Efficient biodiesel production from Jatropha curcus

Journal of Cleaner Production 208 (2019) 816e826

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Efficient biodiesel production from Jatropha curcus using CaSO4/ Fe2O3-SiO2 core-shell magnetic nanoparticles Siow Hwa Teo a, b, **, Aminul Islam b, c, Eng Seng Chan d, S.Y. Thomas Choong e, Nabeel H. Alharthi g, Yun Hin Taufiq-Yap b, f, ***, Md Rabiul Awual g, h, * a

Graduate School of Life Science and Systems Engineering, Kyushu Institute of Technology, Kitakyushu, Fukuoka, 808-0196, Japan Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia Department of Petroleum and Mining Engineering, Faculty of Engineering and Technology, Jessore University of Science and Technology, Bangladesh d Chemical Engineering Discipline, School of Engineering, Monash University, Jalan Lagoon Selatan, 46150 Bandar Sunway, Selangor, Malaysia e Department of Chemical and Environmental Engineering, Faculty of Engineering, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia f Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, 43400 Serdang, Selangor, Malaysia g Mechanical Engineering Department, College of Engineering, King Saud University, Riyadh 11421, Saudi Arabia h Department of Chemical Engineering, Curtin University, GPO BoxU1987, Perth, WA 6845, Australia b c

a r t i c l e i n f o

a b s t r a c t

Article history: Received 18 June 2018 Received in revised form 7 September 2018 Accepted 10 October 2018 Available online 13 October 2018

Core shell nanostructures have endorsed great enhancements in the production of biodiesel with wellcontrolled size, shape, and surface properties. A simple and reproducible hierarchically porous core-shell CaSO4/Fe2O3-SiO2 material with controllable core morphology was developed. The materials with a well mesoporous structure were prepared by ethanol/H2O media using NaNO3 as the etchant to construct the co-valent bond in Fe2O3 framework, and the CH3COONa was an electrostatic supporter and subordinate reducing agent under mild. Solvothermal conditions. The morphology, porosity and conjugated structure of CaSO4/Fe2O3-SiO2 were measured systematically. The materials of CaSO4/Fe2O3-SiO2 showed remarkable performance in biodiesel production with crude Jatropha curcus and methanol. At suitable state, the biodiesel production reached 94%. Furthermore, the material was easily dispersed in the reaction system, quickly separated from the reaction products without using centrifugation or filtration, and satisfactory catalytic activity maintained after being recycled nine. Controlling the interaction among the active phases of core shell structure might boost structural stability of the material. In addition, the performance was compared with several forms of material in the case of biodiesel production. Therefore, the data are remarkable for offering a new juncture for the fabrication of novel and eco-friendly procedure of hierarchically porous material in the potential biodiesel production. Moreover, the easy separation of material from process fluid and the safe handling were the main impacts to imply the CaSO4/ Fe2O3-SiO2 core-shell material for biodiesel production. © 2018 Elsevier Ltd. All rights reserved.

Keywords: Core-shell composite Biodiesel Solvothermal Jatropha curcus

1. Introduction Global racing towards alternatives to fossil fuels to beat climate change has received great attention recently. The forecasting of

* Corresponding author. Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia. ** Corresponding author. Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia. *** Corresponding author. Department of Chemical Engineering, Curtin University, GPO Box U1987, Perth, WA 6845, Australia. E-mail addresses: [email protected] (S.H. Teo), taufi[email protected] (Y.H. Taufiq-Yap), [email protected], [email protected] (M.R. Awual). https://doi.org/10.1016/j.jclepro.2018.10.107 0959-6526/© 2018 Elsevier Ltd. All rights reserved.

global biodiesel production is raised by 14% from 2016 to 2020 to drive the climate change mitigation. The estimated biodiesel production capacity in 2020 is to be 33.2 billion liters, much higher than that in 2016 (Hajjari et al., 2017). In the biodiesel production, the glycerol or glycerin is a major secondary byproduct. It is also noted that glycerol is produced with methanol as unwanted byproduct in the preparation of fatty acid methyl ester (FAME). Moreover, around 10 pounds of crude glycerol are produced even in the biodiesel production of 100 pounds (McGinnis, 2007). Thus, the biodiesel production could also contribute to expand the production of valuable chemicals in food, pharmaceutical and or cosmetics industries.

S.H. Teo et al. / Journal of Cleaner Production 208 (2019) 816e826

Several studies have been reported for the biodiesel production based on the basic or acidic catalyst under suitable procedures (Theam et al., 2015; Islam et al., 2014, 2015). However, the CaO is particularly drawn the attention through the scientific community in terms of being less toxic, cost-effective and highly basic among the several catalytic compositions. Different sources of CaO and their supported catalysts have been studied, including CaO, Ni-CaOMMT, MgO-Al2O3-CaO/TiO2, Li/CaO, CaO/C (Shaheen et al., 2018; Dalibor et al., 2017; Asikin-Mijan et al., 2015; Ye et al., 2018; Sudsakorn et al., 2017; Abdel-Rahman et al., 2017; Boro et al., 2014; Hebbar et al., 2018; Jiang et al., 2017). However, many reports reveal that Ca ions are drained from the material due to the transesterification for the fact of the CaO soluble in methanol and then the biodiesel product demands to be purified by decalcifying process which increases the cost of final product (Sharma et al., 2015). In addition, CaO reacts with atmospheric CO2 producing carbonate, where also water is formed by hydration. Therefore, the calcination is necessary for the fact of high temperature concerning to revivify the material (Asikin-Mijan et al., 2015; Sharma et al., 2015). This is also noted that nanomaterials have drawn specific attention for diver's organic and metal ions attraction due to the binding affinity at optimum condition (Awual, 2016a; Awual, 2017a; Awual et al., 2016b; Awual et al., 2016c; Awual, 2017b; Awual, 2014; Awual, 2016b; Awual et al., 2017a; Awual et al., 2017b; Sheikh et al., 2017; Awual et al., 2018; Awual, 2016c; Awual, 2015; Awual et al., 2015a; Awual and Hasan, 2015a; Awual et al., 2016a). Zeolites have been used as carrier material in terms of porosity and accessibility of active phase to the internal surface to ensure the high activity/selectivity. By using FAU-type zeolite catalysts, the transesterification reaction was performed in the reflux condition in methanol at atmospheric pressure for high productivity (Doyle et al., 2017; Nilavunesan et al., 2017). Recently, porous resin catalyst was used for the production of fuel additives or biomass hydrolysate (Zheng et al., 2018; Lin et al., 2017; Huang et al., 2018). Very recently, the zeolite/chitosan material was used for biodiesel production from waste cooking oil (Fereidooni and Mehdi, 2017). While this approach is promising, the triglycercides can barely access of the micropores contained in the zeolite (pore space 8 Å) (Sharma et al., 2015). The sol-gel fabricated materials have exhibited high surface area with large pore volume for high adsorption of specific compound and ions (Awual et al., 2013a, 2013b, 2013c, 2013d, 2014a, 2014b, 2014c, 2014d, 2015b, 2015c, 2015d; Awual and Hasan, 2014a, 2014b, 2015b; Awual and Ismael, 2014; Awual and Yaita, 2013). Hence, the diffusional constrains to catalyze reactions for the biodiesel production limit their applications in practical feasibility. A new advanced application of nanocatalyst is emerging in order to boost the transesterification of vegetable oils (Pandit and Fulekar, 2017). In a recent study microwave-enhanced fabrication of KOH/Ca12Al14O33 nanocatalysts have been exposed as potential heterogeneous catalyst in the production of biodiesel due to its large specific surface areas (Nayebzadeh et al., 2017a, 2017b). Most of the recent research has focused on the development of supported nanocatalysts including Ni/ZnO, MgO/MgAl2O4, sonosulphated zirconia/MCM, MgO/La2O3 and heteropolyacid catalysts (Baskar et al., 2018; Vahid and Haghighi, 2017; Dehghani and ~ iz-Monge et al., 2018; Haghighi, 2017; Feyzi et al., 2017; Alcan Carvalho et al., 2017). A number of catalytic schemes have not been potential in real use commercially due to the large amount of fatty acid methyl esters obtained by nanocatalysts during the separation of material from the reaction methods. Therefore, heterogeneous catalysis is accounted for large-scale process due to the simple material separation in subsequent reaction process. Also the investment for the machinery is more than 50% of the total cost in

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chemical and fuel industries (King, 2007). Herein, we demonstrate for the first time on the development of hierarchically porous CaSO4/Fe2O3-SiO2 core-shell magnetic nanoparticles based on the excellent proficiency with high reusability for easy biodiesel production from crude Jatropha curcus (Fig. 1). The material preparation, morphology and reusability performance were evaluated for biodiesel production using crude Jatropha curcus oil. Effect of material loading, temperature, reaction time and recycle performance were measured to know the potentiality of the proposed material. The material characterization including SEM, TEM and BET surface area studies before and after transesterification reaction were also performed to understand the nature of material. 2. Materials and methods 2.1. Materials All chemicals were of analytical grade and used as received without further purification. Ferrous sulphate (FeSO47H2O), sodium acetate (NaAc), sodium bromide (NaBr), sodium hydroxide (NaOH) and aqueous ammonia (NH3OH) were of analytical grade purchased from Merck (Germany). The cetyltrimethylammonium bromide (CTAB) and tetraethyl orthosilicate (TEOS) were obtained from Merck Chemical Reagent Co., Ltd. (USA). Sulphuric acid (assay 97e99%) and anhydrous ethanol and ethanol (assay >99.8%) were supplied from SigmaeAldrich Company, respectively. The crude Jatropha curcas oil was purchased from Bionas Sdn Bhd, Malaysia. 2.2. Synthesis of surface-functionalized magnetic nanoparticle The steps of CaSO4/Fe2O3-SiO2 core-shell magnetic nanomaterial preparation are shown in Fig. 1. In typical procedure, NaAc (0.29 g), NaOH (0.16 g) and NaNO3 (17.0 g) were dissolved in 19 mL water solution. Then the mixture solution formed a clear solution after heating at 100 C. The solution (1 mL) of 2 mmol FeSO47H2O was quickly dissolved into the solution. Then the solution was cooled down to ambient temperature after keeping the mixture solution at 100 C for 1 h. A black precipitate of Fe2O3 nanoparticle was isolated from magnetic field solution, collected and washed with ultrapure water and ethanol for four times to prepare to use for next step or dried at 65 C for 24 h. The required amount of iron oxide was dissolved in solution with ethanol and distilled water ratio of 2:1. After that 9 mL aqueous ammonia (25 wt%) was dissolved to the mixture to attain pH 9.0. Next, cetyltrimethylammonium bromide (CTAB, 0.2 g) was added to the mixture and tetraethoxysilane (TEOS, 0.625 mL) was added slowly at the end. At room temperature, the mixture was stirred for 24 h and then the nanoparticles were isolated with a magnetic field from the solution and rinsing with water and ethanol, and then dried at 100 C until complete drying. The calcination of the core-shell composite nanoparticles was performed for 5 h at 550 C in the presence of atmospheric air (Zhang et al., 2013). Then the core-shell based mesoporous structure material was achieved with iron oxides coated mesoporous silica nano-composites. Dust and all impurities were removed from the Cockle-seashells with deionized water. Detergent was used to eliminate the oil covered surface from the shells. The water from the shell was removed by drying at 110 C for 12 h. The calcination was performed at 800 C in an open-tube furnace (Carbolite) for 3 h to convert CaCO3 into CaO. Finally, the shells were ground to make it powder form. Mesoporous silica embedded Fe2O3 to CaO (produced from combustion of cockle seashells derived CaCO3) was used to prepare calcium sulphate supported on sulphated silica core-shell

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Step 1

Step 2

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Fig. 1. Synthesis of CaSO4/Fe2O3-SiO2 particle as hierarchically porous core-shell magnetic nanoparticles.

composite nanoparticles by 1:1 of CaO to SiO2 weight ratio. For preparing CaSO4/Fe2O3-SiO2, 1:1 SiO2 to CaO weight ratio, 5 g CaO and 5 g amorphous core-shell SiO2 were slowly added to 300 mL of 2.0 M H2SO4 solutions. The mixture was agitated continuously for 6 h at ambient temperature and 600 rpm. The resulting solid precipitate was isolated from the solution with a magnetic field and then dried in an oven at 110 C for 12 h.

2.3. Material characterization Infrared spectra analysed using attenuated total reflectionFourier transforminfrared (ATR-FTIR) spectroscopy was used to measure the functional group of the material (PerkinElmer (PC) Spectrum 100 FTIR spectrometer). The TG/DTA data were recorded by Mettler Toledo thermogravimetric analyser. Crystalline


structures of the material were carried out by X-ray diffraction (Shimadzu, XRD-6000). The diffractometer was used CuKa radiation (l ¼ 1.541 Å) to get the diffraction patterns from powder crystalline samples. The specific surface area (SBET), pore volume, and pore size of the material were measured by N2 adsorption isotherms using BrunauereEmmetteTeller (Thermo Finnigan Sorptomatic 1900 series, BET) theory. The materials characterizations of mesoporous structure material were evaluated by FESEM (JOEL JSM6700F) and HRTEM (JOEL, JEM-2800). 2.4. Catalytic activity The prepared CaSO4/Fe2O3-SiO2 material was used in the Transesterification of crude Jatropha curcas oil. The analysis data of properties for crude Jatropha curcas oil is present in Table Supp X. 10 g of Jatropha curcas oil and methanol were added stoichiometrically in the required amount and CaSO4/Fe2O3-SiO2 was also added. The mixture was kept up to 7 h for complete reaction. The temperature was varied between 60 and 160 C. The variation of material amount (based on total reactants) was from 3 to 16 wt.%. Magnetic force was used to separate the material and subsequently washed with hexane and diethyl ether to evaluate the recyclability. The yield of crude Jatropha curcas oil to biodiesel was determined based on data obtained from GC-FID (Islam et al., 2015). All data were obtained in duplicated at least and average data are stated in this study. Using response factor, Rf of each compound with respect to the standard compound, the biodiesel production was calculated from the following equation: Rf ¼ (Ais/Ars) x (Crs/Cis)

(1)

Internal standard's area, Ais; Internal standard's concentration Cis; Standard reference area, Ars; Standard reference concentration, Crs. The methyl ester (ME) conversion was determined by the following equation: ME¼ (Ciss x Aif x Rf)/ Aiss

(2)

where amount of internal standard concentration in the sample, Ciss; Internal standard's area in the sample, Aiss; Separable FAMEs compound's area of in the sample, Aif. The biodiesel production (BY, %) of was determined using the following equation: BY ¼ Mme/ (3 Mtgly) x 100%

(3)

where total quantity of methyl ester (mol) in the sample, Mme and charge amount of triglycerols (mol) in the sample, Mtgly. 3. Results and discussion 3.1. Synthesis and characterization of material The solvothermal reduction conditions were controlled to obtain monodisperse Fe2O3 magnetic microspheres. A reduction reaction in a solvothermal system was performed between the solution of FeCl3, CH3COONa, NaOH and NaNO3 to produce the microspheres of magnetic Fe2O3 particle. In the solvothermal reduction method, NaNO3 is used as the etchant to construct the co-valent bond in Fe2O3 framework, CH3COONa is also used as electrostatic stabilizer for reducing agent, and NaOH is used for the pH adjustment system (Li et al., 2015). Self-assembly of CTAB and TEOS precursor favored the formation of hierarchical mesoporous

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core shell (Wang et al., 2011). In the fabrication of SiO2-coated Fe2O3 magnetic nanoparticles, the mixture of Fe2O3, CTAB and TEOS were mixed at ambient temperature in an EtOH/H2O medium to form core shell Fe2O3/SiO2 framework due to the matter of hydrolysis and condensation of TEOS. In this method, limiting the nucleation and growth of nanoparticle by emulsion generated from CTAB was given additional platform for the precise control of coreeshell structure of nanoparticles. It was reported by Hanrahan et al. (2007) that the CTAB acts as the emulsion forming additive during the formation mesoporous silica spheres. Addition of small amount of TEOS by post synthesis grafting decreases the CTAB functional groups. However, the agglomeration phenomenon of suspended CTAB was increased by addition of the disproportionate amount of TEOS due to electrostatic interface between CTAB and TEOS (Li et al., 2015; Hanrahan et al., 2007). Therefore, a small amount of TEOS (0.5 mL) was used to favor the more CTAB activesites for specific surface active site in the reaction system. After calcining the resulting mixture, the samples were further acidified with H2SO4 and CaO to form CaSO4/Fe2O3-SiO2 framework structure. This data indicated that the CTAB catalyzed the core shell structures formation and develop porous structure during calcination mainly because of the release of volatile matter in the preparation of high surface and large pore volume nanoparticles. Topological construction of CaSO4/Fe2O3-SiO2 core-shell magnetic nanomaterial is optimized based on the above discussion, as shown in Fig. 2a. Similar observations were made during pinewood sawdust carbonization using pyrolysisesulfonation process (Liu et al., 2013). The data also indicated that the nanosphere surface was densely packed in mesopores interwoven among them as judged in Fig. 2bec. Porous structures both the surface and inside (Fig. 2dee) of the nanospheres are detected in the TEM images. At high magnification, the particles were found with specific size and shape to clarify as the building blocks structural materials (Fig. 2dee, inset of the Figs.). The isotherms for CaSO4/Fe2O3-SiO2 material confirmed the porous structures with increased surface area. The pore size is around 90 nm and the pore volume is 0.55 cm3 g1 as shown in Fig. 3a. The nitrogen adsorptionedesorption isotherms of the synthesized material displayed type IV isotherms, indicating the formation of uniform mesoporous structure (Fig. 3b). Hysteresis loop at low relative pressure (0.0e0.3 p/po) in nitrogen adsorptionedesorption isotherms assumes the capillary condensation of the liquid nitrogen at the small diameter of the pores. The surface area of the CaSO4/Fe2O3-SiO2 core-shell magnetic nanoparticles was 391 m2/g. Comparing with our previous materials, the core-shell materials are exhibited low surface area and low pore volume (Arshad et al., 2017; Awual et al., 2015e; Shahat et al., 2015a; Awual et al., 2015f; Shahat et al., 2015b; Awual et al., 2015g; Awual et al., 2015h; Awual et al., 2014e; Awual et al., 2014f; Awual et al., 2013e; El-Safty et al., 2013; Awual et al., 2014g; Awual et al., 2014h; Awual et al., 2013f; Awual et al., 2013g; Abbas et al., 2018; Shahat et al., 2018a; Shahat et al., 2018b; Shahat et al., 2018c; Rahman et al., 2017). The functional group presence on the CaSO4/Fe2O3-SiO2 coreshell magnetic nanoparticles (Fig. 4) was determined by the FTIR. The peaks at 1088 cm1 indicated the presence of FeeOeFe group (Karimi et al., 2014; Jafari et al., 2017) suggesting the presence of iron phases in the nanoparticles (Fig. 4a). Additional band around 2980 cm1 was assigned to C]C, C]N, aromatic CeH and aliphatic CeH (Fig. 4b), confirming the successful immobilization of CTAB on magnetic nanoparticles (Karimi et al., 2014). After calcination, the band of stretching vibrations of the C]C double bonds and deformation of the alkyl chain was disappeared which might be indicative of removal CTAB from the material, as shown in Fig. 4ced.

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Fig. 4. FTIR spectra of (a) Fe2O3; (b) Fe2O3-SiO2-CTAB; (c) Fe2O3-SiO2 and (d) CaSO4/ Fe2O3-SiO2.

Fig. 2. (a) The proposed constructed wall component of porous CaSO4/Fe2O3-SiO2 core-shell magnetic nanoparticles and the interaction mechanism between TEOS molecule and CTAB functional groups; (bec) SEM and (dee) TEM images of CaSO4/ Fe2O3-SiO2 core-shell magnetic nanoparticle.

identified in the graph (Fig. 5aed). At temperatures below 300 C, the weight loss was observed because of the vaporization of water present in the sample (Fig. 5a). The weight loss was detected in the 2nd time when the temperature was higher than 300 C due to the gradual decomposition. In view of the functional group of the samples and the temperature range, the weight loss can be attributed to the presence of polymer carbonized at high temperatures. Thus, the significant weight losses (80%) of the samples indicate that the polymer species were completely removed from the hybrid microsphere as shown in Fig. 5b. According to the mass loss in TGA, about 20 wt% of Fe2O3-SiO2 was silicon-iron oxide nanoparticles which remained unchanged above 400 C (Fig. 5c). The weight loss of 75% as shown in Fig. 5d occurred in the range of 200e300 C and could be due to the complete removal of solvent molecules of metal oxide framework. The X-ray diffraction patterns of CaSO4/Fe2O3-SiO2 are shown in Fig. 6. In both cases, the broad diffraction peaks of 2q value at ~23.0 were observed, which demonstrate the existence of amorphous SiO2 Fig. 6a. The XRD peaks at 2q values of 30.5 , 35.9 , 37.1, 43.5 , 54.0 , 57.7, 63.2 and 74.6 indicate the formation of Fe2O3 according to JCPDS File No. 01-075-0449 as shown in Fig. 6b. The broad diffraction peaks from 2q ¼ 25.6 , 38.8 , 41.0 , 45.7, 48.8 , 52.6 and 55.9 in Fig. 6c indexed to a CaSO4 phase suggesting the insertion of CaSO4 into the silica matrix (JCPDS File No. 01-0742421).

3.2. Material performance

Fig. 3. (a) The BJH pore-size distribution curves and (b) N2 adsorptionedesorption isotherms of CaSO4/Fe2O3-SiO2 core-shell magnetic nanoparticles.

The thermogravimetric analysis of core-shell magnetic particle was performed using TGA, as shown in Fig. 5. Weight loss of two different temperature ranges of 25e300 C and 300e600 C were

We used crude Jatropha oil directly as raw material for biodiesel production without a pretreatment step (or esterification). Our previous study (Teo et al., 2015), the properties of crude Jatropha oil was measured, as shown in Table 1. The conventional method of producing biodiesel from Jatropha oil involves esterification and transesterification reactions. However, in this study, a one-step conversion method was selected due to its simple process. The influences of reaction time, temperature and amount of material (wt.%), were evaluated. The molar ratio between methanol and oil was considered to be 9:1 in this study for the completion of transesterification process, described in the previous study for the case of Jatropha oil (Sahoo and Das, 2009). The biodiesel production in function of reaction time is shown in Fig. 7a. With increase from 0.5 to 4 h of reaction time, biodiesel production was also increased


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Table 1 Properties of crude Jatropha curcas oil (Teo et al., 2015). Test

Analysis results

Moisture contents (%w/w) Density (g/cm3) Free fatty acid (%w/w) Acid value (mg KOH/g1) Saponification value (mg KOH/g1) Fatty acids Compositions% Palmitic (C16:0) Palmitoleic (C16:1) Stearic (C18:0) Oleic (C18:1) Linoleic (C18:2)

0.09 0.92 6.80 13.60 188.40 20.16 1.32 7.22 39.77 31.53

b

a

c

Fig. 7. (a) Effect reaction time on biodiesel yield using CaSO4/Fe2O3-SiO2 material, [Transesterification process in the conditions of 9:1 methanol to oil molar ratio at 120 C and 300 rpm with 10 wt.% material loading]; (b) Effect of transesterification reaction temperature on % biodiesel yield, [Transesterification process in the conditions of 9:1 methanol to oil molar ratio and 300 rpm with 10 wt.% of material loading for 4 h]; (c) Effect of material loading on biodiesel yield, [Transesterification process in the conditions of 9:1 methanol to oil molar ratio at 120 C and 300 rpm for 4 h reaction time].

from 41% to 94%, respectively. Enhancement of biodiesel yield was observed when the reaction was enhanced up to 3 h. However, the relatively slow conversion rate was observed for the increment of time from 3 to 4 h because of the reduction of fatty acid (Sahoo and Das, 2009). No further enhancement in biodiesel production was observed beyond 4 h. The effect of reaction temperature on the yield of crude Jatropha curcas is depicted in Fig. 7b. The impact of reaction temperature was assessed between 60 and 160 C (Fig. 7b) for 9:1 methanol:oil molar ratio after 4 h reaction. Basically an enhanced reaction rate and the yield were observed at high temperature. FAME yield increased continuously for temperatures from 60 to 120 C, reaching a limiting value of 94%, probably reflecting both increased reactant activation and higher oil miscibility (Gardy et al., 2018). Higher temperatures had negligible impact on FAME production indicating that the reaction had reached equilibrium. The suitable temperature was set as 90 C. The biodiesel production was also determined as function of material wt% and the data are shown in Fig. 7c. With the addition of lower material concentration

Fig. 8. Gas chromatography of (a) standard references of fatty acid methyl esters and (b) transesterified produced FAME.

(3 wt%), the biodiesel production was low owing because of the presence insufficient amount of active sites. With increase in the catalyst amount up to 12 wt%, the maximum biodiesel production of 94% was achieved. However, a significant change in production was observed with the high amounts of catalyst wt%. It is speculated that the protonation of crude Jatropha curcas at the active sites could be hindered by the excess amount of material in the reaction (Sahoo and Das, 2009). On the basis experimental observation, optimum conditions for transesterification of crude Jatropha curcas are determined as 4 h for completion of reaction, optimum temperature at 120 C, methanol and oil ratio was 9:1, and material amount was 12 wt%. In such optimum conditions, the biodiesel production was reached to 94%. Other than being magnetic, and its ease for separation, it was anticipated that template-containing catalysts showed high efficiency for one step esterification and transesterification because of coexistence of acidic and basic sites on catalyst surface. It was reported (Poonjarernsilp et al., 2015) that

a

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Fig. 9. Recycling and reuse of CaSO4/Fe2O3-SiO2 material in the transformation of jatropha caracus oil to biodiesel (Reaction conditions: methanol/grease molar ratio of 9: 1, material loading of 12 wt%, 120 C, and 4 h); (b) Photographs of the above corresponding samples separated from solution under an external magnetic field.


Fig. 10. (aec) FESEM images (def) TEM images of CaSO4/Fe2O3-SiO2 core-shell magnetic nanoparticles after recycling of 4, 7 and 9 tomes respectively; (geh) the material morphologies after 9th recycle of N2 adsorption-desorption isotherms and pore size distribution plot.

the surface acidity could be modified by the introduction of some ferric compounds such as ferric oxide (Fe2O3), ferric alginate, and Fe-Ti mixed oxide. In this study, the surface acid and basic sites were produced by the incorporation of Fe2O3 and SiO2, respectively. A conclusion has been reached by researchers (Poonjarernsilp et al., 2014) that the metal ion works as a Lewis acid, and SiO works as a Lewis base. In addition, the removal of the template by calcination, th catalyst could possess high porosity and surface area as evident from FESEM and TEM (Fig. 2) and subsequently could increase the density of the active sites. So, the achievement of high biodiesel (FAMEs) yield (94%) after a one-step direct conversion of Jatropha oil could be due to the synergetic catalytic effect in acidic sites esterifing FFAs and basic sites transesterifing triglycerides. Fig. 8 shows the gas chromatograph (GC) chromatogram for the biodiesel produced from Jatropha oil. It can be concluded that the acidic and basic sites of this catalyst was sufficient for conversion of crude Jatropha curcas. 3.3. Reusability parameters The reuse data of CaSO4/Fe2O3-SiO2 materials are summarized

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in Fig. 9. The optimum reaction parameters for biodiesel production were followed in each cycle. Gradually decreasing trend from 94% to 85% in the first four cycles was observed and hardly reduced the performance from 5th to 9th cycles. This happened because of the deactivation of CaSO4/Fe2O3-SiO2 material nanoparticles. A general conclusion has been reached by researchers (Jin et al., 2017) that material with the hierarchical porosity and interconnectivity between the pore channels plays an important role to observe catalytic performance. It is required to create of ideal space for deposition of active catalytic phases to achieve maximum dispersion and strong interface between material and the reaction medium (Wan et al., 2018). Deactivation could be associated to pores blockage on the material's external and internal surfaces (Wan et al., 2018). Hence, the effect of CaSO4/Fe2O3-SiO2 material pores was investigated by FESEM, TEM and BET surface area to evaluate the deactivation of material. It can be seen that pores of the material was blocked after the 4th, 7th and 9th cycle as shown in Fig. 10aef. However, this mass loss of observed in the rinsing of the nanoparticles for subsequent use of material could be attributed the decrement of the biodiesel production. The total surface area and pore volume of the reused CaSO4/Fe2O3-SiO2 material are 252 m2/g and in range of 0.36e0.7 cm3/g, respectively, and this was lower than the fresh material (Fig. 10geh). The considerable decrease in the surface area of the CaSO4/Fe2O3-SiO2 catalyst technique can be attributed to pore blockage as evident from SEM and TEM Images of the reused material (Fig. 10aeh). Thus, the blockage of the active sites on the surfaces of the pores may limit the mass transfer, which gives rise to low catalytic activity. Table 2 compared the performance of CaSO4/Fe2O3-SiO2 coreshell material with some solid material from literature (Teo et al., 2015; Sahoo and Das, 2009; Gardy et al., 2018; Poonjarernsilp et al., 2014, 2015; Jin et al., 2017; Wan et al., 2018; Mardhiah et al., 2017), showing that the material synthesized in this study was produced similar amount of FAME (94%) at much milder reaction temperature and shorter time. After nine recycle, the material was maintained satisfactory catalytic activity after being quickly separated from the reaction products without using centrifugation or filtration. One of the main reasons to consider heterogeneous catalysis for industrial processes is the ease of material separation after the reaction. Therefore, the easy separation of material from process fluid and the safe handling are the two of the main rationale to select the CaSO4/Fe2O3-SiO2 core-shell material for biodiesel production. 4. Conclusions Hierarchically porous, active and recyclable acid-functionalized CaSO4/Fe2O3-SiO2 core-shell magnetic nanoparticles were successfully synthesized. Under the reaction conditions of material dosage 12 wt%, methanol:crude Jatropha curcas oil ratio of 9:1, optimum temperature 120 C, reaction time 4 h, the CaSO4/Fe2O3-

Table 2 Comparison of the CaSO4/Fe2O3-SiO2 core-shell material for biodiesel production from Jatropha oil. Comparison

This work

Mardhiah et al. (Mardhiah et al., 2017)

Wang et al. (Wang et al., 2018)

Wei et al. (Wei et al., 2018)

Feedstock Methanol: Oil ratio Material Material loading/wt% Reaction time/h Particle size/nm Surface area/m2.g1 Temperature/oC FAME yield/% Recycles

Jatropha oil 9:1 CaSO4/Fe2O3-SiO2 core-shell 12 4 39 391 120 94 83% after 9 cycles

Jatropha oil 12:1 SO3H/C 7.5 1 e e 60 99 81% after 4 cycles

Jatropha oil 40:1 Mg2Fe/C600 7 4 100 34 160 94.8 94% after 3 cycles

Jatropha oil 18:1 Raney-Ni 8 1 e e 85 91 e

() indicates no information available in the literature.

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SiO2 material showed the high activity in the transesterification of crude Jatropha curcas in the media of methanol. The material demonstrated high catalytic performance (94%) for one-pot transformation of crude Jatropha curcas oil to biodiesel. The high performance of the nanoparticles in the biodiesel production can be stated to the small size of crystalline nanoparticle with the large specific surface area in combination with the well-defined hierarchically porous structure of the material. Moreover, no observable decrease of catalytic performance was observed after successive reuse of material. The material maintained high yield in the biodiesel production even after reuse for nine times demonstrating good stability and recyclability. Thus, the developed CaSO4/Fe2O3SiO2 material would be useful for green biodiesel production from crude Jatropha curcas oil. Acknowledgment The Authors would like to acknowledge the financial grant from the Universiti Putra Malaysia, Malaysia for its funding through the research group project GP-IPB/2016/9490400. The authors extend their appreciation to the International Scientific Partnership Program ISPP at King Saud University for funding this research work through ISPP# 87. References Abbas, K., Znad, H., Awual, M.R., 2018. A ligand anchored conjugate adsorbent for effective mercury(II) detection and removal from aqueous media. Chem. Eng. J. 334, 432e443. Abdel-Rahman, Z.A., Wiheeb, A.D., Juma, M.M., 2017. Commercial CaO catalyzed biodiesel production process. Al-Nahrain J. Eng. Sci. 20 (4), 846e852. ~ iz-Monge, J., El Bakkali, B., Trautwein, G., Reinoso, S., 2018. Zirconia-supported Alcan tungstophosphoric heteropolyacid as heterogeneous acid catalyst for biodiesel production. Appl. Catal. B Environ. 224, 194e203. Arshad, M.N., Sheikh, T.A., Rahman, M.M., Asiri, A.M., Marwani, H.M., Awual, M.R., 2017. Fabrication of cadmium ionic sensor based on (E)-4-Methyl-N0-(1-(pyridin-2-yl)ethylidene)benzenesulfonohydrazide (MPEBSH) by electrochemical approach. J. Organomet. Chem. 827, 49e55. Asikin-Mijan, N., Lee, H.V., Taufiq-Yap, Y.H., 2015. Synthesis and catalytic activity of hydrationedehydration treated clamshell derived CaO for biodiesel production. Chem. Eng. Res. Des. 102, 368e377. Awual, M.R., 2014. Investigation of potential conjugate adsorbent for efficient ultraetrace gold(III) detection and recovery. J. Ind. Eng. Chem. 20, 3493e3501. Awual, M.R., 2015. A novel facial composite adsorbent for enhanced copper(II) detection and removal from wastewater. Chem. Eng. J. 266, 368e375. Awual, M.R., 2016. Ring size dependent crown ether based mesoporous adsorbent for high cesium adsorption from wastewater. Chem. Eng. J. 303, 539e546. Awual, M.R., 2016. Solid phase sensitive palladium(II) ions detection and recovery using ligand based efficient conjugate nanomaterials. Chem. Eng. J. 300, 264e272. Awual, M.R., 2016. Assessing of lead(II) capturing from contaminated wastewater using ligand doped conjugate adsorbent. Chem. Eng. J. 289, 65e73. Awual, M.R., 2017. New type mesoporous conjugate material for selective optical copper(II) ions monitoring & removal from polluted waters. Chem. Eng. J. 307, 85e94. Awual, M.R., 2017. Novel nanocomposite materials for efficient and selective mercury ions capturing from wastewater. Chem. Eng. J. 307, 456e465. Awual, M.R., Hasan, M.M., 2014. A novel fine-tuning mesoporous adsorbent for simultaneous lead(II) detection and removal from wastewater. Sensor. Actuator. B Chem. 202, 395e403. Awual, M.R., Hasan, M.M., 2014. Novel conjugate adsorbent for visual detection and removal of toxic lead(II) ions from water. Microporous Mesoporous Mater. 196, 261e269. Awual, M.R., Hasan, M.M., 2015. Fine-tuning mesoporous adsorbent for simultaneous ultra-trace palladium(II) detection, separation and recovery. J. Ind. Eng. Chem. 21, 507e515. Awual, M.R., Hasan, M.M., 2015. Colorimetric detection and removal of copper(II) ions from wastewater samples using tailor-made composite adsorbent. Sensor. Actuator. B Chem. 206, 692e700. Awual, M.R., Ismael, M., 2014. Efficient gold(III) detection, separation and recovery from urban mining waste using a facial conjugate adsorbent. Sensor. Actuator. B Chem. 196, 457e466. Awual, M.R., Yaita, T., 2013. Rapid sensing and recovery of palladium(II) using N,Nbis(salicylidene)1,2-bis(2-aminophenylthio)ethane modified sensor ensemble adsorbent. Sensor. Actuator. B Chem. 183, 332e341. Awual, M.R., Yaita, T., El-Safty, S.A., Shiwaku, H., Suzuki, S., Okamoto, Y., 2013. Copper(II) ions capturing from water using ligand modified a new type

mesoporous adsorbent. Chem. Eng. J. 221, 322e330. Awual, M.R., Yaita, T., El-Safty, S.A., Shiwaku, H., Okamoto, Y., Suzuki, S., 2013. Investigation of palladium(II) detection and recovery using ligand modified conjugate adsorbent. Chem. Eng. J. 222, 172e179. Awual, M.R., Ismael, M., Yaita, T., El-Safty, S.A., Shiwaku, H., Okamoto, Y., Suzuki, S., 2013. Trace copper(II) ions detection and removal from water using novel ligand modified composite adsorbent. Chem. Eng. J. 222, 67e76. Awual, M.R., Yaita, T., Shiwaku, H., 2013. Design a novel optical adsorbent for simultaneous ultra-trace cerium(III) detection, sorption and recovery. Chem. Eng. J. 228, 327e335. Awual, M.R., Khaleque, M.A., Ferdows, M., Chowdhury, A.M.S., Yaita, T., 2013. Rapid recognition and recovery of gold(III) with functional ligand immobilized novel mesoporous adsorbent. Microchem. J. 110, 591e598. Awual, M.R., Kobayashi, T., Shiwaku, H., Miyazaki, Y., Motokawa, R., Suzuki, S., Okamoto, Y., Yaita, T., 2013. Evaluation of lanthanide sorption and their coordination mechanism by EXAFS measurement using novel hybrid adsorbent. Chem. Eng. J. 225, 558e566. Awual, M.R., Kobayashi, T., Miyazaki, Y., Motokawa, R., Shiwaku, H., Suzuki, S., Okamoto, Y., Yaita, T., 2013. Selective lanthanide sorption and mechanism using novel hybrid Lewis base (NemethyleN-phenyle1,10ephenanthrolinee2ecarboxamide) ligand modified adsorbent. J. Hazard Mater. 252e253, 313e320. Awual, M.R., Yaita, T., Okamoto, Y., 2014. A novel ligand based dual conjugate adsorbent for cobalt(II) and copper(II) ions capturing from water. Sensor. Actuator. B Chem. 203, 71e80. Awual, M.R., Hasan, M.M., Shahat, A., 2014. Functionalized novel mesoporous adsorbent for selective lead(II) ions monitoring and removal from wastewater. Sensor. Actuator. B Chem. 203, 854e863. Awual, M.R., Ismael, M., Yaita, T., 2014. Efficient detection and extraction of cobalt(II) from lithium ion batteries and wastewater by novel composite adsorbent. Sensor. Actuator. B Chem. 191, 9e18. Awual, M.R., Rahman, I.M.M., Yaita, T., Khaleque, M.A., Ferdows, M., 2014. pH dependent Cu(II) and Pd(II) ions detection and removal from aqueous media by an efficient mesoporous adsorbent. Chem. Eng. J. 236, 100e109. Awual, M.R., Hasan, M.M., Ihara, T., Yaita, T., 2014. Mesoporous silica based novel conjugate adsorbent for efficient selenium(IV) detection and removal from water. Microporous Mesoporous Mater. 197, 331e338. Awual, M.R., Ismael, M., Khaleque, M.A., Yaita, T., 2014. Ultra-trace copper(II) detection and removal from wastewater using novel meso-adsorbent. J. Ind. Eng. Chem. 20, 2332e2340. Awual, M.R., Yaita, T., Taguchi, T., Shiwaku, H., Suzuki, S., Okamoto, Y., 2014. Selective cesium removal from radioactive liquid waste by crown ether immobilized new class conjugate adsorbent. J. Hazard Mater. 278, 227e235. Awual, M.R., Suzuki, S., Taguchi, T., Shiwaku, H., Okamoto, Y., Yaita, T., 2014. Radioactive cesium removal from nuclear wastewater by novel inorganic and conjugate adsorbents. Chem. Eng. J. 242, 127e135. Awual, M.R., Khaleque, M.A., Ratna, Y., Znad, H., 2015. Simultaneous ultra-trace palladium(II) detection and recovery from wastewater using new class mesoadsorbent. J. Ind. Eng. Chem. 21, 405e413. Awual, M.R., Hasan, M.M., Khaleque, M.A., 2015. Efficient selenium(IV) detection and removal from water by tailor-made novel conjugate adsorbent. Sensor. Actuator. B Chem. 209, 194e202. Awual, M.R., Hasan, M.M., Naushad, M., Shiwaku, H., Yaita, T., 2015. Preparation of new class composite adsorbent for enhanced palladium(II) detection and recovery. Sensor. Actuator. B Chem. 209, 790e797. Awual, M.R., Hasan, M.M., Znad, H., 2015. Organic-inorganic based nano-conjugate adsorbent for selective palladium(II) detection, separation and recovery. Chem. Eng. J. 259, 611e619. Awual, M.R., Eldesoky, G.E., Yaita, T., Naushad, M., Shiwaku, H., AlOthman, Z.A., Suzuki, S., 2015. Schiff based ligand containing nano-composite adsorbent for optical copper(II) ions removal from aqueous solutions. Chem. Eng. J. 279, 639e647. Awual, M.R., Yaita, T., Shiwaku, H., Suzuki, S., 2015. A sensitive ligand embedded nano-conjugate adsorbent for effective cobalt(II) ions capturing from contaminated water. Chem. Eng. J. 276, 1e10. Awual, M.R., Yaita, T., Suzuki, S., Shiwaku, H., 2015. Ultimate selenium(IV) monitoring and removal from water using a new class of organic ligand based composite adsorbent. J. Hazard Mater. 291, 111e119. Awual, M.R., Hasan, M.M., Shahat, A., Naushad, M., Shiwaku, H., Yaita, T., 2015. Investigation of ligand immobilized nano-composite adsorbent for efficient cerium(III) detection and recovery. Chem. Eng. J. 265, 210e218. Awual, M.R., Hasan, M.M., Eldesoky, G.E., Khaleque, M.A., Rahman, M.M., Naushad, M., 2016. Facile mercury detection and removal from aqueous media involving ligand impregnated conjugate nanomaterials. Chem. Eng. J. 290, 243e251. Awual, M.R., Miyazaki, M., Taguchi, T., Shiwaku, H., Yaita, T., 2016. Encapsulation of cesium from contaminated water with highly selective facial organic-inorganic mesoporous hybrid adsorbent. Chem. Eng. J. 291, 128e137. Awual, M.R., Hasan, M.M., Khaleque, M.A., Shiekh, M.S., 2016. Treatment of copper(II) containing wastewater by a newly developed ligand based facial conjugate materials. Chem. Eng. J. 288, 368e376. Awual, M.R., Alharthi, N.H., Hasan, M.M., Karim, M.R., Islam, A., Znad, H., Hossain, M.A., Halim, M.E., Rahman, M.M., Khaleque, M.A., 2017. Inorganicorganic based novel nano-conjugate material for effective cobalt(II) ions capturing from wastewater. Chem. Eng. J. 324, 130e139.

S.H. Teo et al. / Journal of Cleaner Production 208 (2019) 816e826 Awual, M.R., Alharthi, N.H., Okamoto, Y., Karim, M.R., Halim, M.E., Hasan, M.M., Rahman, M.M., Islam, M.M., Khaleque, M.A., Sheikh, M.C., 2017. Ligand field effect for Dysprosium(III) and Lutetium(III) adsorption and EXAFS coordination with novel composite nanomaterials. Chem. Eng. J. 320, 427e435. Awual, M.R., Khraisheh, M., Alharthi, N.H., Luqman, M., Islam, A., Karim, M.R., Rahman, M.M., Khaleque, M.A., 2018. Efficient detection and adsorption of cadmium(II) ions using innovative nano-composite materials. Chem. Eng. J. 343, 118e127. Baskar, G., Selvakumari, I.A.E., Aiswarya, R., 2018. Biodiesel production from castor oil using heterogeneous Ni doped ZnO nanocatalyst. Bioresour. Technol. 250, 793e798. Boro, J., Lakhya, J.K., Dhanapati, D., 2014. Transesterification of non edible feedstock with lithium incorporated egg shell derived CaO for biodiesel production. Fuel Process. Technol. 122, 72e78. Carvalho, A.K.F., da Conceiç~ ao, L.R.V., Silva, J.P.V., Perez, V.H., de Castro, H.F., 2017. Biodiesel production from Mucor circinelloides using ethanol and heteropolyacid in one and two-step transesterification. Fuel 202, 503e511. Dalibor, M.M., Jelena, M.A., Miroslav, V.S., Olivera, S.S., Dusan, M.J., Veljkovi c, B.V., 2017. Synthesis and characterization of spherically-shaped CaO/g-Al2O3 catalyst and its application in biodiesel production. Energy Convers. Manag. 44, 399e413. Dehghani, S., Haghighi, M., 2017. Sono-sulfated zirconia nanocatalyst supported on MCM-41 for biodiesel production from sunflower oil: influence of ultrasound irradiation power on catalytic properties and performance. Ultrason. Sonochem. 35, 142e151. Doyle, A.M., Ziadl, T.A., Talib, M.A., Ammar, S.A., 2017. High purity FAU-type zeolite catalysts from shale rock for biodiesel production. Fuel 199, 394e402. El-Safty, S.A., Awual, M.R., Shenashen, M.A., Shahat, A., 2013. Simultaneous optical detection and extraction of cobalt(II) from lithium ion batteries using nanocollector monoliths. Sensor. Actuator. B Chem. 176, 1015e1025. Fereidooni, L., Mehdi, M., 2017. Experimental assessment of electrolysis method in production of biodiesel from waste cooking oil using zeolite/chitosan catalyst with a focus on waste biorefinery. Energy Convers. Manag. 147, 145e154. Feyzi, M., Hosseini, N., Yaghobi, N., Ezzati, R., 2017. Preparation, characterization, kinetic and thermodynamic studies of MgO-La2O3 nanocatalysts for biodiesel production from sunflower oil. Chem. Phys. Lett. 677 (2017), 19e29. spedes, O., Hassanpour, A., Lai, X., Lee, A.F., Rehan, M., Gardy, J., Osatiashtiani, A., Ce 2018. A magnetically separable SO4/Fe-Al-TiO2 solid acid catalyst for biodiesel production from waste cooking oil. Appl. Catal., B 234, 268e278. Hajjari, M., Tabatabaei, M., Aghbashlo, M., Ghanavati, H., 2017. A review on the prospects of sustainable biodiesel production: a global scenario with an emphasis on waste-oil biodiesel utilization. Renew. Sustain. Energy Rev. 72, 445e464. Hanrahan, J.P., Donovan, A., Morris, M.A., Holmes, J.D., 2007. Synthesis and swelling of large pore diameter mesoporous silica spheres. J. Mater. Chem. 17, 3881e3887. Hebbar, H.R.H., Math, M.C., Yatish, K.V., 2018. Optimization and kinetic study of CaO nano-particles catalyzed biodiesel production from Bombax ceiba oil. Energy 143, 25e34. Huang, Q., Zhang, H., Xiong, L., Huang, C., Guo, H., Chen, X., M Luo, L., Tian, Lin, X., Chen, X., 2018. Controllable synthesis of styrene-divinylbenzene adsorption resins and the effect of textural properties on removal performance of fermentation inhibitors from rice straw hydrolysate. Ind. Eng. Chem. Res. 57, 5119e5127. Islam, M., Ahmed, A.S., Islam, A., Abdul Aziz, S., Xian, L.C., Mridha, M., 2014. Study on emission and performance of diesel engine using castor biodiesel. J. Chem. 1e8. Islam, A., Yaufiq-Yap, Y.H., Ravindra, P., Teo, S.H., Sivasangar, S., Chan, E.S., 2015. Biodiesel synthesis over millimetric g-Al2O3/KI catalyst. Energy 89, 965e973. Jafari, L., Pourahmad, A., Asadpour, L., 2017. Rice husk based MCM-41 nanoparticles loaded with Ag2S nanostructures by a green and room temperature method and its antimicrobial property. Inorg. Nano Metal Chem. 47, 1552e1559. Jiang, B., Dou, B., Wang, K., Zhang, C., Li, M., Chen, H., Xu, Y., 2017. Sorption enhanced steam reforming of biodiesel by-product glycerol on Ni-CaO-MMT multifunctional catalysts. Chem. Eng. J. 313, 207e216. Jin, Q., Ren, B., Li, D., Cuiand, H., Wang, C., 2017. Plasma-Assisted Synthesis of Selfsupporting porous CoNPs@ C nanosheet as efficient and stable bifunctional electrocatalysts for overall water splitting. ACS Appl. Mater. Interfaces 9, 31913e31921. Karimi, B., Mansouri, F., Vali, H., 2014. A highly water-dispersible/magnetically separable palladium catalyst based on a Fe 3 O 4@ SiO 2 anchored TEGimidazolium ionic liquid for the SuzukieMiyaura coupling reaction in water. Green Chem. 16, 2587e2596. King, C.J., 2007. In Ullmann's Encyclopedia of Industrial Chemistry, Weinheim, Electronic Version. Li, K., Zeng, Z., Xiong, J., Yan, L., Guo, H., Liu, S., Chen, T., 2015. Fabrication of mesoporous Fe3O4@ SiO2@ CTABeSiO2 magnetic microspheres with a core/shell structure and their efficient adsorption performance for the removal of trace PFOS from water. Colloids Surf. A Physicochem. Eng. Asp. 465, 113e123. Lin, X.Q., Huang, Q.L., Qi, G.X., Xiong, L., Huang, C., Chen, X.F., Li, H.L., Chen, X.D., 2017. Adsorption behavior of levulinic acid onto microporous hyper-crosslinked polymers in aqueous solution: equilibrium, thermodynamic, kinetic simulation and fixed-bed column studies. Chemosphere 171, 231e239. Liu, W.J., Tian, K., Jiang, H., Yu, H.Q., 2013. Facile synthesis of highly efficient and recyclable magnetic solid acid from biomass waste. Sci. Rep. 3, 2419. Mardhiah, H.H., Ong, H.C., Masjuki, H.H., Lim, S., Pang, Y.L., 2017. Investigation of

825

carbon-based solid acid catalyst from Jatropha curcas biomass in biodiesel production. Energy Convers. Manag. 144, 10e17. McGinnis, L., 2007. Fueling America-without petroleum. Agric. Res. 55 (4), 10e13. Nayebzadeh, H., Saghatoleslami, N., Haghighi, M., Tabasizadeh, M., 2017a. Influence of fuel type on microwave-enhanced fabrication of KOH/Ca12Al14O33 nanocatalyst for biodiesel production via microwave heating. J. Taiwan Ins. Chem. Eng. 75, 148e155. Nayebzadeh, H., Saghatoleslami, N., Tabasizadeh, M., 2017b. Application of microwave Irradiation for preparation of KOH/calcium aluminate nanocatalyst and biodiesel. Chem. Eng. Technol. 40 (10), 1826e1834. Nilavunesan, D., Thiruvengadaravi, K.V., Yuvarani, M., Sivanesan, S., 2017. Modified zeolite as a catalyst for Pongamia pinnata oil esterification in biodiesel production. Int. J. Mater. Prod. Technol. 55, 278e285. Pandit, P.R., Fulekar, M.H., 2017. Egg shell waste as heterogeneous nanocatalyst for biodiesel production: optimized by response surface methodology. J. Environ. Manag. 198, 319e329. Poonjarernsilp, C., Sano, N., Sawangpanich, N., Charinpanitkul, T., Tamon, H., 2014. Effect of Fe/Fe2O3 loading on the catalytic activity of sulfonated single-walled carbon nanohorns for the esterification of palmitic acid. Green Chem. 16, 4936e4943. Poonjarernsilp, C., Sano, N., Tamon, H., 2015. Simultaneous esterification and transesterification for biodiesel synthesis by a catalyst consisting of sulfonated single-walled carbon nanohorn dispersed with Fe/Fe2O3 nanoparticles. Appl. Catal., A 497, 145e152. Rahman, M.M., Alam, M.M., Asiri, A.M., Awual, M.R., 2017. Fabrication of 4aminophenol sensor based on hydrothermally prepared ZnO/Yb2O3 nanosheets. New J. Chem. 41, 9159e9169. Sahoo, P.K., Das, L.M., 2009. Process optimization for biodiesel production from Jatropha, Karanja and Polanga oils. Fuel 88, 1588e1594. Shahat, A., Awual, M.R., Khaleque, M.A., Alam, M.Z., Naushad, M., Chowdhury, A.M.S., 2015. Large-pore diameter nano-adsorbent and its application for rapid lead(II) detection and removal from aqueous media. Chem. Eng. J. 273, 286e295. Shahat, A., Awual, M.R., Naushad, M., 2015. Functional ligand anchored nanomaterial based facial adsorbent for cobalt(II) detection and removal from water samples. Chem. Eng. J. 271, 155e163. Shahat, A., Hassan, H.M.A., El-Shahat, M.F., El Shahawy, O., Awual, M.R., 2018. Visual nickel(II) ions treatment in petroleum samples using a mesoporous composite adsorbent. Chem. Eng. J. 334, 957e967. Shahat, A., Hassan, H.M.A., Azzazy, H.M.E., El-Sharkawy, E.A., Abdou, H.M., Awual, M.R., 2018. Novel hierarchical composite adsorbent for selective lead(II) ions capturing from wastewater samples. Chem. Eng. J. 332, 377e386. Shahat, A., Hassan, H.M.A., Azzazy, H.M.E., Hosni, M., Awual, M.R., 2018. Novel nanoconjugate materials for effective arsenic(V) and phosphate capturing in aqueous media. Chem. Eng. J. 331, 54e63. Shaheen, A., Sultana, S., Lu, H., Ahmad, M., Asma, M., Mahmood, T., 2018. Assessing the potential of different nano-composite (MgO, Al2O3-CaO and TiO2) for efficient conversion of Silybum eburneum seed oil to liquid biodiesel. J. Mol. Liq. 249, 511e521. Sharma, S., Dinesh, M., Chen, S., Seo, D.K., 2015. Calcium-modified hierarchically porous aluminosilicate geopolymer as a highly efficient regenerable catalyst for biodiesel production. RSC Adv. 5, 65454e65461. Sheikh, T.A., Arshad, M.N., Rahman, M.M., Asiri, A.M., Marwani, H.M., Awual, M.R., Bawazir, W.A., 2017. Trace electrochemical detection of Ni2þ ions with bidentate N, N'-(ethane-1,2-diyl)bis(3,4-dimethoxybenzenesulfonamide) [EDBDMBS] as a chelating agent. Inorg. Chim. Acta. 464, 157e166. Sudsakorn, K., Surachet, S., Supaphorn, P., Anusorn, S., Jumras, L., 2017. Biodiesel production from Jatropha Curcas oil using strontium-doped CaO/MgO catalyst. J. Environ. Chem. Eng 5 (3), 2845e2852. Teo, S.H., Taufiq-Yap, Y.H., Rashid, U., Islam, A., 2015. Hydrothermal effect on synthesis, characterization and catalytic properties of calcium methoxide for biodiesel production from crude Jatropha curcas. RSC Adv. 5, 4266e4276. Theam, K.L., Islam, A., Choo, Y.M., Taufiq-Yap, Y.H., 2015. Biodiesel from low cost palm stearin using metal doped methoxide solid catalyst. Ind. Crop. Prod. 76, 281e289. Vahid, B.R., Haghighi, M., 2017. Biodiesel production from sunflower oil over MgO/ MgAl2O4 nanocatalyst: effect of fuel type on catalyst nanostructure and performance. Energy Convers. Manag. 134, 290e300. Wan, Z., Li, G.K., Wang, C., Yang, H., Zhang, D., 2018. Relating coke formation and characteristics to deactivation of ZSM-5 zeolite in methanol to gasoline conversion. Appl. Catal., A 549, 141e151. Wang, S., Zhang, M., Wang, D., Zhang, W., Liu, S., 2011. Synthesis of hollow mesoporous silica microspheres through surface solegel process on polystyrene-copoly (4-vinylpyridine) coreeshell microspheres. Microporous Mesoporous Mater. 139, 1e7. Wang, Y.T., Fang, Z., Yang, X.X., Yang, Y.T., Luo, J., Xu, K., Bao, G.R., 2018. One-step production of biodiesel from Jatropha oils with high acid value at low temperature by magnetic acid-base amphoteric nanoparticles. J. Chem. Eng. 348, 929e939. Wei, G., Liu, Z., Zhang, L., Li, Z., 2018. Catalytic upgrading of Jatropha oil biodiesel by partial hydrogenation using Raney-Ni as catalyst under microwave heating. Energy Convers. Manag. 163, 208e218. Ye, X., Wang, W., Zhao, X., Wen, T., Li, Y., Ma, Z., Wen, L., Ye, J., Wang, Y., 2018. The role of the KCaF3 crystalline phase on the activity of KF/CaO biodiesel synthesis catalyst. Catal. Commun. 116, 72e75.

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Zhang, M., Fang, K., Lin, M., Hou, B., Zhong, L., Zhu, Y., Wei, W., Sun, Y., 2013. Controlled fabrication of iron oxide/mesoporous silica core-shell nanostructures. J. Phys. Chem. C 117, 21529e21538. Zheng, J., Pan, B., Xiao, J., He, X., Chen, Z., Huang, Q., Lin, X., 2018. Experimental and

mathematical simulation of noncompetitive and competitive adsorption dynamic of formic acid-levulinic acid-5-hydroxymethylfurfural from single, binary, and ternary systems in a fixed-bed column of SY-01 resin. Ind. Eng. Chem. Res. 57, 8518e8528.