You are on page 1of 6

Industrial Crops and Products 62 (2014) 8–13

Contents lists available at ScienceDirect

Industrial Crops and Products


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

Biodiesel production from Stauntonia chinensis seed oil (waste from


food processing): Heterogeneous catalysis by modified calcite,
biodiesel purification, and fuel properties
Rui Wang a,∗ , Lili Sun b , Xiaolin Xie a , Lizhi Ma a , Zhigang Liu a , Xiaoyan Liu a ,
Ning Ji a , Guofang Xie a
a
Guizhou Engineering Research Center for Fruit Processing, Food and Pharmaceutical Engineering Institute, Guiyang College, Guiyang 550003, China
b
Patent Examination Cooperation Center of the Patent Office, SIPO, Beijing 100081, China

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

Article history: In the present research, the potential of Stauntonia chinensis (SC) seed oil obtained from processing waste
Received 15 May 2014 was investigated for the first time as biodiesel feedstock, including physicochemical properties of the oil,
Received in revised form 31 July 2014 the heterogeneous catalysis process, purification, and fuel properties. A 29.37 ± 0.64 wt.% of oil content
Accepted 4 August 2014
and 2.41 mg KOH/g of acid value was found. Under the optimised reaction conditions in the presence of
Available online 29 August 2014
modified calcite, an 88.02% of yield and a 98.90 wt.% of FAME content were achieved. According to EN
14124 (2012), SC biodiesel exhibited superior fuel properties compared to the most of other feedstock
Keywords:
oils since it had an ideal fatty acid composition (low Cn:0 (8.06 wt.%), high Cn:1 (80.16 wt.%), and low
Biodiesel
Stauntonia chinensis
Cn:2,3 (8.45 wt.%)). It was absolutely vital that the use of SC seed oil as a biodiesel feedstock would not
Heterogeneous catalysis compete with its use in food. In summary, SC seed oil should be recommended as a promising feedstock
Modified calcite for biodiesel.
Fuel properties © 2014 Elsevier B.V. All rights reserved.

1. Introduction to the exploration of highly effective heterogeneous catalysts and


corresponding processes.
Recently, increasing concerns about diminishing petroleum Lately, waste has been becoming increasingly important in the
reserves, security of energy supply, pollutant emission, environ- energy industry. According to previous reports, utilisation of waste
mental protection, and food security have been driving an intensive cooking oil could reduce biodiesel production costs by 60–90%,
search for new biomass-based energy sources. Because biodiesel which was much lower than the costs for nonedible plant oils
(fatty acid methyl ester, FAME) is regarded as one of the promising (Yaakob et al., 2013). Therefore, food waste should be regarded as
environment-friendly nonpetroleum alternative fuels, consider- an important and valuable resource for the biodiesel production,
able efforts have been devoted to the exploration and development for example, waste animal fats, waste cooking oil, and industrial
of an ideal feedstock, a highly effective heterogeneous catalyst, and residue (Banković-Ilić et al., 2014; Cho et al., 2012; Hernández
an efficient production process (Borges and Díaz, 2012; Hernández et al., 2014). According to the project (World Agriculture Towards
et al., 2014; Reyes-Trejo et al., 2014). Feedstock-related cost, which 2030/2050: 2012) initiated by the Food and Agriculture Organisa-
constitutes approximately 60–90% of the total biodiesel production tion (FAO), a 70% increase in food production will be implemented
cost, has been regarded as a principal obstacle (Mohammadshirazi in the next 40 years. Food waste should not be overlooked as an
et al., 2014). Therefore, selecting the best feedstock is vital for important raw material source. Besides as an abundant feedstock
ensuring low production costs. Great efforts have been devoted resource, food waste has fuel properties also regarded as a key
parameter contributing to the potential of biodiesel. These proper-
ties depend on the fatty acid composition (FAC). Currently, biodiesel
can be produced using a great variety of animal or plant oil sources,
∗ Corresponding author. Tel.: +86 13985138961; fax: +86 851 540 7613.
but the oxidation stability and cold flow performance of the result-
E-mail addresses: wangrui961@gmail.com, wangrui060729@gmail.com
ing biodiesel samples derived from different animal or plant oils are
(R. Wang). unsatisfactory. Previous studies concluded that the ideal vegetable

http://dx.doi.org/10.1016/j.indcrop.2014.08.002
0926-6690/© 2014 Elsevier B.V. All rights reserved.
R. Wang et al. / Industrial Crops and Products 62 (2014) 8–13 9

oil-based biodiesel should possess high C16:1 and C18:1 content, Table 1
Physicochemical properties of SC seed oil.
low polyunsaturated fatty acid content, and limited saturated fatty
acid content (Pinzi et al., 2009; Ramos et al., 2009). Physicochemical properties Mean ± SD
As mentioned above, the other important technological chal- Oil content (wt%) 29.37 ± 0.64
lenge for biodiesel production is a feasible production process, Acid acid (mg KOH/g) 2.70 ± 0.14
which includes highly effective heterogeneous catalysts and the Saponification value (mg KOH/g) 154.43 ± 2.12
corresponding equipment and techniques. Among numerous basic Iodine value (g I2 /100 g) 72.45 ± 1.13
Average molecular weight 1107.43 ± 5.19
heterogeneous catalysts reported in the literature and patents,
CaO is a promising candidate because of its heterogeneous cat-
alytic behaviour, low cost, environmental benefits, and reusability.
O 33.4 wt.%, Si 0.6 wt.%, Fe 0.1 wt.%, and S 0.2 wt.%. Anhydrous
Apart from these, CaO is also cheap and widely available from such
methanol, boron trifluoride, and all other regents were analytical
sources as natural dolomite, calcite, and lime-stone. Despite the
grade and were purchased from Sinopharm Chemical Reagent Co.,
potential for transesterification catalysis, common CaO is employed
Ltd., Shanghai. All FAME standards, including palmitic acid (C16:0),
at the expense of large catalyst amount, high methanol-to-oil molar
palmitoleic acid (C16:1), stearic acid (C18:0), oleic acid (C18:1),
ratio, long time, and severe conditions because of its low sur-
linoleic acid (C18:2), linolenic acid (C18:3), cis-11-eicosanoic acid
face area, low active site density, and mass transfer limitations. To
(C20:1), and erucic acid (C22:1) methyl ester were purchased from
enhance its catalytic performance, great research efforts have been
Sigma–Aldrich (USA).
devoted and are currently underway in such areas as nanotech-
nology, hydration–dehydration technique, surface modification,
and loading onto supports (Kouzu and Hidaka, 2012; Wang et al., 2.2. Characterisation of physicochemical properties of SC seed oil
2013; Yoosuk et al., 2011). When CaO is used as a catalyst for
biodiesel preparation, residual Ca2+ is always observed in the prod- The SC seed sample was dried in vacuum (100 ◦ C, 0.08 MPa) for
ucts (biodiesel and glycerol) because of calcium soaps and solution 1 h to remove excess moisture. Then, the dried seeds were ground
(Granados et al., 2009; Wang et al., 2013). Ca2+ concentration in the using a laboratory attrition mill and passed through a 20-mesh
final biodiesel product should be below 5 ppm, which is specified (0.9 mm) sieve. The seed oil content (wt.%), acid value (mg KOH/g),
by biodiesel standards (European Standard EN 14124, Australian saponification value (mg KOH/g), and iodine value (g I2 /100 g) were
Biodiesel Standard, and South African Standard). Therefore, a feasi- determined according to ISO 659: 1998, ISO 660: 1996, ISO 3657:
ble purification process is essential (Atadashi et al., 2011). To date, 2002, and ISO 3961: 1996. For the trans-esterification reaction,
vacuum distillation has been one of the most economic and feasible average molecular weight of SC seed oil was deduced according
industrial processes for biodiesel purification, which can simulta- to the method of Zhu et al. (2006). All data were listed in Table 1.
neously remove the residual methanol, catalyst, glycerol, and other
impurities from biodiesel. 2.3. Catalyst preparation, characterisation, and regeneration
Different from Carica papaya L. (CP) (Winayanuwattikun et al.,
2008), Stauntonia chinensis (SC) is a member of the Rosaceae fam- In a typical preparatory reaction, 200 g of calcite powder was cal-
ily and is native to and widely spread in southern China. Although cined at 800 ◦ C for 3 h in static air. Then, the calcined calcite (100 g)
the pulp of SC is edible, the edibility of SC seed oil is unascertained was refluxed in distilled water (400 g) at 80 ◦ C for 6 h, and the reac-
at present. And the poisoning incidents have occurred in Zhengan tion mixture was filtered and dried in vacuum (100 ◦ C, 0.08 MPa)
country, Gui zhou province, China. Up to data, approximate 60,000 for 1 h in static air. According to the thermogravimetric analysis
acres of SC were cultivated in Guizhou and Sichuan province and (TGA) results shown in Fig. 1, the hydrated sample was calcined at
Chongqing city of China, and most of the SC fruit (approximately 750 ◦ C for 1 h. The final product was named as modified calcite. To
250,000 t/a) is processed into beverage, tin, and sweetmeat. As a avoid poisoning by CO2 and H2 O, all calcined products were stored
result, biomass in the form of SC seed is generated in large quan- in a desiccator containing silica gel and KOH pellets.
tities (approximately 15,000 t/a) as waste from the SC-processing The TGA data of hydrated sample was recorded by a Netzsch
industry. That means about 5000 t/a of seed oil is discarded. In the STA449C at a heating rate of 4 ◦ C min−1 in an atmosphere of pure
present study, SC seed oil, known as the waste of food processing, nitrogen. BET measurement was performed by a Micromeritics
was catalysed to biodiesel by modified calcite. The modified calcite TriStar II 3020 system (adsorption of N2 at 77 K). After degassing for
was prepared by means of the hydration–dehydration technique 3 h at 573 K, we calculated the special surface area (SSA) of the mod-
(Yoosuk et al., 2011). Then, the crude biodiesel sample was refined ified calcite by BET method over the relative pressure range (P/P0 ) of
using vacuum distillation. Finally, the fuel properties of the refined 0.05–0.20. The morphological characteristics of the modified calcite
biodiesel sample were determined and evaluated. To our knowl- were examined using scanning electron microscopy (SEM; Zeiss
edge, there were no studies reported on SC seed oil as a feedstock EVO 15LS) operated at an accelerating voltage of 20 kV. Powder X-
for biodiesel production and on the related heterogeneous catalytic ray diffraction (XRD) patterns with a step size of 0.02 from 10◦ to
processes. 70◦ of the catalyst samples were obtained using a Bruker D8 X-ray
diffractometer equipped with a Cu Ka radiation ( = 0.154 nm) at
40 kV and 30 mA. The base strength was determined using Ham-
2. Materials and methods mett indicators.
During the operation, the surface of CaO was prone to be con-
2.1. Materials and reagents taminated by CO2 and H2 O within a few minutes (Granados et al.,
2009). Therefore, reclaimed modified catalysts were regenerated
SC seed was obtained from Zhunyi Tianlou Wild Pawpaw Co., by recalcination at 850 ◦ C for 1 h after every reaction cycle.
Ltd. (Zhengan county, Guizhou, China), as waste from a bever-
age production process. Natural calcite powder (400-mesh) was 2.4. Quantification of FAC and FAME content, FAME yield, and
collected in Guizhou Province, China. The elemental composition Ca2+ content of the biodiesel sample
analysis was performed using an energy-dispersive X-ray spec-
trometer (Oxford INCA-350), and the components (wt.%) were To measure the FAC and FAME content of the biodiesel sam-
determined as follows: Ca 46.2 wt.%, Mg 1.2 wt.%, C 18.2 wt.%, ple, we employed a Shimazhu GC/MS-QP2010E equipped with
10 R. Wang et al. / Industrial Crops and Products 62 (2014) 8–13

Fig. 1. The patterns of catalyst characterisation: (A) TGA of precursor for modified calcite; (B) XRD for calcined calcite and modified calcite; (C) N2 adsorption–desorption
isotherms of calcined calcite and modified calcite; (D) Scanning electron microscopy (SEM) pattern of modified calcite.

an HP-Innowax column (30 m × 0.32 mm, 0.5 ␮m) and a flame 2.5. Heterogeneous transesterification catalysis and purification
ionisation detector. After methylation according to ISO 5509- of biodiesel product
2001, the main fatty acid species were identified by GC/MS. The
chromatographic conditions reported in our previous work were Expressed oil with a 2.41 mg KOH/g of acid value was obtained
used as follows (Wang et al., 2011): inlet temperature: 523 K; using a vertical hydraulic oil press (6YZ-180) after SC seed was
detector temperature: 553 K; split ratio: 25:1; oven temperature stir-fried at 150 ± 5 ◦ C for 20 min. A heterogeneous basic catalytic
programme: 463 K for 3 min, ramp rate of 15 K min−1 to 513 K, process was chosen because the acid value of expressed oil was
then hold for 10 min; injection volume: 1 ␮L; carrier gas: helium, below 4 mg KOH/g (Ramadhas et al., 2005). Transesterification
at a flow rate of 1.0 mL min−1 ; air flow: 450 mL min−1 ; H2 flow: reactions were performed in an oil bath in a 500 mL 3-necked
40 mL min−1 . Mass spectrometry was conducted according to the glass flask equipped with a thermometer. The flask was loaded
following conditions: carrier gas: helium; electron energy: 70 eV; with 200 g of seed oil, the prescribed amounts of the cata-
interface temperature: 553 K; ion source temperature: 503 K; lyst and methanol, and then was subjected to magnetic mixing.
quadrupole temperature: 423 K; mass scan range: 50–550 m/z; sol- The mixture was vigorously stirred (600 rpm) for the required
vent delay: 3.0 min. FAC and FAME contents were obtained by the reaction time at 338 K in an inert atmosphere (N2 ). After the
external standard method that GC data was compared to that of reaction, the mixture was immediately immersed into an ice
known standards. The FAME yield was calculated using the follow- salt bath to stop the reaction. The mixture was filtered, and
ing Eq. (1): excess methanol was removed via rotary evaporation (373 K,
0.08 MPa for 20 min). After that, the liquid phase was transferred
Total weight of FAME
FAME yield(%) = × 100% (1) into a separating funnel and allowed to settle overnight. Crude
Total weight of oil SC biodiesel samples were purified by means of vacuum dis-
After digestion according to the method of Verziu et al. (2008), tillation. The distillation fraction was collected between 175 ◦ C
Ca2+ residue in the resulting biodiesel samples was measured using and 230 ◦ C under 35 ± 5 mmHg, and was named as fined SC
atomic absorption photospectrometry (Shimazu AA-7000). biodiesel.
R. Wang et al. / Industrial Crops and Products 62 (2014) 8–13 11

2.6. Fuel properties XRD pattern (Fig. 1(B)), CaO (32.26, 37.33, 53.84, 64.20, and 67.33◦ )
was the major active species on the surface of the catalyst samples.
The fined SC biodiesel sample was characterised using the CaO diffraction peaks of modified calcite were wider and shorter
standard test methods according to European standards (EN 14214 than those of calcined calcite. The mean primary crystallite size of
(2012)). For comparison and evaluation, we used palm and CP the modified calcite (39 nm) was smaller than that of calcined cal-
biodiesel samples described in earlier studies (Ramos et al., 2009). cite (61 nm), which were deduced using the Scherrer equation. In
contrast to the SEM pattern of calcined calcite reported in our pre-
2.7. Statistical analysis vious study (Wang et al., 2013), sizeable particles (approximately
200 nm in diameter) aggregated in the modified calcite sample,
All experiments were performed in triplicate, and the data were which corresponded to the results of N2 adsorption–desorption
expressed as mean ± standard deviation except for the data of fuel isotherms. In accordance with our previous study (Wang et al.,
properties. 2013), the difference of SSA between the two samples could be
attributed to their different precursors. According to the Hammett
indicators, the basicity of two catalyst samples was determined as
3. Results and discussion
8.2 < pKBH+ < 10.1.
3.1. Characterisation of SC seed oil and comparison to oil from
3.3. Biodiesel production and purification
other plants

We first tested the catalytic activities of calcined calcite and


According to the standard set by ISO 658-2002, the oil con-
modified calcite under the same reaction conditions (SC oil 200 g,
tent of SC seed was 29.37 ± 0.64 wt.% as shown in Table 1. Then
catalyst 3 wt.%, methanol-to-oil molar ratio 10: 1; and 338 K for
a series of characteristics were determined, including acid value
3 h). Because of mass transfer limitations, heterogeneous catalysts
(2.70 ± 0.14 mg KOH/g), saponification (154.43 ± 2.12 mg KOH/g),
also exhibited weaker activity than that of a homogeneous cat-
and iodine value (72.45 ± 1.13 mg I2 /100 g). The FAC of SC, Palm,
alyst. This drawback could be overcome by increasing SSA and
and CP were shown in Table 2. Compared to the other two samples,
active site density (Wang et al., 2013). As illustrated in Fig. 2(A),
the SC oil sample possessed the lowest saturated fatty acid con-
calcined calcite with 5.2 m2 g−1 of SSA provided a 31.54 ± 2.71%
tent (8.06 wt.%), the highest monounsaturated fatty acid content
yield of FAME. When modified calcite with 11.3 m2 g−1 of SSA was
(80.07 wt.%), and the highest degree of unsaturation (96.97%).
tested, the FAME yield was drastically increased to 67.02 ± 1.12%.
According to the characterisation results (XRD, SEM, SSA, and
3.2. Catalyst characterisation
Hammett basicity), we attributed the strong catalytic performance
of modified calcite to its increased SSA. Then the optimal cat-
According to the TGA curve shown in Fig. 1(A), the calcination
alytic conditions for modified calcite were obtained by means of
temperature of the hydrated sample (catalyst precursor) was con-
single-factor experiments. The catalyst amount (3, 5, and 7 wt.%)
firmed to be 750 ◦ C, corresponding to a total 25.91 wt.% loss of the
was first optimised with a 10:1 molar ratio of methanol to oil
initial weight. After the hydration–dehydration procedure, the SSA
at 338 K for 3 h. After the comparison, the highest FAME yield
of calcined calcite and modified calcite samples were analysed.
(91.13 ± 2.46%) was achieved at 5 wt.% of modified calcite. When
Modified calcite possessed higher SSA (11.3 m2 g−1 ) than calcined
the transesterification reaction was completed at 7 wt.% of modified
calcite (5.7 m2 g−1 ). The N2 adsorption–desorption isotherms of
calcite, the interface of phase separation was ambiguous, indi-
the two samples were classified as type III isotherms with type
cating that the saponification occurred and an excessive amount
H3 hysteresis loops (Fig. 1(C)). This result meant that there were
of the catalyst was used. The FAME yield was also decreased to
irregular slit-shaped pores in the two samples, which were formed
74.52 ± 4.14%. Methanol-to-oil molar ratio (8:1, 10:1, 12:1) was
by the aggregation of plate-like particles (Gregg and Sing, 1982).
optimised with a 5 wt.% of the catalyst amount for 3 h. After com-
Furthermore, the latter provided a smaller average pore diame-
parison, the 10:1 stoichiometric ratio was selected, which resulted
ter (33.1 nm) compared to the former (51.9 nm). According to the
in an appropriate FAME yield (91.13 ± 2.46%). When the molar
ratio was increased to 12:1, there was no obvious improvement.
Finally, the effect of reaction time (2, 2.5, and 3 h) on the FAME
Table 2
yield was illustrated in Fig. 2(d). The results showed that a sat-
The FAC of three biodiesel samples.
isfactory FAME yield (90.72 ± 1.92%) with a 97.04 ± 0.32 wt.% of
FAC (wt%) SC Palm CP FAME content was achieved at 2.5 h. Thus, the optimised catalytic
(Ramos (Winayanuwattikun
conditions for modified calcite were as follows: 5 wt.% modi-
et al., 2009) et al., 2008)
fied calcite, methanol-to-oil molar ratio of 10:1, and 338 K for
Lauric acid (C12:0) – 0.1 0.26 2.5 h.
Myristic acid (C14:0) – 0.7 0.46
Palmitic acid (C16:0) 6.87 36.7 17.12
Reclaimed modified calcite was used directly without recalci-
Palmitoleic acid (C16:1) 0.21 0.1 0.45 nation in the next catalytic reaction. As a result, the FAME yield
Stearic acid (C18:0) 1.19 6.6 2.98 decreased to 79.17%, indicating that the active sites of the modified
Oleic acid (C18:1) 79.95 46.1 72.91 calcite were poisoned by CO2 and H2 O, which was in good agree-
Linoleic acid (C18:2) 8.32 8.6 4.83
ment with the data in the literature (Granados et al., 2007). After
Linolenic acid (C18:3) 0.13 0.3 0.29
11-Eicosenoic acid (20:0) 1.72 0.4 0.67 every reaction, the reclaimed modified calcite samples were recal-
11-Eicosenoic acid (20:1) 0.51 0.2 – cined at 850 ◦ C for 1 h. The yields had being stayed above 89.27%
Docosanoic acid (C22:0) – 0.1 0.07 until the fifth time.
Lignoceric acid (C24:0) – 0.1 – Because of saponification and dissolution, the leach of Ca2+ was
Proportion of saturation (Cn: 0) 8.06 44.7 21.56
Proportion of 80.67 46.4 73.36
observed in unrefined crude biodiesel samples prepared by cataly-
monounsaturation (Cn: 1) sis of CaO (Atadashi et al., 2011; Granados et al., 2009; Wang et al.,
Proportion of polyunsaturation 8.45 8.9 5.12 2013). Under the optimised conditions, Ca2+ content in the crude
(Cn: 2, 3) biodiesel samples was 113.62 ± 4.11 ppm in the present study,
Degree of unsaturation [10] 96.97 64.2 83.6
which far exceeded the limits prescribed by EN 14124 (≤5 ppm).
12 R. Wang et al. / Industrial Crops and Products 62 (2014) 8–13

Fig. 2. Effect of catalyst samples (A), modified calcite amount (B), molar ratio of methanol to oil (C), and reaction time (D) on the FAME yield (%).

Consequently, crude biodiesel samples were refined using vacuum parameters of biodisel quality, oxidation stability and cetane num-
distillation (30 ± 5 mmHg), and the fraction from 175 ◦ C to 230 ◦ C ber were inversely proportional to the degree of unsaturation, and
was collected. At the end of distillation, a small amount of solid a higher cetane number was always observed for a higher propor-
was observed at the bottom of the Claisen flask, which was cal- tion of saturated FAME (Ramos et al., 2009). Because SC had the
cium soap synthesised by CaO glyceride under heating. The yield of highest degree of unsaturation (96.97 vs. 64.2 and 83.6, Table 2)
the vacuum distillation procedure was 97.02 ± 4.43%, and the total and the lowest proportion of saturation (8.06 vs. 44.7 and 21.56,
yield including synthesis and purification reached 88.02 ± 3.62%. Table 2), palm and CP biodiesel could provide superior oxidation
Finally, there were no Ca2+ ions detected in the refined biodiesel stability and cetane number than SC, while their cold flow perfor-
sample, and FAME content increased from 97.04 ± 0.32 wt.% to mance and kinematic viscosity were worse than those of the SC
98.90 ± 0.09 wt.%. biodiesel. This finding could be explained as follows: the cold filter
plug point and kinematic viscosity increased with the increase in
3.4. Fuel properties the degree of unsaturation. Some studies revealed that ideal veg-
etable oil-based biodiesel should possess high C16:1 and C18:1
The measured characteristics of SC and palm biodiesel samples content, low polyunsaturated fatty acid content, and limited sat-
were determined according to EN 14124 (2012) and summari- urated acid content [9,10]. According to FAC of the three plant oils
sed in Table 3. For comparison, the predicted properties of CP summarised in Table 2, SC had the lowest proportion of satura-
biodiesel sample which were deduced by fitting of equations tion (Cn: 0, 8.06 wt.%), the highest proportion of C16:1 and C18:1
(Ramírez-Verduzco et al., 2012; Ramos et al., 2009), were also content (80.16 wt.%), and the lowest polyunsaturated fatty acid
listed because there were no measured values reported in the content (Cn: 2, 3, 8.45 wt.%). The only drawback was the weak oxi-
previous study (Winayanuwattikun et al., 2008). Furthermore, dation stability of SC biodiesel, which was a common problem for
some important properties of the three samples were compared most of the vegetable oil-based biodiesel samples. Nonetheless,
and evaluated based on the relationship between fuel properties this problem could be easily resolved by addition of an antioxi-
and FAC content. For the SC biodiesel, all properties met the EN dant. Thus, SC seed oil should be regarded as an ideal biodiesel
14124 standard except the oxidation stability. As two important feedstock.
R. Wang et al. / Industrial Crops and Products 62 (2014) 8–13 13

Table 3
Fuel properties of biodiesel samples.

Fuel properties Test method Limits Samples

SCa Palma (Ramos CPb (Winayanuwattikun


et al., 2009) et al., 2008)

FAME content (wt%) GCc 96.5 min 98.90 97.7 –


Linolenic acid content (wt%) GCc 12.0 max 0.13 0.2 0.29
Density at 15 ◦ C (kg/m3 ) EN ISO 3675 860–900 875 – –
Cetane number EN ISO 5165 51 min 52.1 61 56.27
Oxidation stability (110 ◦ C, h) pr EN 14112 6 min 2 4.0 –
Cold filter plug point (CFPP, ◦ C) DIN EN 116 – −9 10 −7
Kinematic viscosity (mm2 /s; 40 ◦ C) EN ISO 3104 3.5–5.0 4.48 4.5 4.5
Condradson carbon residue (10%) EN ISO 10370 0.30 max 0.05 –
Flash point ( ◦ C) EN ISO 2719 120.0 min 167 176 –
Sulfated ash content (wt%) ISO 3987 0.02 max 0.001 – –
Sulfur content (mg/kg) DIN 51680 10.0 max 5 – –
Acid value (mg KOH/g) pr EN 14104 0.50 max 0.12 0.12 –
Copper strip corrosion at 50 ◦ C, 3 h EN ISO 2160 Class 1 1a – –
Water content (mg/kg) EN ISO 12937 500 max 290 – –
Free glycerol (wt%) pr EN 14 105 0.02 max 0.003 0.01 –
Total glycerol (wt%) pr EN 14 105 0.25 max 0.14 0.06 –
a
Measured value.
b
Predicted value.
c
FAME content (wt%) was determined by GC.

4. Conclusion the case of triglycerides methanolysis using CaO. Appl. Catal. B: Environ. 89,
265–272.
Granados, M.L., Poves, M.D.Z., Alonso, D.M., Mariscal, R., Galisteo, F.C., Moreno-Tost,
The use of waste to produce biodiesel has received wide atten- R., Santamaria, J., Fierro, J.L.G., 2007. Biodiesel from sunflower oil by using acti-
tion worldwide because of the low cost compared to those of vated calcium oxide. Appl. Catal. B: Environ. 73, 317–326.
other sources. Feasibility and characteristics of S. chinensis seed Gregg, S.J., Sing, K.S.W., 1982. Adsorption, Surface Area, and Porosity, 2nd ed. Aca-
demic Press, London, UK.
oil, food processing waste, as biodiesel feedstock were studied Hernández, D., Astudillo, L., Gutiérrez, M., Tenreiro, C., Retamal, C., Rojas, C., 2014.
here and evaluated for the first time. We analysed physicochem- Biodiesel production from an industrial residue: Alperujo. Ind. Crop. Prod. 52,
ical properties of SC seed oil, heterogeneous catalyst (modified 495–498.
Kouzu, M., Hidaka, J.-s., 2012. Transesterification of vegetable oil into biodiesel cat-
calcite) preparation and characterisation, optimisation of cataly- alyzed by CaO: a review. Fuel 93, 1–12.
sis conditions, crude product purification, and fuel properties. The Mohammadshirazi, A., Akram, A., Rafiee, S., Bagheri Kalhor, E., 2014. Energy and cost
results showed that SC seed oil had relatively high oil content analyses of biodiesel production from waste cooking oil. Renew. Sust. Energ. Rev.
33, 44–49.
(29.37 ± 0.64 wt.%), appropriate acid value (2.70 ± 0.14 mg KOH/g)
Pinzi, S., Garcia, I., Lopez-Gimenez, F., Luque de Castro, M., Dorado, G., Dorado, M.,
for direct alkaline catalysis, and low iodine value (72.45 ± 1.13 g 2009. The ideal vegetable oil-based biodiesel composition: a review of social,
I2 /100 g). With the low proportion of saturation (Cn: 0, 8.06 wt.%), economical and technical implications. Energ. Fuels 23, 2325–2341.
high C16:1 and C18:1 content (80.16 wt.%), and the low polyun- Ramírez-Verduzco, L.F., Rodríguez-Rodríguez, J.E., Jaramillo-Jacob, A.d.R., 2012.
Predicting cetane number, kinematic viscosity, density and higher heating
saturated fatty acid content (Cn: 2, 3, and 8.45 wt.%), SC biodiesel value of biodiesel from its fatty acid methyl ester composition. Fuel 91,
demonstrated superior fuel properties. Apart from the advantages 102–111.
mentioned above, the use of SC seed oil as a biodiesel feedstock will Ramadhas, A.S., Jayaraj, S., Muraleedharan, C., 2005. Biodiesel production from high
FFA rubber seed oil. Fuel 84, 335–340.
not compete with food uses. SC seed oil from food processing waste Ramos, M.J., Fernández, C.M., Casas, A., Rodríguez, L., Pérez, Á., 2009. Influence of fatty
should be recommended as a promising feedstock for biodiesel. acid composition of raw materials on biodiesel properties. Bioresour. Technol.
100, 261–268.
Reyes-Trejo, B., Guerra-Ramírez, D., Zuleta-Prada, H., Cuevas-Sánchez, J.A., Reyes, L.,
Acknowledgements Reyes-Chumacero, A., Rodríguez-Salazar, J.A., 2014. Annona diversifolia seed oil
as a promising non-edible feedstock for biodiesel production. Ind. Crop. Prod.
52, 400–404.
The authors gratefully acknowledge the financial supports by Verziu, M., Cojocaru, B., Hu, J., Richards, R., Ciuculescu, C., Filip, P., Parvulescu, V.I.,
the Science and Technology Foundation of Guizhou Province, 2008. Sunflower and rapeseed oil transesterification to biodiesel over different
nanocrystalline MgO catalysts. Green Chem. 10, 373–381.
China (No. [2012]2023); Key Subject Construction Programme for
Wang, R., Li, H., Chang, F., Luo, J., Hanna, M.A., Tan, D., Hu, D., Zhang, Y., Song, B.,
Guizhou, China (No. 2012); Scientific and Technological Innovation Yang, S., 2013. A facile, low-cost route for the preparation of calcined porous cal-
Team for Guizhou Fruit Processing and Storage, China (No. (2013) cite and dolomite and their application as heterogeneous catalysts in biodiesel
production. Catal. Sci. Technol. 3, 2244–2251.
4028).
Wang, R., Song, B., Zhou, W., Zhang, Y., Hu, D., Bhadury, P.S., Yang, S., 2011. A facile
and feasible method to evaluate and control the quality of Jatropha curcus L.
seed oil for biodiesel feedstock: gas chromatographic fingerprint. Appl. Energ.
References 88, 2064–2070.
Winayanuwattikun, P., Kaewpiboon, C., Piriyakananon, K., Tantong, S., Thak-
Atadashi, I.M., Aroua, M.K., Aziz, A.R.A., Sulaiman, N.M.N., 2011. Refining technolo- ernkarnkit, W., Chulalaksananukul, W., Yongvanich, T., 2008. Potential plant oil
gies for the purification of crude biodiesel. Appl. Energ. 88, 4239–4251. feedstock for lipase-catalyzed biodiesel production in Thailand. Biomass Bioen-
Banković-Ilić, I.B., Stojković, I.J., Stamenković, O.S., Veljkovic, V.B., Hung, Y.-T., 2014. erg. 32, 1279–1286.
Waste animal fats as feedstocks for biodiesel production. Renew. Sust. Energ. Yaakob, Z., Mohammad, M., Alherbawi, M., Alam, Z., Sopian, K., 2013. Overview of
Rev. 32, 238–254. the production of biodiesel from Waste cooking oil. Renew. Sust. Energ. Rev. 18,
Borges, M.E., Díaz, L., 2012. Recent developments on heterogeneous catalysts for 184–193.
biodiesel production by oil esterification and transesterification reactions: a Yoosuk, B., Udomsap, P., Puttasawat, B., 2011. Hydration–dehydration technique
review. Renew. Sust. Energ. Rev. 16, 2839–2849. for property and activity improvement of calcined natural dolomite in hetero-
Cho, H.J., Kim, J.K., Hong, S.W., Yeo, Y.K., 2012. Development of a novel process geneous biodiesel production: structural transformation aspect. Appl. Catal. A:
for biodiesel production from palm fatty acid distillate (PFAD). Fuel Process. Gen. 395, 87–94.
Technol. 104, 271–280. Zhu, H., Wu, Z., Chen, Y., Zhang, P., Duan, S., Liu, X., MAO, Z., 2006. Preparation of
Granados, M.L., Alonso, D.M., Sádaba, I., Mariscal, R., Ocón, P., 2009. Leaching biodiesel catalyzed by solid super base of calcium oxide and its refining process.
and homogeneous contribution in liquid phase reaction catalysed by solids: Chin. J. Catal. 27, 391–396.

You might also like