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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.
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
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.
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