew nut shell liquid

Hydrogenated cardanol

with 50% wt. of ethyl acetate enhanced the miscibility of the bio-oils
Table 1 (continued)

with the biodiesel and the pine and malle induction periods of the
doped biodiesel increased from 10.2 to 28.1 and 26.0 h, respectively.
Overall, it could be concluded that the bio-oils obtained from the woods
Additive(s)

bio-oil

could serve as the most reliable bio-additive for the improvement of

oxidation stability of the biodiesel.
Also, a number of literatures attributed the antioxidation effects of

86
I. Lawan et al.
Fig. 1. Induction Periods for Various Mix-Ratios. (a) Natural Additives (b) Synthetic Additives.
Fig. 2. Induction Period of Neat and Doped Sunflower Biodiesel.
the bio-oils to the presence of phenolic compounds [62–64]. Miscibility
of bio-oils with biodiesels is considered a fundamental factor for effi-
cient activity of the bio-oils as biodiesel additives. This factor has been
shown to depend on the type and amount of alcohol used as co-solvent
[65]. For instance, 1-butanol and 2-propanol produce homogenous
blends resulting to higher miscibility of bio-oils as compared to ethanol
(1-butanol can dissolve up 60% wt bio-oils, 2-propanol can dissolve up
to 50% while ethanol dissolves only about 35%). However, studies on
the economic feasibility of bio-oils as bio-additives and the use of sui-
table solvents to aid bio-oils miscibility with the biodiesel or possible
modification of the bio-oils to aid miscibility without solvents are
lacking. Despite that, the sustainable nature and the appreciable yield
of the bio-oils from woods have been studied to some extent [66–71].
2.1.3. Effects of cashew nut shell liquid on oxidative stability
Cardanol from cashew nut shell liquid (CNSL) has been thought of
to possess antioxidant effects to biodiesel. In fact, a biodiesel doped
with hydrogenated cardanol showed high oxidation stability [72].
However, it remains to be established whether the hydrogenation
treatment play any contributing role to the observed effect of the car-
danol on the biodiesel. Lomonaco et al. [73] synthesized the phos-
phorylated compounds diethyl phosphate (CDN-P), diethyl phos-
phothioate (CDN-S) and phynyldiphenyl phosphate (CDN-Ph)) from the
cardanol component of CNSL and compared their antioxidation
87
Renewable and Sustainable Energy Reviews 102 (2019) 83–95
Fig. 3. Thermogravimetric values obtained from the analysis of neat and doped
biodiesel (1000 ppm) samples.
properties with BHT on biodiesel. The doped biodiesel samples ex-
hibited delay in the onset temperature (Te), offset temperature(To) and
maximum degradation temperature (Tmax) as well as the internal pro-
cedure degradation temperature (IPDT) as compared to BHT as shown
in Fig. 3. Delayed thermo-oxidation of biodiesel has also been reported
previously [74].
In another independent study, CNSL was extracted and modified by
electrochemical method and the modified CNSL (eCNSL) and crude
CNSL samples were analyzed using gas chromatography coupled to
mass spectrometry (GC-MS) and nuclear magnetic resonance (NMR)
tests [75]. A dramatic reduction in the amount of cardanol after the
modification was observed; and the eCNSL exhibited greater anti-
oxidation effects with an additional~1.47 h in the value of the induc-
tion period than the CNSL. The reduction in the concentration of car-
danol due to this modification is likely the cause of the observed
difference in the effects of the CNSL and eCNSL.
The activities of the synthetic antioxidants BHT, TBHQ, tri-tert-
I. Lawan et al. Renewable and Sustainable Energy Reviews 102 (2019) 83–95

butyl phenol (IONOL) and the CNSL (using both neat and dec- respectively [85]. In a similar attempt, Hamada et al. [86]made com-
arboxylated CNSL)on beef tallow biodiesel have been investigated [76]. parison of the effects of poly glycerol esters (PGE) of fatty acids and
The decarboxylated CNSL had the least activity compared to the BHT EVAC on the crystallization behavior of biodiesel at low temperatures.
and TBHQ but still had an induction period of 8 h, which exceeded the The study demonstrated that the crystallization temperature of the
standard 6 h minimum induction period. Generally, studies on CNSL as biodiesel (11.3 °C for neat PME) decreased to 9.8, 7.8 and 9.2 °C by 2%
a biodiesel additive suggest that modified CNSL is more effective. For (wt.) of the EVAC, PGE and EVAC+PGE, respectively. The additives
instance hydrogenation of cardanol and synthesis of phosphorylated depressed the growth of PFME crystals at lower temperatures due to the
compounds from cardanol exhibited considerable activity as reported disruption of nucleation and crystal growth processes.
by Rodrigues et al. [72] and Lomonaco et al. [73], respectively. On the
other hand, electrochemical modification of the CNSL [75]resulted to a 2.2.2. Effects of bio-oils on cold flow properties
remarkable reduction in the amount of cardanol but still the modified Mohanan et al. [87] studied the effects of metathesized soybean oil
CNSL performed more effectively, suggesting that either the modifica- (MSBO) and metathesized triolein (MTO) on the crystallization tem-
tion method used or other composition of the CNSL could be re- perature of biodiesel. The study demonstrated that MSBO fractions
sponsible for the antioxidation activity. In this case, we hypothesize exhibited higher freezing point-reduction activity than the MTO due
that other phenolic compounds like cardol and 2-methyl cardol present largely to the nature of the monomers as well as the saturated nature of
in the CNSL could be responsible for this activity. Therefore, there is the the components of MSBO fractions. The PP and CP of a doped biodiesel
need to investigate the most efficient and economical method of mod- have been reported to be significantly affected when treated with
ifying the CNSL considering its various compositions for effective and ozonated sunflower oil (SFO) [88]. However, the activity of the ad-
sustainable application as a biodiesel antioxidant. ditive was less effective when the biodiesel contains high amount of
Moreover, the inedible nature of CNSL, its viability as a feedstock saturated methyl esters. El Rafie and Attia [89] reported an improve-
[77–80]and, most importantly, its moderate effects on improvement of ment in the PP of a doped biodiesel with an unchanged effect on its CP
biodiesel oxidation stability make it a better sustainable substance for following treatment with ozonated SFO. Also, the doped biodiesel did
the production of bio-additives. Table 1 presents the summary of the not agglomerate in sub-ambient condition, suggesting that the ozonated
effects of the various bio-based additives on biodiesel. Specifically, bio- sunflower oil had inhibited nucleation and crystal growth. In another
based additives and the amounts of the additives used, the type of independent report on oil modifications, the activity exhibited by an
solvent and biodiesel used by different authors were tabulated. Most ozonated SFO at low dosage on biodiesel appeared to be a result of
importantly, the major findings of the respective literatures have also some bifunctional compounds with the required geometry and config-
been pointed out. uration to inhibit oxidation from ozonolysis of the SFO (Table 2) [90].
Quite a number of articles attributed the performance of the various Estolides and esters (from castor and lesquerella oils) slightly reduced
additives to the presence of phenolic compounds in them. The hydroxyl the PP of palm oil methyl esters, whereas methyl esters from soybean
(-OH) groups present in the phenolic compounds react with the fatty showed no obvious impact on both the CP and PP even at the maximum
acid free radicals, where the antioxidants donate hydrogen to the oxi- dosage used [91].
dized free radicals which results to inhibition of oxidation. Also, the
more the number of the –OH group present in the aromatic ring of the
2.2.3. Effects of transesterification/esterification products on cold flow
phenolic compounds the more effective the antioxidants become and
properties
where phenolic compounds with three –OH groups are liable to having
The use of glycerol derivatives as additives for the improvement of
more antioxidation effects than those with less –OH groups [81]. From
low temperature properties of biodiesels has also been investigated
Fig. 4, the phenolic compounds I and II donate hydrogen to the bio-
from different angles. The effects of ketals synthesized from glycerol
diesel free radical making it stable, thereby preventing its oxidation.
(using acetone, 2-butanone, cyclopentanone,4-methyl-2-pentanone and
This suggest that higher dosage of bio-based additive with phenolic
3,3-dimethyl-2-butanone) on the CFPP of biodiesel generated CFPP
compound I is needed to achieve the activity of bio-based additive with
values of −6 °C and −5 °C for the biodiesel at the maximum dosage of
phenolic compound II. This scenario could be responsible for the var-
the glycerol derived from 2-butanone and cyclopentanone, respectively
iations in the performance of the various bio-based additives reviewed.
[92]. This suggests that different ketone precursors could yield glycerol
ketal additives with different activities for the improvement of low
2.2. Effects of bio-based additives on cold flow properties of biodiesel
temperature properties of biodiesel. Comparison has also been made on
the effects of glycerol ketals, glycerol acetates and branched alcohol-
2.2.1. Effects of cellulosic derivatives on cold flow properties
In an effort to discover the best bio-based additives for the im-
provement of low temperature properties of biodiesel, various ap-
proaches have been applied by different groups. Some cellulose deri-
vatives including ethyl levulinate (EL), ethyl acetoacetate (EAA) and
ethylene-vinyl acetate co-polymer (EVAC) have been used as additives
for the improvement of biodiesel cold flow properties. Addition of EL to
biodiesel resulted in significant (P < 0.05) decrease in cloud point
(CP), pour point (PP) and cold filter plugging point (CFPP) at the
maximum dosage (20% vol./vol.) [82]. These effects have been at-
tributed to the simple dilution of the saturated esters that are vulner-
able to crystallization at low temperatures, taking advantage of the low
freezing point of EL (-790C). Treatment with EAA also caused appre-
ciable decrease in the CP, PP and CFPP values, respectively [83]. Fur-
thermore, combined application of EAA and EL as additives sig-
nificantly (P < 0.05) reduced CP, PP and CFPP of the biodiesel, where
increase in the dosage of the additives caused a corresponding decrease
in the trend of the values [84]. Substantial achievement using EVAC
was also recorded for B20 and B100 biodiesel, where −12, −16 and Fig. 4. Mechanism for the antioxidant effects of phenolic compound present in
−18 °C and 5, 2 and 1 °C were achieved for CP, PP and CFPP the bio-additive.

88
 Table 2
Summary on the effects of bio-based additives on the cold flow properties of biodiesel.
Additive (s) Amount (s) Biodiesel (s) Findings Ref.
I. Lawan et al.

Ethyl levulinate 2.5–20% (vol.) B100-Cotton seed oil/Poultry fat biodiesel • Blending the biodiesels with the EL have significantly improved the cold [82]
flow properties
• Reductions of 4–5 °C in CP, 3–4 °C in PP and 3 °C in CFPP were recorded
Ethyl acetoacetate (EAA) 2.5–20%(vol.) B100-Waste cooking oil biodiesel • Increase in dosage has resulted to decrease in PP and CFPP [83]
of 4 °C was recorded for the PP and CFPP
0
Ethyl acetoacetate (EAA)/ Ethyl levulinate (EL) 5–20% (vol/vol.) B100- Milk scum biodiesel
• Reduction
PP and CFPP of 8 ± 0.33, 4 ± 0.57, and 7 ± 1.15 C were [84]
• CP,
achieved with the EL using 20% vol./vol.
0
• CP, PP and CFPP of 8 ± 0.33, 6 ± 0.66, and 7 ± 0.66 C were
achieved with the EL using 20% vol./vol.
Ethyl vinyl acetate copolymer (EVAC) 0.04% (wt.) B20/B100- Waste cooking oil biodiesel 2 and 1 °C were obtained for the CP, CFPP and PP of the doped B100
• 5,biodiesel [85]
samples
• Reduction of 8, 10 and 11 °C were achieved for the CP, PP and CFPP of
B20 biodiesel
Polyglycerol esters (PGE) and EVAC 0–2% (wt.) B100-Palm oil biodiesel (PFME) • Reduction of 1.5, 3.5 and 3.1 °C in crystallization temperature with [86]
EVAC, PGE and EVAC + PGE respectively
Pine pellets/chips oil 10–50% (wt.) B100-Poultry fat biodiesel • Reduction of more than 5 °C for completion of melt onset temperature [59]
and onset temperature with addition of bio-oil
Metathesized soybean oil (MSBO) and Triolein 1–4% (wt.) B100-Soy 1500 biodiesel • Reduction of 1–4 °C was achieved for the crystallization onset [87]
temperature with the MSBO fractions
• The maximum reduction was obtained with the 3% (wt.) dosage
Ozonized sunflower oil 1–1.5% (wt.) B100-Sunflower oil (SFO), soybean oil (SBO), • Significant reduction in pour points were achieved even at the least [88]
rapeseed oil (RSO) , palm oil (PMO) biodiesels dosage in all the biodiesels
• Pour point of − 24.0 ± 1 °C, − 9.0 ± 1 °C, − 30 ± 1 °C and 11 °C
were achieved for the biodiesels respectively
poor result achieved with the PMO was attributed to the higher

89
• The
saturated contents
Ozonated sunflower oil 1% (wt.) B100- Soybean oil, linseed oil, mixed oil (soybean • The PP values were decreased to 0,− 3 and 0 °C for the biodiesels [89]
+sunflower) biodiesels respectively
• The CP has not change with the addition of the additive
• The agglomeration of biodiesel crystals were inhibited at low
temperature
Castor and lesquerella oil derivatives ≤ 5% (wt.) B100-soybean oil (SME) and paalm oil biodiesel of PME was reduced by 3 °C with all the derivatives at the maximum [91]
(PME)
• PPdosage
• CP of both the biodiesels was not affected by all the derivatives even at
the maximum dosage
Glycerol ketals 1–20% (vol.) NS • Reduction of 3 °C and 2 °C were achieved for the CFPP with glycerol [92]
derived with 2-butanone and cyclopentane ketones respectively
Glycerol ketals, glycerol acetate, BC-FAME 1–10% B100-Palm oil biodiesel • The BC-FAME was found to be the best additive [93]
• The PP and CP were reduced to 6 °C at 5% dosage and 5 °C at 1% dosage
Glycerol acetal/butanal, glycerol acetal/pentanal, glycerol acetal/ 1–5% (vol.) B100-Animal fat biodiesel • Reduction in PP from 18 °C to 13 °C was achieved with 5% (vol.) dosage [94]
hexanal, glycerol acetal/octanal, glycerol acetal/decanal of glycerol acetal derived using butanal
Solketal, TAG, TBGs, AGs 5–25.8 g/100 g B100- Soybean biodiesel • Reduction in PP from − 4 to − 7 °C was achieved [95]
• Reduction of 3 °C in CFPP was achieved
Castor and lesquerella oil derivatives ≤ 5% (wt.) B100-soybean oil (SME) and paalm oil biodiesel of PME was reduced by 30C with all the derivatives at the maximum [91]
(PME)
• PPdosage
• CP of both the biodiesels was not affected by all the derivatives even at
the maximum dosage
BC-Ethers 0.5–2.0% (wt.) B100-Soybean oil biodiesel • Reduction in CP from 2 to − 1 °C and PP from 1 to − 2 °C were achieved [96]
with 2-ethyl-hexyl ether at the maximum dosage
(continued on next page)
Renewable and Sustainable Energy Reviews 102 (2019) 83–95
I. Lawan et al. Renewable and Sustainable Energy Reviews 102 (2019) 83–95

CP: Cloud point, CFPP: Cold filter plugging point, PP: Pour point, TAG: Tri-acetyl glycerol, TBGs: Mixture of tert-butylated glycerol, AGs: Mixture of glycerol. BC-Ethers: Branched-chain ethers, BC-FAME: Branched-chain
derived fatty esters (isobutyl esters, isopropyl esters and 2-butyl esters)

[97]

[98]
Ref.
on the cold flow properties of biodiesel [93]. The findings reveal a
decreasing trend in the cold flow properties of the biodiesel with in-

and PP of −14 and −21 °C were achieved with the additives at 30%

and PP of −28 and −33 °C were achieved with the additives at 50%
and PP were significantly improved at 17% and 39% (wt.) dosage

lowest CP and PP achieved were − 10.1 ± 0.60 and − 17.0 °C creasing dosage of the additives, with 2-butyl esters being the most
effective of all. Also, there were reductions in the doped biodiesel
additives have drastically reduced the crystallization onset crystal sizes at the sub-ambient conditions.
temperature by up to 12–14 °C compared to the neat samples
Silva et al. [94] investigated the effects of glycerol acetals synthe-
sized from butanal, pentanal, hexanal, octanal and decanal as anti-
freezing additives for biodiesel. The PP of the synthesized acetals were
reported to be −66, −66, −63, −39 and −12 °C, respectively. A
decreasing trend in the PP of the biodiesel has also been reported with
increasing dosage where the glycerol acetal derived from butanal de-
monstrated the most effective performance. This performance could be
attributed to the lowest PP exhibited by the glycerol actals derived from
using the BC-FAME as diluents

butanal due to the size of the hydrocarbon chain and reduced aldehyde
chain.
The effects of some oxygenated compounds derived from glycerol,
including solketal (2,2-Dimethyl-4-hydroxymethyl-1,3-dioxolane),
triacetin (Tri-acetyl glycerol (TAG), mixture of tert-butylated glycerol
(wt.) dosage

(wt.) dosage
respectively

(TBGs) and mixture of glycerol esters (AGs),on the low temperature

properties of biodiesel have also been tested previously [95]. The re-
Findings

• The
• The

sults reveal a drastic improvement in the cold flow properties of the

• CP

• CP
• CP

doped biodiesel. The best PP and CFPP were obtained from the solketal
and the TBGs, and thus TBGs could serve as an effective bio-additive for
the improvement of cold flow properties of the biodiesel. Critical con-
B100-Canola oil, palm oil, soybean oil biodiesels

siderations of the studies reported by Torres et al. [92], Giraldo et al.

[93] and Silva et al. [94] on the application of glycerol derivatives to
biodiesel suggested their strong viability as bio-additives for the bio-
diesel. Large amount of glycerol was produced following biodiesel
production and this makes the glycerol easily obtainable, thereby
making the entire biodiesel production more profitable and sustainable.
B100-Soybean oil biodiesel

Branched-chain ethers demonstrated a CP of −23 °C and PP of

−25 °C at the maximum dosage, where 2-ethylhexyl ethers exhibited
the highest activity in contrast with isopropyl ester and isobutyl es-
teronon the cold flow properties of soybean oil methyl esters [96].
Biodiesel (s)

Furthermore, Dunn et al. [97] studied the effects of branched-chain

fatty acid methyl esters (BC-FAME) on the cold flow properties of
biodiesel. The BC-FAMEs methyl isooleate (Me iso-C18:1) and methyl
iso-stearate isomers (Me iso-C18:0) were investigated at relatively low
fatty acid, B100: 100% biodiesel, B20: 20% biodiesel + 80% petro diesel, NS: Not stated.
0.5–2% (wt.) and 0.5–50%

dosage as additives and very high dosage as diluents. The authors reveal
that as additives, the BC-FAMEs did not impact any improvement on the
30% and 50% (wt.)

cold flow properties of soybean methyl ester as a biodiesel. However,

the BC-FAMEs as diluents have impacted positively by drastically re-
Amount (s)

ducing the PP and CP of the doped biodiesel and the PP and CP values
increased with increase in the degree of saturation of the biodiesel
(wt.)

doped (50.30% < 15.71% < 6.87% for the palm, soybean and canola
oil biodiesel, respectively). It has been concluded that Me iso-C18:0 BC-
FAME had a better performance attributed to the structural nature of
the compounds. Similarly, the crystallization onset temperatures (TCO)
of the branched-chain esters obtained from soybean oil (SBO), low-
palmitate soybean oil (LPSBO), canola oil, tallow, lard, branched-chain
alcohols (isopropyl and 2-butyl esters) and their corresponding methyl
esters were compared where the branched esters obtained from the SBO
exhibited the lowest reduction in the TCO with further significant re-
duction in its TCO when blended as a diluents [98]. The performance of
the BC-FAMEs as bio-based additives may be due to the disruption of
the molecules nucleation process caused by the bulky structure of al-
cohol present in the BC-FAME molecules.
Considering the fact that biodiesel is made up of saturated and
unsaturated methyl esters, high dosages may not affect the minimum
Table 2 (continued)

content of the methyl esters (96.5% mol/mol) as suggested by the EN

14103. The effects of the additives/diluents at such dosage could
Additive (s)

therefore be explained by simple dilution effects of the esters in relation

BC-FAME

BC-FAME

to their structures, which is a well-established concept referred to as

biodiesel-biodiesel blends as reported by some groups [99–104].
Furthermore, studies on the low temperature improvement using

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I. Lawan et al.
the bio-based additives have attributed the effects of their additives to
the simple dilution effect. The mechanism involved in the simple di-
lution effects could be explained by the various stages described in
Fig. 5. At equilibrium condition, the saturated and unsaturated mole-
cules of the biodiesel remain free. However, when the bio-diesel is
exposed to temperature that is lower than the equilibrium temperature,
the saturated molecules begin homogenous nucleation which results to
the flocculation of the molecules as the first stage of the crystallization
as shown in Fig. 5(B). At the second stage (Fig. 5(C)), homogenous
nucleation of the unsaturated molecules will also occur and finally,
crystal-like particles will be formed at the final stage (Fig. 5(D)) by the
heterogeneous nucleation of the flocculants formed by homogenous
nucleation.
Conversely, in the case of the biodiesel doped with the bio-based
additive (Fig. 5(E)), the additive forms a membrane that covers the
surface of the molecules thereby preventing them from coming together
which disrupts the nucleation process. This effect reduces the rate of
nucleation and flocculation. Thus, freezing point and amount of the
additive used would be the major factor that would dictate the reduc-
tion in the rate of nucleation. Therefore, besides the variations in the
type of biodiesel used by different authors in Table 2, the above ex-
plained phenomenon could also explain the differences in the perfor-
mance of the various bio-based additives reported.
Oxidation stability of biodiesel was greatly investigated by different
research groups working on a number of additives for the improvement
of the cold flow properties of the biodiesel; and different groups have
reported different findings. For instance, some groups established po-
sitive effects of the additives on both cold flow properties and oxidation
stability of the biodiesel [96,85 and 59]. Others, however, reported null
effects of the additives on the oxidation stability of the biodiesel
[82,93]; whereas some [92,95] reported negative effects of the ad-
ditives on the oxidation stability of the biodiesel, even though values of
the induction period obtained were still within the limits suggested by
the standards. Table 2 presents the summary of the effects of the bio-
based additives on the cold flow properties of the biodiesels.
2.3. Effects of bio-based additives on other fuel properties of biodiesel
In addition to the established effects of bio-based additives on the
oxidation stability and cold flow properties of biodiesel (Table 1 and
Table 2), the impacts of those additives on some other fuel properties of
the biodiesel have also been analyzed to certain extents. These other
properties include flash point, acid number, kinematic viscosity, den-
sity, heating value, water content, carbon residue, cetane number,
sulfate ash, iodine value and peroxide value of the biodiesel.
Fig. 5. Mechanism for the inhibition of nucleation and flocculation of biodiesel.
91
Renewable and Sustainable Energy Reviews 102 (2019) 83–95
2.3.1. Effects of bio-based additives on flash point
The flash point of a biodiesel is the lowest temperature at which the
biodiesel ignites when exposed to a flame. Thus, higher flash points
make biodiesel safer. Minimum flash point of 52 °C for B6-B20 biodiesel
was suggested by ASTM D7467 and 93 and 1200C for B100 biodiesel
was suggested by EN 14214 and ASTM D6751, respectively. Among the
various additives used as presented in Table 3, a decrease in flash point
value of the doped biodiesel was observed and in most cases, the de-
creasing trend of the flash point with increase in the amount of the
additive was also observed by all the studies reported [65,88,89,84,93
and 95] except one [85] where an increase in flash point with increase
in the additive dosage was observed. This maybe a result of the re-
spective flash point values of the various additives used. Although all
the authors believed that the values of the flash points obtained were all
within the limits suggested by the ASTM D6751, ASTM D7467 and EN
14214, the variations in the flash points of the doped biodiesel due to
addition of the additives could limit the utilization of the additives on
other biodiesels with relatively lower flash points. Thus, this highlights
the need to investigate bio-based additives that could either be neutral
or have positive impact on the flash points of the biodiesel, though the
effective methods to investigate these are currently lacking.
2.3.2. Effects of bio-based additives on acid number
The acid number of a biodiesel refers to the minimum milligrams of
potassium hydroxide that is required to neutralize one gram of the
biodiesel sample. The maximum acid number of 0.50 mg KOH/g has
been suggested by both EN 14214 and ASTN D6751 for the B100 bio-
diesel and 0.30 mg KOH/g has been suggested by ASTM D7467 for B6-
B20 biodiesel. Sousa et al.[35] established an additive with neutral ef-
fects on the acid number of a doped biodiesel whereas contrary findings
were reported by some other groups. For instance, some studies have
observed an increasing trend of the acid number of the doped biodiesel
with increase in the additive dosage [59,61,65,85,89] while others
demonstrated otherwise [76,82–84]. In spite of the increase or decrease
in the acid numbers, as the case may be, the values were still within the
aforesaid standard limits. However, the increasing trend exhibited by
these additives could limit their application on biodiesels with rela-
tively higher acid numbers. We therefore hypothesize that the in-
creasing trend caused by the bio-based additives could be attributed to
the acidic nature of the various additives used. Considering the effects
biodiesels with high acid numbers could have on fuel storage tank and
engine components, additives with little or no acidity should be con-
sidered for investigation.
I. Lawan et al. Renewable and Sustainable Energy Reviews 102 (2019) 83–95

Table 3
Summary on the effects of bio-based additives on other fuel properties of biodiesel.
Additive (s) Amount (s) Solvent (s) Effects of additives on other fuel properties of biodiesel Ref.

FP AV V D LHV HHV WC CR CN SA IV PV
Curcumin 500–1500 ppm Methanol nd ▬ ▬ nd nd nd nd nd nd nd ↓ ↓ [35]
β- carotene 500–1500 ppm Methanol nd ▬ ↑ nd nd nd nd nd nd nd ↓ ↓ [35]
Pine wood oil 1–8% (wt.) AC, CH, TO, nd nd ▬ nd nd nd nd nd nd nd nd nd [57]
IPP,2HE, DE, MA,
EA, ISPPA, Nba
Pine wood oil < 2% (wt.) H2O, H2O/BT, H2O/ nd nd ▬ nd nd nd nd nd nd nd nd nd [58]
EA, H2O/ISPPA
Pine wood oil 20% (wt.) EA nd ↑ nd nd nd nd ↑ ↑ ↓ ▬ nd nd [61]
Male wood oil 20% (wt.) EA nd ↑ nd nd nd nd ↑ ↑ ↓ ▬ nd nd [61]
Pine wood oil 20% (wt.) 2-propanol ↓ ↑ nd ↓ ↑ nd ↓ nd nd nd nd nd [65]
CNSL 5000 mg/kg Solvent nd ↓ ↑ ↑ nd nd nd nd nd nd nd ↓ [76]
Pine wood oil 10–50% (wt.) nd ↑ ↑ ↑ nd ↓ ↑ nd nd nd nd nd [59]
Ozonized sunflower oil 1–1.5% (wt.) None ↓ nd ↑ ↑ nd nd nd nd nd nd nd nd [88]
Ozonized sunflower oil 1% (wt.) None ↓ ↑ ↓ nd nd nd nd nd nd nd nd nd [89]
EL 5–20% (vol.) None ↓ ↓ ↓ nd nd nd nd nd nd nd nd nd [84]
EAA 5–20% (vol.) None ↓ ↓ ↓ nd nd nd nd nd nd nd nd nd [84]
EL 2.5–20% (vol.) None ↓ ↓ ↓ nd nd nd nd nd nd nd nd nd [82]
EVAC 0.04% (wt.) None ↑ ↑ ↑ nd nd nd nd nd nd nd nd nd [85]
EAA 2.5–20% None ↓ ↓ ↓ nd nd nd nd nd nd nd nd nd [83]
BC-FAME 5–50% (wt.) None nd nd ↑ nd nd nd nd nd nd nd nd nd [97]
BC-FAME 5% None ↓ nd ↑ ↓ nd nd nd nd ↑ nd nd nd [93]
BC-Ethers 0.5–2.0% (wt.) None nd nd ↑ nd nd nd nd nd nd nd nd nd [96]
FP AV V D LHV HHV WC CR CN SA IV PV
Glycerol ketals 1–20% (vol.) None nd nd ↑ nd nd nd nd nd nd nd ▬ nd [92]
Glycerol-solketal 5–25.8 g/100 g None ↓ nd ↓ ↑ nd nd nd nd nd nd nd nd [95]
Glycerol-triacetin 5–25.8 g/100 g None ▬ nd ↑ ↑ nd nd nd nd nd nd nd nd [95]
Glycerol-mix of ethers 5–25.8 g/100 g None ↓ nd ↓ ↑ nd nd nd nd nd nd nd nd [96]
(TBGs)
Glycerol-mix of esters 5–25.8 g/100 g None ▬ nd ↑ ↑ nd nd nd nd nd nd nd nd [35]
(AGs)

FP: Flash point, AV: Acid value, V: Viscosity, D: Density, LHV: Lower heating value, HHV: Higher heating value, WC: Water content, CR: Carbon residue, CN: Cetane
number, SA: Sulfate ash, IV: Iodine value, PV: Peroxide value, ↑: Increase in numerical value,↓: Decrease in numerical value, ▬:No effects, nd: Not determined, AC:
Acetone, CH: Cyclohexane, TO: Toluene, IPP: Isopropanol, 2EH: 2-ethyl-1-hexanol, DE: Diethyl ether, MA: Methyl acetate, EA: Ethyl acetate, ISPPA: Isopropyl
acetate, nBA: n-butyl acetate, BT: Butanol, CNSL: Cashew nut shell liquid, EL: Ethyl levulinate, EAA: Ethyl acetoacetate, EVAC: Ethylene vinyl acetate copolymer, BC-
FAME: Brached-chain fatty acid methyl esters.

2.3.3. Effects of bio-based additives on kinematic viscosity
Kinematic viscosity is the main reason why biodiesel are used in-
stead of the crude vegetable oils or animal fats, since high kinematic
viscosity of vegetable oils or animal fats ultimately cause engine op-
erational problems and deposits [105]. The limits suggested by the EN
14214 and ASTM D6751 for B100 biodiesel are 3.5–5.0 mm2/s and
1.9–6.0 mm2/s, respectively, while 1.9–4.1 mm2/s was suggested for
B6-B20 biodiesel by the ASTM D7467. Findings from some studies
[35,57,58] reveal that the effects of additives that involved curcumin
extract and pine wood oil were neutral to the kinematic viscosity of the
doped biodiesels. Conversely, β-carotene extract, CNSL, pinewood oil,
ozonized sunflower oil, EVAC, BC-Ethers, BC-FAME and glycerol deri-
vatives were found to increase the kinematic viscosity of the doped
biodiesel [35,59,76,85,88,92,93,95–97]. Conflicting findings were
presented by Gil-Lalaguna et al. [58] and Garcia-Perez et al.[59], where
neutral and increasing acidity effects were achieved, respectively,
which could be explained from the higher dosage used by the latter
group and the additional solvents used by the former group as shown in
Table 3. On the other hand, some of the findings presented by the au-
thors reveal that the additives caused a decrease in the kinematic
viscosity of the doped biodiesel [82–84,89]. The variations observed
from the different reports could be attributed to the differences in the
rheological properties of the additives used, amount of the additives
used, solvent used and the kinematic viscosities of the various biodiesel
used before doping with the additives. Despite those variations, the
values of the kinematic viscosities were still within the standard limits.
2.3.4. Effects of bio-based additives on density
Density is another fuel property of remarkable importance. It has
been established that bio-based additives like the pinewood oil, CNSL,
ozonised sunflower oil and the glycerol derivatives were found to in-
crease the density of the doped biodiesel [59,76,88,95] while other
studies reported a decrease in density of the doped biodiesel [65,93].
The conflicting findings between the studies on pinewood oil (Table 3)
[59,65] could also be explain by the differences in the solvents and
dosages used, though both generated data were still within the re-
commended range. Table 3 presents the effects of the heating value,
water content, carbon residue, cetane number, sulfate ash, iodine and
peroxide values.
2.4. Effects of bio-based additives on CI engine characteristics
Ramalingam et al. [32] studied the performance and emission of the
CI engine with B20 calophyllum biodiesel. The characteristics indices
studied include brake thermal efficiency (BTE),brake specific fuel
consumption (BSFC),carbon monoxide (CO),hydrocarbon(HC), smoke
and oxides of nitrogen(NOX) emission. Their findings reveal that the
BTE increased with increase in the loading condition and the average
BTE of the neat B20 sample was 19.598%. When doped with pongamia
pinnata leaves extract, however, there was slight increase in BTE with
increase in the additive dosage meaning that the trend established was
B20A15 > B20A10 > B20A5 > B20. Similar results have also been
reported in some independent investigations [106,107]. This trend
might be a consequence of the increased ethanol content of the ad-
ditives in relation to increase in the additive dosage.
Conversely, an insignificant change in the BTE was reported when a
bio-oil obtained from pine wood was supplemented to sunflower bio-
diesel [108]. This contrast could be a result of the differences in the
dosage, solvents used and the molecular composition of the additives.
As regards to BSFC, Ramalingam et al [32] reported a slight increase

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I. Lawan et al.
this index with increase in the amounts of the said additive, where an
average of 0.4218, 0.4481, 0.448, 0.4532 and 0.4582 kg/kWh were
recorded for B20, B20A5, B20A10 and B20A15, respectively [32].
However, this is contrary to a previous report [106], probably due to
low calorific values of the additives which lead to increased con-
sumption of the experimental samples since ethanol could have nega-
tive effects on some additives [107].
Limited data have so far been generated investigating the effects of
additive-doped biodiesels on CI engine characteristics as regards to
emission. Significant increase in carbon monoxide (CO) emission with
corresponding increase in the dosage of the additives [32,108] were
recorded, which was attributed to increase in the ignition delay, that
possibly resulted from the increased in additive dosage [32], although
how this additive influences the ignition delay still remains a puzzle.
The latter team also recorded a marked increase in hydrocarbon (HC)
emission, owing to the high latent heat of vaporization of the ethanol
present in the additive. Smoke and oxides of nitrogen (NOX) on the
other hand were found to decreased when pin wood bio-oil, soy-lecithin
and pongamia pinnata leaves extract were used as additives
[32,108,109]. The observed reduction in NOX could have arose from
the low adiabatic flame temperature of the ethanol present in the ad-
ditive as well as free radical scavenging effects of the carotenoid found
in the extract [32]. However, the actual component of the additive that
is responsible for the decrease in NOX requires further exploration.
3. Future perspective
A number of reports have adequately suggested the various ways of
improving biodiesel quality via supplementation of bio-additives.
However, only little attention is paid to the utilization of non-edible
bio-oils as additives for the improvement of the oxidation stability of
biodiesels. In-depth studies are also required to establish the specific
component(s) of the bio-oils responsible for their immiscibility, high
acidity, high viscosity and high density so as to come up with better
strategy of refining the bio-oils for better activity as antioxidants. This
will not only solve the problem of using extra solvents to achieve a
desired miscibility of bio-oils with the biodiesels but also alleviates the
negative effects of the bio-oils on the other fuel properties of the bio-
diesels. Studies should also focus on the appropriate treatment methods
of the already established bio-based additives in order to come up with
additives with little or no negative effects on other fuel properties,
diesel engine performance and emissions. Considering the fact that
studies on bio-based additives that could provide protection of biodie-
sels against microbial degradation are presently inadequate, bio-based
additives with bio-active compounds that could prevent microbial de-
gradation of the biodiesel should also be investigated.
Sampling some of the findings from the antioxidant additives re-
viewed reveals that Sousa et al. [35], Rocha et al. [34] and Devi et al.
[46] achieved 6.35, 8.75 and 23.99 h induction period using 5000,
4000 and 2000 ppm dosages, respectively. Projections of these findings
show that22.73, 18.18 and 9.09 mL/gallon of the curcumin/β-carotene,
Moringa oleifera and ginger extracts need to be used on B100-Soybean
oil, B100-Commercial oil blends and B100-Pongamia pinnata oil bio-
diesel, respectively. From the temperature depressants reviewed ,re-
duction of 4–5 °C in cold flow properties was recorded [82] using 20%
vol/vol. dosage and projection of this finding reveals that ~1 l/gallon
of EL is needed on B100-Cotton seed oil and poultry fat biodiesel.
However, these sampled findings did not report whether their resulting
blends is within the acceptable limits considering the high dosages used
and the minimum ester content of biodiesels(96.5% mol./mol and
6–20% vol. for B100 and B20, respectively) acceptable by the EN 14103
and ASTM D7371. Thus, feedstock with high amount of poly-phenols,
other bio-active compounds and extremely low temperature properties
should be used so that very low dosage could be employed to achieve
the desired results without exceeding the aforesaid limits.
93
Renewable and Sustainable Energy Reviews 102 (2019) 83–95
4. Conclusions
Various efforts have been made by different groups to investigate
different bio-based additives and substantial achievements have been
recorded towards the improvement of oxidation stability and cold flow
properties of biodiesels. Moreover, some of the reports established the
effects of the additives on the other fuel properties of biodiesels. Herein,
the findings were discussed; the mechanisms responsible for the anti-
oxidation and cold flow properties depression were explained. The
findings suggests that the efficacy of the bio-based additives depends on
the content and type of phenolic compounds present in the feedstock
used for the antioxidation effects and freezing point level of the feed-
stock used for the cold flow depressing effects. Also, it is established
that the effects bio-based additives exhibited on other fuel properties of
the biodiesels such as acid number, kinematic viscosity and flash point
are consequent to the acidic nature, magnitude of viscosity and flash
point level of the feedstock used in the synthesis of the additive. The
bio-based additives used have been classified based on their types and
the methods used for the investigation. These classes include plant
extracts, bio-oils, CNSL, cellulosic derivatives and transestrification/
esterification products. Moreover, recommendations that may provide
the basis for the synthesis of biodiesel additives that will offer more
effective and comprehensive solution to the biodiesel fuel instability
have been raised.
Acknowledgements
The authors would like to acknowledge the funding provided
by the Fujian Agriculture and Forestry University (KXB16001A) and
the Department of Science and Technology of Fujian Province
(2017H6003), PR China.
Conflict of interest
The authors would like to declare that they have no conflict of in-
terest with regards to the submission and publication of their findings.
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