- Email: [email protected]
Biodiesel production using a renewable mesoporous solid catalyst
Industrial Crops & Products xxx (xxxx) xxxx
Contents lists available at ScienceDirect
Industrial Crops & Products journal homepage: www.elsevier.com/locate/indcrop
Biodiesel production using a renewable mesoporous solid catalyst Bishwajit Changmaia, Putla Sudarsanamb, Lalthazuala Rokhuma,* a b
Department of Chemistry, National Institute of Technology Silchar, Silchar, 788010, Assam, India Center for Sustainable Catalysis and Engineering, Faculty of Bioscience Engineering, KU Leuven, Celestijnenlaan 200f, Heverlee, Belgium
A R T I C LE I N FO
A B S T R A C T
Keywords: Fatty acid methyl ester Soybean oil Orange peel ash Reusability Biomass
Heterogeneous solid catalysts have been largely developed for biodiesel production, because of their attractive acid-base properties, strong hydrothermal stability, and efficient recovery/reusability. In this framework, developing bio-waste derived heterogeneous catalysts has attracted immense attention for several catalytic applications, owing to their inexpensive, high abundance, non-toxic, and adequate acid-base properties. In the present work, we investigated the catalytic performance of a biomass-derived orange peel ash (OPA), which contains a porous structure, as a raw heterogeneous catalyst for the transesterification of soybean oil to biodiesel. About 98 % conversion of soybean oil to biodiesel was obtained under the optimized reaction conditions i.e., 6:1 methanol:oil ratio, 7 wt. % catalyst loading, 7 h reaction time at ambient reaction temperature, which ascribed to the presence of abundant basic sites in the developed OPA catalyst. The catalyst can be reused for five successive cycles and shows good stability towards the biodiesel production.
1. Introduction Increasing rate of energy consumption and abnormal climate change, due to the rapid population growth and the emission of environmental pollutants (e.g., CO2), respectively, have led to the search for new, sustainable, and renewable energy sources. Presently, nonrenewable fossil fuels are the major source for the production of energy, fuels, and chemicals (Sahaym and Norton, 2008; Putla et al., 2019). Concurrently, the resources of fossil fuels are declining gradually as the consumption rate is increasing drastically to meet our energy needs. In addition, fossil fuels emit various greenhouse gases like CO2, S, NOx, etc., which are the key factors for global warming, a major threat facing humankind in the 21st century (Agarwal, 2007; Ambursa et al., 2016; Caliskan, 2017). To minimize the emission of greenhouse gas and to meet increasing energy demand, the use of an alternative renewable, sustainable, and safer energy source is essential (Panwar et al., 2011). Biofuels, like biodiesel and biogas are the excellent sources to meet the future energy demand (Kumar et al., 2018; Gilbert and Perl, 2008). Currently, biodiesel, also known as fatty acid alkyl esters (FAMEs), has attracted much attention due to its biodegradability, low emission of CO2 and CO, low sulphur content, renewable, and environmental friendly nature. Moreover, biodiesel is compatible to normal diesel engine without any modification (Kulkarni et al., 2006; Kralova and Sjöblom, 2010; Maeda et al., 2011; Ong et al., 2011). It is an esterification product of long chain fatty acids or transesterification product
⁎
of triglycerides, and is mainly produced from vegetable oils, waste cooking oils, non-edible oils, etc. (Agarwal and Das, 2001; Ma et al., 2018). In particular, biodiesel is largely produced by transesterification of long chain fatty acids using homogeneous catalysts, like KOH, NaOH, etc. (Likozar et al., 2016) Although homogeneous catalysts showed good activity in terms of conversions and yields, their toxic and corrosive nature, problems associated with product purification and as well as with catalyst recovery and its reusability limit their applications in chemical industry. Thus, the overall cost of biodiesel production increases hugely (Likozar and Levec, 2014; Mardhiah et al., 2017). In recent years, heterogeneous catalysts have attracted much interest as a potential substitute to homogenous catalysts because of their interesting properties, such as non-toxic, easy separation and recyclable, and non-corrosive nature (Sharma et al., 2011). Several heterogeneous catalysts, such as Zn@CaO (Kumar and Ali, 2013), CaO@SnO2 (Xie and Zhao, 2013), biguanide-functionalized hydroxyapatite encapsulated-γFe2O3 nanoparticles (Lee et al., 2015), CaO@La2O3 (Xie et al., 2017) etc. were reported for the production of biodiesel. However, the chemical synthesis of such catalysts is quite complicated and often involves drastic reaction conditions and multi steps, resulting in increased catalyst synthesis costs (Correia et al., 2014). In this context, the use of waste biomass-derived material as a heterogeneous solid catalyst is an excellent choice for a more sustainable biodiesel production (Sudarsanam et al., 2018; Shan et al., 2018).
Corresponding author. E-mail address: [email protected] (L. Rokhum).
https://doi.org/10.1016/j.indcrop.2019.111911 Received 8 July 2019; Received in revised form 22 October 2019; Accepted 26 October 2019 0926-6690/ © 2019 Elsevier B.V. All rights reserved.
Please cite this article as: Bishwajit Changmai, Putla Sudarsanam and Lalthazuala Rokhum, Industrial Crops & Products, https://doi.org/10.1016/j.indcrop.2019.111911
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
electron microscope), XPS (X-ray photoelectron spectroscopy), EDX (energy dispersive X-ray spectroscopy), BET (Brunauer-Emmett-Teller) and TGA (thermogravimetric analysis) techniques. The FTIR spectra was taken in a Spectrum 100 spectrophotometer. HRTEM was taken in an electron microscope JEM-2100 instrument. SEM and element distribution of the catalyst i.e., EDX were taken in JSM-6360 (JEOL) instrument. XRF analysis was performed on Bruker S4 Poinner instrument. XPS analysis was performed using a ESCALAB Xi + instrument. XRD analysis was performed on an ULTIMA IV. The N2 adsorption–desorption analysis was carried out using a Micromeritics ASAP 2010. The TGA analysis was performed using SII 6300 EXSTAR instrument under N2 atmosphere.
In spite of its wide availability and renewable nature, little attention has been directed towards modification of the waste biomass for improving its catalytic performance. A few studies have reported on the modification of waste biomass via surface functionalization using conventional bases and acids. In this regard, functionalized coconut husk (Vadery et al., 2014), palm trunk (Ezebor et al., 2014), wood ash (Sharma et al., 2012) and rice husk (Zhao et al., 2018) were reported as heterogeneous catalysts for the production of biodiesel. Although functionalized bio-waste derived carbon-based solid catalyst has its own merits, functionalization of waste biomass involves some drawbacks, such as high cost, high temperature for carbonization and tedious preparation steps, which limits its applications. Hence, using a raw biomass waste as an effective and recyclable heterogeneous catalyst is essential for sustainable biodiesel production in industrial scale. In this line, limited literature reported the application of raw biowaste (without functionalization) as a heterogeneous catalyst in the production of FAME (Betiku et al., 2016; Betiku and Ajala, 2014; Gohain et al., 2017). Recently, our research group has successfully utilized biowaste, banana (Musa acuminata species (available in Southeast Asia) peel ash as a heterogeneous catalyst for the production of biodiesel (Pathak et al., 2018). The catalyst shows excellent activity with a very high oil conversion of 98.95 %. Despite the high activity of the catalyst, the reusability of the catalyst limits its application in industrial scale. Among all the citrus fruit produced annually, about 75 % is contributed by orange (Citrus sinensis) (Li et al., 2008). The global orange production is about 49.3 million metric tons in the year 2017-2018. Therefore, the disposal of waste orange peel is a major concern. Nonetheless, orange peel is considered as a valuable agricultural biomass waste, composed of cellulose, carbohydrates, fats, etc. (Chutia et al., 2009). Several reports had been already published regarding the applications of orange peel in the field of pollution abatement, like removal of heavy metals from wastewater and production of solid biofuels (Biswas et al., 2008; Santos et al., 2015). Until now, there are no literature reports on the production of FAME by using orange peel ash. In this present work, in continuation of our interest in the development of economic heterogeneous catalysts, green synthetic methodologies (Rajkumari et al., 2017; Das et al., 2016) and renewable energy (Pathak et al., 2018; Laskar et al., 2018a; Chatterjee et al., 2017; Laskar et al., 2018b), we used waste biomass (orange peel ash) as a heterogeneous catalyst for the conversion of soybean oil to biodiesel at room temperature (RT). The investigated orange peel ash catalyst is highly abundant, renewable, and cost-effective. In addition, it is easily prepared by burning the dried orange peel and can be used for biodiesel production without further modification.
2.3. Transesterification of soybean oil 14 g of soybean oil was taken in a round bottom flask, followed by the addition of 4 mL methanol and 1 g catalyst (7 wt. % w.r.t soybean oil) and then, stirred at ambient temperature. The progress of the transesterification reaction was observed by taking thin layer chromatography (TLC). The reaction was completed after 7 h, as confirmed by TLC. The catalyst was recovered by centrifugation at 3500 rpm for 25 min. Biodiesel and glycerol were separated via separating funnel followed by evaporation of excess methanol via rotary evaporator. 2.4. Characterization of FAME The synthesized FAME was characterized by 1H NMR, 13C NMR and GC–MS (gas chromatography-mass spectrometry) analytic techniques. 1 H NMR and 13C NMR was carried out in Mercury Plus 300 MHz NMR spectrometer. GC–MS analysis was carried out in JEOL AccuTOF GCV instrument. 2.5. Reusability of the catalyst Prior to catalyst reusability test, the catalyst was recovered using centrifugation, washed with methanol and kept in an oven at 100 °C for 5 h to dry out the catalyst. Reusability test was investigated under the optimized reaction conditions i.e., 6:1 methanol:oil ratio, 7 wt.% catalyst, 7 h and room temperature. 3. Results and discussion 3.1. Characterization of orange peel (OP) and orange peel ash (OPA) catalyst EDX was performed to investigate the elemental composition of the orange peel (SI, Fig. S1) and the OPA catalyst (Fig. 1A). EDX data shows the presence of K, Ca, O, C, P, Mg, and Cl in both samples. The elemental distribution along with their atomic wt.% are shown in Table 1. The wt.% of K and Ca increased from 0.18 % and 0.03 % (in the dried orange peel) to 14.67 % and 7.34 % (in the OPA), respectively, due to the burning of organic matters present in the dried orange peel to produce OPA. Due to the presence of basic sites (e.g., K and Ca) OPA could show good catalytic activity in the base-catalyzed reactions like transesterification reaction of soybean oil to biodiesel. TGA analysis was performed under N2 atmosphere to verify the stability of the OPA catalyst with temperature. TGA thermogram displays an initial weight loss of 6 % up to 181 °C, due to the removal of adsorbed moisture from the catalyst. The further weight loss of the catalyst under high temperature might be due to the oxidation of the carboneous materials in the form of CO and CO2 (Chouhan and Sarma, 2013) (Fig. 1B). To investigate the pore volume, pore diameter and BET surface area of the prepared catalyst, N2 adsorption-desorption analysis was carried out. Fig. 1C shows N2 adsorption–desorption isotherm of type IV, which indicates that the catalyst is mesoporous in nature. BJH model (Fig. 1D)
2. Materials and methods 2.1. Chemicals used Soybean oil was purchased from the local market in Silchar, Assam, India. Methanol (analytical grade) was purchased from Merck, India. The chemicals were used without further purification. 2.2. Preparation and characterization of the catalysts The fresh orange were collected from Silchar, Assam, India. The peels were separated, washed properly with distilled water, cut into small pieces and then dried under sun for 3 days. Afterwards, about 50 g of dried orange peels were burnt in open air for 30 min and ground to produce orange peel ash (OPA) weighing 4.94 g. The structure, morphology, crystallinity and composition of the resultant catalyst were characterized by FTIR (Fourier transform infrared spectroscopy), XRF (X-ray fluorescence), XRD (powder X-ray diffraction), SEM (scanning electron microscope), HRTEM (high resolution transmission 2
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 1. EDX spectrum of OPA catalyst (A), TGA thermogram (B), N2 adsorption-desorption isotherm (C), and BJH pore size distribution (D). Table 1 EDX data for elemental composition of OP and OPA catalyst.
Table 2 Composition of OP and OPA as determined by XRF analysis.
Sl. No
Element
OP (Atomic %)
OPA (Atomic %)
1 2 3 4 5 6
O C K Ca Mg P
42.00 57.73 0.18 0.03 0.04 0.01
40.86 32.50 14.67 7.34 2.02 1.57
depicted high pore density in the mesoporous region centered at 2.85 nm. The pore volume and BET surface area of the catalyst were found to be 0.428 cc/g and 605.60 m2/g, respectively. Due to the high BET surface area and mesoporous nature of the catalyst, it may show good catalytic activity towards the production of FAME from soybean oil. To investigate the composition of OPA catalyst, XRF analysis was performed. The composition of the catalyst listed in Table 2, shows that alkaline K2O and CaO are the major components present in the catalyst (OPA). Thus, K2O and CaO could play a major catalytic role in the production of biodiesel from soybean oil. To investigate the basicity of the catalyst, Hammett indicator method was performed and it was found to be 9.8 < H_ < 12.2 for OPA catalyst. The high basicity of catalyst can be ascribed to the presence of K2O, CaO, MgO, etc., as observed from XRF data (Table 2). Hence, the presence of high basic sites can lead to improved catalytic activity of OPA catalyst towards biodiesel synthesis via transesterification reaction.
Sl. No
Compound formula
OPA (wt. %)
2 3 4 5 6 7 8 9
K2 O CaO SiO2 MgO P2O5 Na2O Fe2O3 MnO TiO2
51.64 25.67 13.24 4.76 2.95 1.81 0.070 0.033 0.114
FTIR analysis was performed to detect the functional groups present in the OPA (Fig. 2). The band at 3251 cm-1 represents the stretching frequency of OeH bond, due to the absorption of water molecules from the atmosphere. The characteristic peaks at 1447 cm-1, 1064 cm-1 and 876 cm-1 were attributed to carbonate stretching and bending vibration. The absorption peaks at 708 cm-1 and 608 cm-1 were attributed to KeO and CaOe stretching frequency, respectively. XRD analysis was performed to investigate the crystalline components present in the catalyst. XRD data (Fig. 3) show the presence of K2O, CaO, K2CO3, CaCO3, MgO, SiO2 etc. The peaks for K2O and K2CO3 were observed at 2θ = 30.106, 41.11, 33.72, and 42.160° (JCPDS file no. 77-2178 and JCPDS file no. 71-1466). The peaks for CaO and CaCO3 were observed at 2θ = 26.007, 39.83, 28.41, and 48.75° (JCPDS file no. 28-0775 and JCPDS file no. 72-1214). The existence of SiO2 and MgO in the catalyst was confirmed by the peaks at 2θ = 33.72, 54.37, 43.60, and 57.83° (JCPDS file no. 89-3609 and JCPDS file no. 57.83). Thus, 3
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 2. FTIR spectrum of fresh OPA.
Table 3, which supports the results obtained from both XRF (Table 2) and EDX data (Table 1). 3.2. Characterization of synthesized biodiesel Once the transesterification reaction to produce FAME was completed, the resultant product was confirmed by performing 1H NMR and 13 C NMR analysis. Fig. 6 shows the 1H NMR spectrum of soybean oil (Fig. 6A) and FAME (Fig. 6B). The appearance of peaks at 4.31 ppm and 5.36 ppm confirms the presence of glyceridic protons and olefinic protons (Fig. 6A) in soybean oil. While the appearance of a peak at 3.68 ppm and disappearance of peak at 4.31 ppm confirms the formation of FAME (Fig. 6B). The singlet peak at 3.68 ppm represents the methoxy protons of FAME and the triplet peak at 2.32 ppm can be attributed for α−CH2 protons. From 13C NMR, the appearance of peak at 51.41 ppm for −OCH3 carbon (SI, Fig. S2B) and disappearance of glyceridic carbon peaks at 68.89 ppm and 62.08 ppm (SI, Fig. S2A) confirms the formation of FAME. The percentage yield of soybean oil to FAME can be determined by using the integration value for methoxy protons and integration value for α−CH2 protons in the equation derived by Knothe and Kenar (Eq. 1). The percentage yield of FAME was calculated and it is found to be 98 % at optimized reaction conditions as discussed in the following sections.
Fig. 3. XRD spectrum of OPA catalyst.
oxides and carbonates of K and Ca are the dominating components in the catalyst, which supports the XRF data (Table 2). TEM and SEM were performed to investigate the external surface morphology and structure of OPA (Fig. 4). The TEM and SEM images showed well-arranged microporous and mesoporous structure with some spongy nature of the OPA catalyst. `To further investigate the elemental composition of the catalyst, XPS analysis was performed. Fig. 5 shows the wide range XPS spectrum along with deconvoluted spectra for C 1s, O 1s, K 2p, Ca 2p and Mg 1s. The catalyst comprises of C, O, K, Ca, Mg, Na, P, etc., as shown in Fig. 5A. The deconvoluted spectrum for C 1s (Fig. 5B) shows two peaks at 283.92 eV and 288.53 eV, which can be ascribed to CeC and CO] bonds, respectively. Fig. 5C shows two peaks for K 2p with binding energies of 291.73 eV and 294.45 eV, which are ascribed to K in the form of metal oxides and metal carbonates. Fig. 5D shows two peaks for Ca 2p with binding energies of 345.94 eV and 349.48 eV, which confirms the presence of CaO and CaCO3. Mg 1 s spectrum contains one peak with binding energy of 1303.72 eV, confirming the presence of MgO (Fig. 5E). The O 1s spectrum shows two peaks at 530.12 eV and 532.07 eV, which can be ascribed to the presence of oxides and carbonates of metals (Fig. 5F). The atomic wt. % of the major elements, obtained from XPS analysis, present in the OPA catalyst are listed in
C = 100 ×
2AMe 3ACH2
(1)
Here, C is the percent conversion of soybean oil, AMe is the integration area of the methoxy protons and ACH2 is the integration area of the α−CH2 protons. The chemical composition of the synthesized FAME was obtained by GC–MS analysis (Fig. 7). Furthermore, the quantitative measurement of FAME components was calculated by using the peak areas of FAME and internal standard peak area (methyl heptadecanoate, C17:0). The obtained data was presented in Table 4. The properties of soybean oil and synthesized FAME were measured by using standard methods depicted in the Table 5. The properties of the synthesized biodiesel meets the standard of ASTM D 6751. 3.3. Influence of reaction parameters on soybean oil to FAME conversion 3.3.1. Influence of catalyst loading The effect of catalyst loading in the conversion of soybean oil to 4
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 4. TEM images (A, B) and SEM images (C and D) of OPA catalyst.
Fig. 5. (A) Wide range XPS spectrum and (B), (C), (D), (E), (F) are the deconvoluted peaks of C1s, K 2p, Ca 2p and Mg 1s and O 1s of OPA catalyst, respectively. 5
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
run. In contrast, orange peel ash catalyst shows very high activity and stability towards the FAME production at room temperature and can be reused for 5 catalytic cycles with high percentage conversion.
Table 3 XPS data for elemental composition and their corresponding amount (%) of the catalyst. Sl. No
Elements
Atomic wt%
1 2 3 4 5 6
O1 s C1 s K2p Ca2p Mg1 s P2p
39.45 33.07 13.53 7.56 2.11 1.23
3.5. Reusability test of OPA catalyst Catalyst reusability is a very important factor to use the catalyst in commercial scale and industrial processes. Reusability test was performed for 5 successive cycles under the optimized reaction conditions i.e., 6:1 methanol:oil ratio with 7 wt.% at RT for 7 h (Fig. 11). The conversion of FAME after each cycle was recorded and it was observed that conversion decreases in each cycle and after the 5th cycle the conversion of FAME was only 85 %. This might be due to the slight leaching of active sites of the catalyst during the reaction and/or weight loss of the catalyst during recovery/purification steps. The XPS analysis of the recovered catalyst after 5th cycle was performed. The wide range XPS spectrum and deconvoluted spectra of K 2p, O 1s and Ca 2p (SI, Fig. S3), show a significant drop of K, O and Ca atomic wt. % from 13.53 %, 39.45 % and 7.56 % to 11.32 %, 34 % and 5.95 %, respectively. The slight loss of K and Ca leads to the slight decrease of catalytic activity towards the transesterification reaction and hence, the yield of FAME was considerably decreased to 85 % after the 5th catalytic cycle. Thus, we can conclude that K and Ca play a major catalytic role in the production of FAME. To investigate the morphology and structure of the recovered catalyst after the 5th cycle, SEM and TEM analyses were performed (SI, Fig. S4), which show an irregular surface, morphology and structure of the catalyst after the 5th cycle. To investigate the functional groups present in the recovered catalyst after the 5th cycle, FTIR analysis was performed (SI, Fig. S5 A). An absorption peak was observed at 3328.31 cm-1, which is due to the presence of moisture absorbed by the catalyst. The peak at 2924.92 cm1 could be attributed for C–H stretching of Ca(OCH3)2, which is formed in little amount on the catalyst surface, due to the reaction of CaO with methanol and glycerin (Gohain et al., 2017). The peaks at 1430.78 cm-1, 1069.53 cm-1 and 874.86 cm-1 could be attributed for carbonate stretching and bending vibration. The spectra also show the peaks at 718 cm-1 and 576.84 cm-1, which are characteristics of KeO and CaOe stretching vibrations. The chemical composition of the recovered OPA catalyst after 5th cycle, investigated via EDX analysis (SI, Fig. S5B), shows a significant loss of K, Ca and O wt. %, from 14.67 %, 40.86 % and 7.34 % to 11.95 %, 34.64 % and 6.10 %, respectively. Due to the slight loss of major catalytic components, such as K, Ca and O, the conversion of soybean oil decreased to 85 % after 5th cycle.
FAME (Fig. 8) was performed by varying the catalyst amount from 2 wt. % to 13 wt. % with 1:6 oil:methanol ratio at RT. When catalyst loading was 2 wt. % the conversion was 76.5 %. Increasing the catalyst loading to 7 wt. %, about 98 % conversion of oil to FAME was found. Further increase in catalyst loading, a decrease in the conversion of oil was observed. This might be due to the initiation of saponification reaction at higher catalyst loadings, which also makes the reaction mixture more viscous, resulting in severe mass transfer limitations (Pathak et al., 2018; Hsiao et al., 2011). Thus, the conversion of oil decreases at higher catalyst loadings and therefore, 7 wt. % is the optimal catalyst loading for achieving high conversion of soybean oil to FAME. 3.3.2. Influence of methanol:oil ratio The significant effect of oil:methanol ranging from 1:3 to 1:12 on the production of FAME (Fig. 9) was investigated with catalyst loading of 7 wt.%, 7 h reaction time and at ambient temperature. 1:3 of oil:methanol ratio gives only 74 % conversion of FAME. While, 1:6 of oil:methanol ratio drastically increases the conversion of FAME to 98 %. Further increase in the oil:methanol ratio upto 1:12; it is expected to exponentially increase the conversion of FAME. However, the conversion decreased to 96 % for 1:12 oil:methanol molar ratio since increase in the amount of methanol will drive the reaction to backward direction to form monoglyceride and diglyceride as the transesterification is a reversible reaction (Laskar et al., 2018a). Thus, 1:6 oil:methanol molar ratio is the optimized condition for the maximum conversion of soybean oil to FAME. 3.3.3. Influence of reaction time on conversion of soybean oil to FAME The influence of reaction time on biodiesel production was also investigated by performing the reaction for different time-period at optimized conditions (Fig. 10). It was observed that after 7 h it gives 98 % conversion of biodiesel. 3.4. Comparison of other reported heterogeneous catalysts with the present catalyst
4. Conclusions
Several literatures were reported on the production of FAME from soybean oil using heterogeneous catalysts. Comparison of reported heterogeneous catalysts with the present catalyst is shown in Table 6. CaO–MoO3–SBA-15 (Xie and Zhao, 2014), CaO/Al2O3 (Pasupulety et al., 2013), WO3/SnO2 (Xie and Wang, 2013) etc., showed very good stability and high conversion of soybean oil to FAME, but they have some drawbacks such as preparation of these catalyst require toxic chemicals, complex chemical process and high cost. However, several heterogeneous catalysts, such as chicken manure (Maneerung et al., 2016), egg shell (Wei et al., 2009), waste carbide slag (Li et al., 2015), snail shell (Laskar et al., 2018a) etc., can be prepared from natural waste which can reduce the total cost of the FAME production. Unfortunately, preparation of these catalyst requires high calcination temperature and longer time, which limits their wide applications in industrial scale. Recently, (Pathak et al. (2018) reported the use of a banana species Musa acuminata peel ash catalyst for the preparation of FAME from soybean oil at room temperature. Despite the high activity of the catalyst, the catalyst shows only 52 % conversion after the 4th
In conclusion, we for the first time reported the application of orange peel ash (OPA) as a raw heterogeneous catalyst for sustainable production of biodiesel via transesterification of soybean oil at room temperature. The mesoporous structure and the high BET surface area of the OPA (605.60 m2/g) enhanced its catalytic activity towards transesterification reaction. Potassium and calcium in the form of their oxides are the major components present in the catalyst, which makes the catalyst highly basic. Owing to heterogeneity and basic nature, OPA catalyst can potentially replace conventionally used homogeneous basic catalysts for biodiesel production. Moreover, the catalyst was used for biodiesel production without any functionalization or post-modification. Our catalyst has the advantages of being renewable, non-toxic, biodegradable, safe to handle and carbon neutral. Although the burning of orange peel produces carbon dioxide, it is considered ‘carbon neutral’ as orange trees absorb carbon dioxide during its whole life cycle. Hence, our catalyst has a huge impact on conserving the environment as compared to chemically synthesized catalysts which are often highly toxic, polluting, unstable and largely non-biodegradable. In addition, 6
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 6. 1H NMR of soybean oil (A) and FAME (B).
scale. The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
owing to its wide availability at low cost, the application of bio-waste materials as a catalyst source not only complements the potential recycling the natural waste resources but also reduce the total cost and negative environmental impact of biodiesel production for industrial 7
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 7. GC–MS spectrum of FAME. Table 4 Components present in the resultant FAME along with their percentage weight and retention time (R.T.). Entry
R.T.
Name of components
Corresponding acids
Amount (%)
1 2 3 4 5 6
18.05 20.13 21.44 24 24.36 27.05
Methyl Methyl Methyl Methyl Methyl Methyl
C16:0 C18:1 C18:2 C20:1 C20:0 C22:0
11.63 25.32 54.34 1.27 2.56 4.88
palmitate oleate linoleate cis-11-eicosenoate eicosenoate docosanoate
Table 5 Physico-chemical properties of soybean oil and soybean oil biodiesel. Properties
ASTM test method
ASTM limits for biodiesel
Soybean oil
Soybean oil biodiesel
Kinematic viscosity (cst at 40 °C) Flash point (°C) Cetane number Cloud point (°C) Pour point(°C) Density (g cm−3) Calorific Value (MJ/kg)
D 445
1.90-6
32.6
5.88
D 93 D 6890 D 2500 D 97 D 1448–1972 D240
< 93 ≥47 −3 to 12 −15 to 6 0.86-0.900 37.27
317 37.9 −9 12 0.93 39.6
146 51 2 −0.2 0.86 38.2
Fig. 9. Influence of oil:methanol molar ratio for the transesterification of soybean oil to biodiesel. Reaction conditions: catalyst loading of 7 wt. %, reaction time of 7 h and room temperature.
Fig. 10. Influence of reaction time for the transesterification of soybean oil to biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, catalyst loading of 7 wt. % and RT. Fig. 8. Influence of catalyst loading for the transesterification of soybean oil to biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, Catalyst loading of 7 wt. % and RT.
Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. 8
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Table 6 Comparison of other reported heterogeneous catalysts with the present catalyst. Entry
Catalyst
Methanol/oil molar ratio
Catalyst amount (wt. %)
Temperature (°C)
Time (h)
Conversion (%)
Reference
1 2 3 4 5 6 7 8 9 10
CaO–MoO3–SBA-15 CaO/Al2O3 WO3/SnO2 Chicken manure Egg shell Waste carbide slag Duck egg shell Snail shells Banana peel ash Orange peel ash
50:1 9:1 30:1 15:1 9:1 9:1 10:1 6:1 6:1 6:1
6 3 5 7.5 3 1 10 3 7 7
63 150 110 65 65 65 60 RT RT RT
50 3 5 3 3 0.5 1.2 7 4 7
83.2 90 79.2 90 95 91.3 94.6 100 98.95 98
(Xie and Zhao, 2014) (Pasupulety et al., 2013) (Xie and Wang, 2013) (Maneerung et al., 2016) (Wei et al., 2009) (Li et al., 2015) (Yin et al., 2016) (Laskar et al., 2018a) (Pathak et al., 2018) Present work
8, 355–357. https://doi.org/10.1016/j.wasman.2018.07.022. Kulkarni, M.G., Dalai, A.K., Bakshi, N.N., 2006. Utilization of green seed canola oil for biodiesel production. J. Chem. Technol. Biotechnol. 81, 1886–1893. https://doi.org/ 10.1002/jctb.1621. Kralova, I., Sjöblom, J., 2010. Biofuels–renewable energy sources: a review. J. Dispersion Sci. Technol. 31, 409–425. https://doi.org/10.1080/01932690903119674. Maeda, Y., Thanh, L.T., Imamura, K., Izutani, K., Okitsu, K., Van Boi, L., Lan, P.N., Tuan, N.C., Yoo, Y.E., Takenaka, N., 2011. New technology for the production of biodiesel fuel. Green Chem. 13, 1124–1128. https://doi.org/10.1039/C1GC15049A. Ong, H.C., Mahlia, T.M.I., Masjuki, H.H., Norhasyima, R.S., 2011. Comparison of palm oil, jatropha curcas and calophyllum inophyllum for biodiesel: a review. Renew. Sust. Energy Rev. 15, 3501–3515. https://doi.org/10.1016/j.rser.2011.05.005. Agarwal, A.K., Das, L.M., 2001. Biodiesel development and characterization for use as a fuel in compression ignition engines. J. Eng Gas Turb Power. 123, 440–447. https:// doi.org/10.1115/1.1364522. Ma, Y., Gao, Z., Wang, Q., Liu, Y., 2018. Biodiesels from microbial oils: opportunity and challenges. Bioresour. Technol. Rep. 263, 631–641. https://doi.org/10.1016/j. biortech.2018.05.028. Likozar, B., Pohar, A., Levec, J., 2016. Transesterification of oil to biodiesel in a continuous tubular reactor with static mixers: modelling reaction minetics, mass transfer, scale-up and optimization considering fatty acid composition. Fuel Process. Technol. 142, 326–336. https://doi.org/10.1016/j.fuproc.2015.10.035. Likozar, B., Levec, J., 2014. Effect of process conditions on equilibrium, reaction kinetics and mass transfer for triglyceride transesterification to biodiesel: experimental and modeling based on fatty acid composition. Fuel Process. Technol. 122, 30–41. https://doi.org/10.1016/j.fuproc.2014.01.017. Mardhiah, H.H., Ong, H.C., Masjuki, H.H., Lim, S., Lee, H.V., 2017. A review on latest developments and future prospects of heterogeneous catalyst in biodiesel production from non-edible oils. Renew. Sust. Energy Rev. 67, 1225–1236. https://doi.org/10. 1016/j.rser.2016.09.036. Sharma, Y.C., Singh, B., Korstad, J., 2011. latest developments on application of heterogenous basic catalysts for an efficient and eco friendly synthesis of biodiesel: A Review. Fuel 90, 1309–1324. https://doi.org/10.1016/j.fuel.2010.10.015. Kumar, D., Ali, A., 2013. Transesterification of low-quality triglycerides over a zn/cao heterogeneous catalyst: kinetics and reusability studies. Energy Fuels 27, 3758–3768. https://doi.org/10.1021/ef400594t. Xie, W., Zhao, L., 2013. Production of biodiesel by transesterification of soybean oil using calcium supported tin oxides as heterogeneous catalysts. Energy Convers. Manage. 76, 55–62. https://doi.org/10.1016/j.enconman.2013.07.027. Lee, H.V., Juan, J.C., Taufiq-Yap, Y.H., 2015. Preparation and application of binary acid–base cao–la2o3 catalyst for biodiesel production. Renew Energy 74, 124–132. https://doi.org/10.1016/j.renene.2014.07.017. Xie, W., Han, Y., Tai, S., 2017. Biodiesel production using biguanide-functionalized hydroxyapatite-encapsulated-γ-fe2o3 nanoparticles. Fuel 210, 83–90. https://doi.org/ 10.1016/j.fuel.2017.08.054. Correia, L.M., Saboya, R.M.A., Campelo, N.S., Cecilia, J.A., Rodrguez-Castelln, E., Cavalcante, C.L., Vieira, R.S., 2014. Characterization of calcium oxide catalysts from natural sources and their application in the transesterification of sunflower oil. Bioresour. Technol. 151, 207–213. https://doi.org/10.1016/j.biortech.2013.10.046. Sudarsanam, P., Zhong, R., den Bosch, S.V., Coman, S.M., Parvulescu, V.I., Sels, B.F., 2018. Functionalised heterogeneous catalysts for sustainable biomass valorisation. Chem. Soc. Rev. 47, 8349–8402. https://doi.org/10.1039/C8CS00410B. Shan, R., Lu, L., Shi, Y., Yuan, H., Shi, J., 2018. Catalysts from renewable resources for biodiesel production. Energ convers. Manage. 178, 277–289. https://doi.org/10. 1016/j.enconman.2018.10.032. Vadery, V., Narayanan, B.N., Ramakrishnan, R.M., Cherikkallinmel, S.K., Sugunan, S., Narayanan, D.P., Sasidharan, S., 2014. Room temperature production of jatropha biodiesel over coconut husk ash. Energy 70, 588–594. https://doi.org/10.1016/j. energy.2014.04.045. Ezebor, F., Khairuddean, M., Abdullah, A.Z., Boey, P.L., 2014. Oil palm trunk and sugarcane bagasse derived heterogeneous acid catalysts for production of fatty acid methyl esters. Energy 70, 493–503. https://doi.org/10.1016/j.energy.2014.04.024. Sharma, M., Khan, A.A., Puri, S.K., Tuli, D.K., 2012. Wood ash as a potential heterogeneous catalyst for biodiesel synthesis. Biomass Bioenergy 41, 94–106. https://doi. org/10.1016/j.biombioe.2012.02.017. Zhao, C., Yang, L., Xing, S., Luo, W., Wang, Z., Lv, P., 2018. Biodiesel production by a highly effective renewable catalyst from pyrolytic rice husk. J. Clean. Prod. 199,
Fig. 11. Reusability of the catalyst for the transesterification of soybean oil to biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, catalyst loading of 7 wt.%, reaction time of 7 h and RT.
Acknowledgements Financial support from the SERB (Grant No. SB/FT/CS-103/2013 and SB/EMEQ-076/2014), New Delhi is acknowledged. We acknowledge MHRD andDST, India for providing fund to BC. We also thank SAIF-NEHU, CSIR-NEIST, IIT-Roorkee, IIT-Bombay, IASST Guwahati and Assam University for analysis. Appendix A. Supplementary data Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.indcrop.2019.111911. References Sahaym, U., Norton, M.G., 2008. Advances in the application of nanotechnology in enabling a hydrogen economy. J. Mater. Sci. 43, 5395–5429. https://doi.org/10.1007/ s10853-008-2749-0. Putla, S., Peeters, E., Makshina, E., Parvulescu, V., Sels, B., 2019. Advances in porous and nanoscale catalysts for viable biomass conversion. Chem. Soc. Rev. 48, 2366–2421. https://doi.org/10.1039/c8cs00452h. Agarwal, A.K., 2007. Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines. Prog. Energy Combust. Sci. 33, 233271–233275. https://doi. org/10.1016/j.pecs.2006.08.003. Ambursa, M.M., Ali, T.H., Voon, L.H., Sudarsanam, P., Bhargava, S.K., Hamid, S.B.A., 2016. Hydrodeoxygenation of dibenzofuran to bicyclic hydrocarbons using bimetallic cu–ni catalysts supported on metal oxides. Fuel 180, 767–776. https://doi.org/10. 1016/j.fuel.2016.04.045. Caliskan, H., 2017. Environmental and enviroeconomic researches on diesel engines with diesel and biodiesel. Fuels. J. Clean. Prod. 154, 125–129. https://doi.org/10.1016/j. jclepro.2017.03.168. Panwar, N.L., Kaushik, S.C., Kothari, S., 2011. Role of renewable energy sources in environmental protection: a review. Renew. Sust. Energy Rev. 15, 1513–1524. https:// doi.org/10.1016/j.rser.2010.11.037. Kumar, A., Gupta, R., Rathod, V.K., 2018. Waste cooking oil and waste chicken eggshells derived solid base catalyst for the biodiesel production: optimization and kinetics. Waste Manag. 79, 169–178. https://doi.org/10.1016/j.wasman.2018.07.022. Gilbert, R., Perl, A., 2008. Book review: rob konings, hugo priemus and peter nijkamp (2008) the future of intermodal freight transport operations, design and policy. EJTIR
9
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Laskar, I.B., Rajkumari, K., Gupta, R., Chatterjee, S., Paul, B., Rokhum, L., 2018a. Waste Snail shell derived heterogeneous catalyst for biodiesel production by the transesterification of soybean oil. RSC Adv. 8, 20131–20142. https://doi.org/10.1039/ C8RA02397B. Chatterjee, S., Dhanurdhar, Rokhum, L., 2017. Extraction of a cardanol based liquid biofuel from waste natural resource and decarboxylation using a silver-based catalyst. Renew. Sust. Energy Rev. 72, 560–564. https://doi.org/10.1016/j.rser.2017.01.035. Laskar, I.B., Rajkumari, K., Gupta, R., Rokhum, L., 2018b. Acid-functionalized mesoporous polymer-catalyzed acetalization of glycerol to solketal, a potential fuel additive under solvent-free conditions. Energy Fuel. https://doi.org/10.1021/acs. energyfuels.8b02948. Chouhan, A.P.S., Sarma, A.K., 2013. Biodiesel production from jatropha curcas l. Oil using lemna perpusilla torrey ash as heterogeneous catalyst. Biomass Bioenergy 55, 386–389. https://doi.org/10.1016/j.biombioe.2013.02.009. Hsiao, M.C., Lin, C.C., Chang, Y.H., 2011. Microwave irradiation-assisted transesterification of soybean oil to biodiesel catalyzed by nanopowder calcium oxide. Fuel 90, 1963–1967. https://doi.org/10.1016/j.fuel.2011.01.004. Xie, W., Zhao, L., 2014. Heterogeneous CaO–MoO3–SBA-15 catalysts for biodiesel production from soybean oil. Energy Conv. Manag. 79, 34–42. https://doi.org/10.1016/ j.enconman.2013.11.041. Pasupulety, N., Gunda, K., Liu, Y., Rempel, G.L., Ng, F.T.T., 2013. Production of biodiesel from soybean oil on CaO/Al2O3 solid base catalysts. Appl. Catal. A Gen. 452, 189–202. https://doi.org/10.1016/j.apcata.2012.10.006. Xie, W., Wang, Tao, 2013. Biodiesel production from soybean oil transesterification using tin oxide-supported WO3 catalysts. Fuel Process Tech. 109, 150–155. https://doi.org/ 10.1016/j.fuproc.2012.09.053. Maneerung, T., Kawi, S., Dai, Y., Wang, C.H., 2016. Sustainable biodiesel production via transesterification of waste cooking oil by using CaO catalysts prepared from chicken manure. Energy Convers. Manage. 123, 487–497. https://doi.org/10.1016/j. enconman.2016.06.071. Wei, Z., Xu, C., Li, B., 2009. Application of waste eggshell as low-cost solid catalyst for biodiesel production. Bioresour. Technol. 100, 2883–2885. Li, F.J., Li, H.Q., Wang, L.G., Cao, Y., 2015. Waste carbide slag as a solid base catalyst for effective synthesis of biodiesel via transesterification of soybean oil with methanol. Fuel Process Tech. 131, 421–429. https://doi.org/10.1016/j.fuproc.2014.12.018. Yin, X., Duan, X., You, Q., Dai, C., Tan, Z., Zhu, X., 2016. Biodiesel production from soybean oil deodorizer distillate using calcined duck eggshell as catalyst. Energy Con Manag. 112, 199–207. https://doi.org/10.1016/j.enconman.2016.01.026.
772–780. https://doi.org/10.1016/j.jclepro.2018.07.242. Betiku, E., Akintunde, A.M., Ojumu, T.V., 2016. Banana peels as a biobase catalyst for fatty acid methyl esters production using Napoleon’s plume (bauhinia monandra) seed oil: a process Parameters Optimization Study. Energy 103, 797–806. https://doi. org/10.1016/j.energy.2016.02.138. Betiku, E., Ajala, S.O., 2014. Modeling and optimization of thevetia peruviana (yellow oleander) oil biodiesel synthesis via musa paradisiacal (plantain) peels as heterogeneous base catalyst: a case of artificial neural network vs. Response surface methodology. Ind. Crops Prod. 53, 314–322. https://doi.org/10.1016/j.indcrop. 2013.12.046. Gohain, M., Devi, A., Deka, D., 2017. Musa Balbisiana colla peel as highly effective renewable heterogeneous base catalyst for biodiesel production. Ind. Crops Prod. 109, 8–18. https://doi.org/10.1016/j.indcrop.2017.08.006. Pathak, G., Das, D., Rajkumari, K., Rokhum, L., 2018. Exploiting waste: towards a sustainable production of biodiesel using Musa acuminata peel ash as a heterogeneous catalyst. Green Chem. 20, 2365–2373. https://doi.org/10.1039/C8GC00071A. Li, X., Tang, Y., Caoa, X., Lua, D., Luoa, F., Shao, W., 2008. Preparation and evaluation of Orange peel cellulose adsorbents for effective removal of cadmium, zinc, cobalt and nickel. Colloid Surf.A 317, 512–521. https://doi.org/10.1016/j.colsurfa.2007.11. 031. Chutia, M., Bhuyan, P.D., Pathak, M.G., Sarma, T.C., Boruah, P., 2009. Antifungal activity and chemical composition of citrus reticulata blanco essential oil against phytopathogens from north east india. LWT - Food Sci. Technol. 42, 777–780. https://doi. org/10.1016/j.lwt.2008.09.015. Biswas, B.K., Inoue, J., Inoue, K., Ghimire, K.N., Harada, H., Ohto, K., Kawakita, H., 2008. Adsorptive removal of As (V) and As (III) from water by a Zr (IV)-loaded Orange waste gel. J. Hazard. Mater. 154, 1066–1074. https://doi.org/10.1016/j.jhazmat. 2007.11.030. Santos, C.M., Dweck, J., Viotto, R.S., Rosa, A.H., de Morais, L.C., 2015. Application of Orange peel waste in the production of solid biofuels and biosorbents. Bioresour. Technol. 196, 469–479. https://doi.org/10.1016/j.biortech.2015.07.114. Rajkumari, K., Kalita, J., Das, D., Rokhum, L., 2017. Magnetic Fe3O4@silica sulfuric acid nanoparticles promoted regioselective protection/deprotection of alcohols with dihydropyran under solvent-free conditions. RSC Adv. 7, 56559–56565. https://doi. org/10.1039/C7RA12458A. Das, D., Pathak, G., Rokhum, L., 2016. Polymer supported DMAP: an easily recyclable organocatalyst for highly atom-economical Henry reaction under solvent-free conditions. RSC Adv. 6, 104154–104163. https://doi.org/10.1039/C6RA23696K.
10
Contents lists available at ScienceDirect
Industrial Crops & Products journal homepage: www.elsevier.com/locate/indcrop
Biodiesel production using a renewable mesoporous solid catalyst Bishwajit Changmaia, Putla Sudarsanamb, Lalthazuala Rokhuma,* a b
Department of Chemistry, National Institute of Technology Silchar, Silchar, 788010, Assam, India Center for Sustainable Catalysis and Engineering, Faculty of Bioscience Engineering, KU Leuven, Celestijnenlaan 200f, Heverlee, Belgium
A R T I C LE I N FO
A B S T R A C T
Keywords: Fatty acid methyl ester Soybean oil Orange peel ash Reusability Biomass
Heterogeneous solid catalysts have been largely developed for biodiesel production, because of their attractive acid-base properties, strong hydrothermal stability, and efficient recovery/reusability. In this framework, developing bio-waste derived heterogeneous catalysts has attracted immense attention for several catalytic applications, owing to their inexpensive, high abundance, non-toxic, and adequate acid-base properties. In the present work, we investigated the catalytic performance of a biomass-derived orange peel ash (OPA), which contains a porous structure, as a raw heterogeneous catalyst for the transesterification of soybean oil to biodiesel. About 98 % conversion of soybean oil to biodiesel was obtained under the optimized reaction conditions i.e., 6:1 methanol:oil ratio, 7 wt. % catalyst loading, 7 h reaction time at ambient reaction temperature, which ascribed to the presence of abundant basic sites in the developed OPA catalyst. The catalyst can be reused for five successive cycles and shows good stability towards the biodiesel production.
1. Introduction Increasing rate of energy consumption and abnormal climate change, due to the rapid population growth and the emission of environmental pollutants (e.g., CO2), respectively, have led to the search for new, sustainable, and renewable energy sources. Presently, nonrenewable fossil fuels are the major source for the production of energy, fuels, and chemicals (Sahaym and Norton, 2008; Putla et al., 2019). Concurrently, the resources of fossil fuels are declining gradually as the consumption rate is increasing drastically to meet our energy needs. In addition, fossil fuels emit various greenhouse gases like CO2, S, NOx, etc., which are the key factors for global warming, a major threat facing humankind in the 21st century (Agarwal, 2007; Ambursa et al., 2016; Caliskan, 2017). To minimize the emission of greenhouse gas and to meet increasing energy demand, the use of an alternative renewable, sustainable, and safer energy source is essential (Panwar et al., 2011). Biofuels, like biodiesel and biogas are the excellent sources to meet the future energy demand (Kumar et al., 2018; Gilbert and Perl, 2008). Currently, biodiesel, also known as fatty acid alkyl esters (FAMEs), has attracted much attention due to its biodegradability, low emission of CO2 and CO, low sulphur content, renewable, and environmental friendly nature. Moreover, biodiesel is compatible to normal diesel engine without any modification (Kulkarni et al., 2006; Kralova and Sjöblom, 2010; Maeda et al., 2011; Ong et al., 2011). It is an esterification product of long chain fatty acids or transesterification product
⁎
of triglycerides, and is mainly produced from vegetable oils, waste cooking oils, non-edible oils, etc. (Agarwal and Das, 2001; Ma et al., 2018). In particular, biodiesel is largely produced by transesterification of long chain fatty acids using homogeneous catalysts, like KOH, NaOH, etc. (Likozar et al., 2016) Although homogeneous catalysts showed good activity in terms of conversions and yields, their toxic and corrosive nature, problems associated with product purification and as well as with catalyst recovery and its reusability limit their applications in chemical industry. Thus, the overall cost of biodiesel production increases hugely (Likozar and Levec, 2014; Mardhiah et al., 2017). In recent years, heterogeneous catalysts have attracted much interest as a potential substitute to homogenous catalysts because of their interesting properties, such as non-toxic, easy separation and recyclable, and non-corrosive nature (Sharma et al., 2011). Several heterogeneous catalysts, such as Zn@CaO (Kumar and Ali, 2013), CaO@SnO2 (Xie and Zhao, 2013), biguanide-functionalized hydroxyapatite encapsulated-γFe2O3 nanoparticles (Lee et al., 2015), CaO@La2O3 (Xie et al., 2017) etc. were reported for the production of biodiesel. However, the chemical synthesis of such catalysts is quite complicated and often involves drastic reaction conditions and multi steps, resulting in increased catalyst synthesis costs (Correia et al., 2014). In this context, the use of waste biomass-derived material as a heterogeneous solid catalyst is an excellent choice for a more sustainable biodiesel production (Sudarsanam et al., 2018; Shan et al., 2018).
Corresponding author. E-mail address: [email protected] (L. Rokhum).
https://doi.org/10.1016/j.indcrop.2019.111911 Received 8 July 2019; Received in revised form 22 October 2019; Accepted 26 October 2019 0926-6690/ © 2019 Elsevier B.V. All rights reserved.
Please cite this article as: Bishwajit Changmai, Putla Sudarsanam and Lalthazuala Rokhum, Industrial Crops & Products, https://doi.org/10.1016/j.indcrop.2019.111911
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
electron microscope), XPS (X-ray photoelectron spectroscopy), EDX (energy dispersive X-ray spectroscopy), BET (Brunauer-Emmett-Teller) and TGA (thermogravimetric analysis) techniques. The FTIR spectra was taken in a Spectrum 100 spectrophotometer. HRTEM was taken in an electron microscope JEM-2100 instrument. SEM and element distribution of the catalyst i.e., EDX were taken in JSM-6360 (JEOL) instrument. XRF analysis was performed on Bruker S4 Poinner instrument. XPS analysis was performed using a ESCALAB Xi + instrument. XRD analysis was performed on an ULTIMA IV. The N2 adsorption–desorption analysis was carried out using a Micromeritics ASAP 2010. The TGA analysis was performed using SII 6300 EXSTAR instrument under N2 atmosphere.
In spite of its wide availability and renewable nature, little attention has been directed towards modification of the waste biomass for improving its catalytic performance. A few studies have reported on the modification of waste biomass via surface functionalization using conventional bases and acids. In this regard, functionalized coconut husk (Vadery et al., 2014), palm trunk (Ezebor et al., 2014), wood ash (Sharma et al., 2012) and rice husk (Zhao et al., 2018) were reported as heterogeneous catalysts for the production of biodiesel. Although functionalized bio-waste derived carbon-based solid catalyst has its own merits, functionalization of waste biomass involves some drawbacks, such as high cost, high temperature for carbonization and tedious preparation steps, which limits its applications. Hence, using a raw biomass waste as an effective and recyclable heterogeneous catalyst is essential for sustainable biodiesel production in industrial scale. In this line, limited literature reported the application of raw biowaste (without functionalization) as a heterogeneous catalyst in the production of FAME (Betiku et al., 2016; Betiku and Ajala, 2014; Gohain et al., 2017). Recently, our research group has successfully utilized biowaste, banana (Musa acuminata species (available in Southeast Asia) peel ash as a heterogeneous catalyst for the production of biodiesel (Pathak et al., 2018). The catalyst shows excellent activity with a very high oil conversion of 98.95 %. Despite the high activity of the catalyst, the reusability of the catalyst limits its application in industrial scale. Among all the citrus fruit produced annually, about 75 % is contributed by orange (Citrus sinensis) (Li et al., 2008). The global orange production is about 49.3 million metric tons in the year 2017-2018. Therefore, the disposal of waste orange peel is a major concern. Nonetheless, orange peel is considered as a valuable agricultural biomass waste, composed of cellulose, carbohydrates, fats, etc. (Chutia et al., 2009). Several reports had been already published regarding the applications of orange peel in the field of pollution abatement, like removal of heavy metals from wastewater and production of solid biofuels (Biswas et al., 2008; Santos et al., 2015). Until now, there are no literature reports on the production of FAME by using orange peel ash. In this present work, in continuation of our interest in the development of economic heterogeneous catalysts, green synthetic methodologies (Rajkumari et al., 2017; Das et al., 2016) and renewable energy (Pathak et al., 2018; Laskar et al., 2018a; Chatterjee et al., 2017; Laskar et al., 2018b), we used waste biomass (orange peel ash) as a heterogeneous catalyst for the conversion of soybean oil to biodiesel at room temperature (RT). The investigated orange peel ash catalyst is highly abundant, renewable, and cost-effective. In addition, it is easily prepared by burning the dried orange peel and can be used for biodiesel production without further modification.
2.3. Transesterification of soybean oil 14 g of soybean oil was taken in a round bottom flask, followed by the addition of 4 mL methanol and 1 g catalyst (7 wt. % w.r.t soybean oil) and then, stirred at ambient temperature. The progress of the transesterification reaction was observed by taking thin layer chromatography (TLC). The reaction was completed after 7 h, as confirmed by TLC. The catalyst was recovered by centrifugation at 3500 rpm for 25 min. Biodiesel and glycerol were separated via separating funnel followed by evaporation of excess methanol via rotary evaporator. 2.4. Characterization of FAME The synthesized FAME was characterized by 1H NMR, 13C NMR and GC–MS (gas chromatography-mass spectrometry) analytic techniques. 1 H NMR and 13C NMR was carried out in Mercury Plus 300 MHz NMR spectrometer. GC–MS analysis was carried out in JEOL AccuTOF GCV instrument. 2.5. Reusability of the catalyst Prior to catalyst reusability test, the catalyst was recovered using centrifugation, washed with methanol and kept in an oven at 100 °C for 5 h to dry out the catalyst. Reusability test was investigated under the optimized reaction conditions i.e., 6:1 methanol:oil ratio, 7 wt.% catalyst, 7 h and room temperature. 3. Results and discussion 3.1. Characterization of orange peel (OP) and orange peel ash (OPA) catalyst EDX was performed to investigate the elemental composition of the orange peel (SI, Fig. S1) and the OPA catalyst (Fig. 1A). EDX data shows the presence of K, Ca, O, C, P, Mg, and Cl in both samples. The elemental distribution along with their atomic wt.% are shown in Table 1. The wt.% of K and Ca increased from 0.18 % and 0.03 % (in the dried orange peel) to 14.67 % and 7.34 % (in the OPA), respectively, due to the burning of organic matters present in the dried orange peel to produce OPA. Due to the presence of basic sites (e.g., K and Ca) OPA could show good catalytic activity in the base-catalyzed reactions like transesterification reaction of soybean oil to biodiesel. TGA analysis was performed under N2 atmosphere to verify the stability of the OPA catalyst with temperature. TGA thermogram displays an initial weight loss of 6 % up to 181 °C, due to the removal of adsorbed moisture from the catalyst. The further weight loss of the catalyst under high temperature might be due to the oxidation of the carboneous materials in the form of CO and CO2 (Chouhan and Sarma, 2013) (Fig. 1B). To investigate the pore volume, pore diameter and BET surface area of the prepared catalyst, N2 adsorption-desorption analysis was carried out. Fig. 1C shows N2 adsorption–desorption isotherm of type IV, which indicates that the catalyst is mesoporous in nature. BJH model (Fig. 1D)
2. Materials and methods 2.1. Chemicals used Soybean oil was purchased from the local market in Silchar, Assam, India. Methanol (analytical grade) was purchased from Merck, India. The chemicals were used without further purification. 2.2. Preparation and characterization of the catalysts The fresh orange were collected from Silchar, Assam, India. The peels were separated, washed properly with distilled water, cut into small pieces and then dried under sun for 3 days. Afterwards, about 50 g of dried orange peels were burnt in open air for 30 min and ground to produce orange peel ash (OPA) weighing 4.94 g. The structure, morphology, crystallinity and composition of the resultant catalyst were characterized by FTIR (Fourier transform infrared spectroscopy), XRF (X-ray fluorescence), XRD (powder X-ray diffraction), SEM (scanning electron microscope), HRTEM (high resolution transmission 2
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 1. EDX spectrum of OPA catalyst (A), TGA thermogram (B), N2 adsorption-desorption isotherm (C), and BJH pore size distribution (D). Table 1 EDX data for elemental composition of OP and OPA catalyst.
Table 2 Composition of OP and OPA as determined by XRF analysis.
Sl. No
Element
OP (Atomic %)
OPA (Atomic %)
1 2 3 4 5 6
O C K Ca Mg P
42.00 57.73 0.18 0.03 0.04 0.01
40.86 32.50 14.67 7.34 2.02 1.57
depicted high pore density in the mesoporous region centered at 2.85 nm. The pore volume and BET surface area of the catalyst were found to be 0.428 cc/g and 605.60 m2/g, respectively. Due to the high BET surface area and mesoporous nature of the catalyst, it may show good catalytic activity towards the production of FAME from soybean oil. To investigate the composition of OPA catalyst, XRF analysis was performed. The composition of the catalyst listed in Table 2, shows that alkaline K2O and CaO are the major components present in the catalyst (OPA). Thus, K2O and CaO could play a major catalytic role in the production of biodiesel from soybean oil. To investigate the basicity of the catalyst, Hammett indicator method was performed and it was found to be 9.8 < H_ < 12.2 for OPA catalyst. The high basicity of catalyst can be ascribed to the presence of K2O, CaO, MgO, etc., as observed from XRF data (Table 2). Hence, the presence of high basic sites can lead to improved catalytic activity of OPA catalyst towards biodiesel synthesis via transesterification reaction.
Sl. No
Compound formula
OPA (wt. %)
2 3 4 5 6 7 8 9
K2 O CaO SiO2 MgO P2O5 Na2O Fe2O3 MnO TiO2
51.64 25.67 13.24 4.76 2.95 1.81 0.070 0.033 0.114
FTIR analysis was performed to detect the functional groups present in the OPA (Fig. 2). The band at 3251 cm-1 represents the stretching frequency of OeH bond, due to the absorption of water molecules from the atmosphere. The characteristic peaks at 1447 cm-1, 1064 cm-1 and 876 cm-1 were attributed to carbonate stretching and bending vibration. The absorption peaks at 708 cm-1 and 608 cm-1 were attributed to KeO and CaOe stretching frequency, respectively. XRD analysis was performed to investigate the crystalline components present in the catalyst. XRD data (Fig. 3) show the presence of K2O, CaO, K2CO3, CaCO3, MgO, SiO2 etc. The peaks for K2O and K2CO3 were observed at 2θ = 30.106, 41.11, 33.72, and 42.160° (JCPDS file no. 77-2178 and JCPDS file no. 71-1466). The peaks for CaO and CaCO3 were observed at 2θ = 26.007, 39.83, 28.41, and 48.75° (JCPDS file no. 28-0775 and JCPDS file no. 72-1214). The existence of SiO2 and MgO in the catalyst was confirmed by the peaks at 2θ = 33.72, 54.37, 43.60, and 57.83° (JCPDS file no. 89-3609 and JCPDS file no. 57.83). Thus, 3
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 2. FTIR spectrum of fresh OPA.
Table 3, which supports the results obtained from both XRF (Table 2) and EDX data (Table 1). 3.2. Characterization of synthesized biodiesel Once the transesterification reaction to produce FAME was completed, the resultant product was confirmed by performing 1H NMR and 13 C NMR analysis. Fig. 6 shows the 1H NMR spectrum of soybean oil (Fig. 6A) and FAME (Fig. 6B). The appearance of peaks at 4.31 ppm and 5.36 ppm confirms the presence of glyceridic protons and olefinic protons (Fig. 6A) in soybean oil. While the appearance of a peak at 3.68 ppm and disappearance of peak at 4.31 ppm confirms the formation of FAME (Fig. 6B). The singlet peak at 3.68 ppm represents the methoxy protons of FAME and the triplet peak at 2.32 ppm can be attributed for α−CH2 protons. From 13C NMR, the appearance of peak at 51.41 ppm for −OCH3 carbon (SI, Fig. S2B) and disappearance of glyceridic carbon peaks at 68.89 ppm and 62.08 ppm (SI, Fig. S2A) confirms the formation of FAME. The percentage yield of soybean oil to FAME can be determined by using the integration value for methoxy protons and integration value for α−CH2 protons in the equation derived by Knothe and Kenar (Eq. 1). The percentage yield of FAME was calculated and it is found to be 98 % at optimized reaction conditions as discussed in the following sections.
Fig. 3. XRD spectrum of OPA catalyst.
oxides and carbonates of K and Ca are the dominating components in the catalyst, which supports the XRF data (Table 2). TEM and SEM were performed to investigate the external surface morphology and structure of OPA (Fig. 4). The TEM and SEM images showed well-arranged microporous and mesoporous structure with some spongy nature of the OPA catalyst. `To further investigate the elemental composition of the catalyst, XPS analysis was performed. Fig. 5 shows the wide range XPS spectrum along with deconvoluted spectra for C 1s, O 1s, K 2p, Ca 2p and Mg 1s. The catalyst comprises of C, O, K, Ca, Mg, Na, P, etc., as shown in Fig. 5A. The deconvoluted spectrum for C 1s (Fig. 5B) shows two peaks at 283.92 eV and 288.53 eV, which can be ascribed to CeC and CO] bonds, respectively. Fig. 5C shows two peaks for K 2p with binding energies of 291.73 eV and 294.45 eV, which are ascribed to K in the form of metal oxides and metal carbonates. Fig. 5D shows two peaks for Ca 2p with binding energies of 345.94 eV and 349.48 eV, which confirms the presence of CaO and CaCO3. Mg 1 s spectrum contains one peak with binding energy of 1303.72 eV, confirming the presence of MgO (Fig. 5E). The O 1s spectrum shows two peaks at 530.12 eV and 532.07 eV, which can be ascribed to the presence of oxides and carbonates of metals (Fig. 5F). The atomic wt. % of the major elements, obtained from XPS analysis, present in the OPA catalyst are listed in
C = 100 ×
2AMe 3ACH2
(1)
Here, C is the percent conversion of soybean oil, AMe is the integration area of the methoxy protons and ACH2 is the integration area of the α−CH2 protons. The chemical composition of the synthesized FAME was obtained by GC–MS analysis (Fig. 7). Furthermore, the quantitative measurement of FAME components was calculated by using the peak areas of FAME and internal standard peak area (methyl heptadecanoate, C17:0). The obtained data was presented in Table 4. The properties of soybean oil and synthesized FAME were measured by using standard methods depicted in the Table 5. The properties of the synthesized biodiesel meets the standard of ASTM D 6751. 3.3. Influence of reaction parameters on soybean oil to FAME conversion 3.3.1. Influence of catalyst loading The effect of catalyst loading in the conversion of soybean oil to 4
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 4. TEM images (A, B) and SEM images (C and D) of OPA catalyst.
Fig. 5. (A) Wide range XPS spectrum and (B), (C), (D), (E), (F) are the deconvoluted peaks of C1s, K 2p, Ca 2p and Mg 1s and O 1s of OPA catalyst, respectively. 5
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
run. In contrast, orange peel ash catalyst shows very high activity and stability towards the FAME production at room temperature and can be reused for 5 catalytic cycles with high percentage conversion.
Table 3 XPS data for elemental composition and their corresponding amount (%) of the catalyst. Sl. No
Elements
Atomic wt%
1 2 3 4 5 6
O1 s C1 s K2p Ca2p Mg1 s P2p
39.45 33.07 13.53 7.56 2.11 1.23
3.5. Reusability test of OPA catalyst Catalyst reusability is a very important factor to use the catalyst in commercial scale and industrial processes. Reusability test was performed for 5 successive cycles under the optimized reaction conditions i.e., 6:1 methanol:oil ratio with 7 wt.% at RT for 7 h (Fig. 11). The conversion of FAME after each cycle was recorded and it was observed that conversion decreases in each cycle and after the 5th cycle the conversion of FAME was only 85 %. This might be due to the slight leaching of active sites of the catalyst during the reaction and/or weight loss of the catalyst during recovery/purification steps. The XPS analysis of the recovered catalyst after 5th cycle was performed. The wide range XPS spectrum and deconvoluted spectra of K 2p, O 1s and Ca 2p (SI, Fig. S3), show a significant drop of K, O and Ca atomic wt. % from 13.53 %, 39.45 % and 7.56 % to 11.32 %, 34 % and 5.95 %, respectively. The slight loss of K and Ca leads to the slight decrease of catalytic activity towards the transesterification reaction and hence, the yield of FAME was considerably decreased to 85 % after the 5th catalytic cycle. Thus, we can conclude that K and Ca play a major catalytic role in the production of FAME. To investigate the morphology and structure of the recovered catalyst after the 5th cycle, SEM and TEM analyses were performed (SI, Fig. S4), which show an irregular surface, morphology and structure of the catalyst after the 5th cycle. To investigate the functional groups present in the recovered catalyst after the 5th cycle, FTIR analysis was performed (SI, Fig. S5 A). An absorption peak was observed at 3328.31 cm-1, which is due to the presence of moisture absorbed by the catalyst. The peak at 2924.92 cm1 could be attributed for C–H stretching of Ca(OCH3)2, which is formed in little amount on the catalyst surface, due to the reaction of CaO with methanol and glycerin (Gohain et al., 2017). The peaks at 1430.78 cm-1, 1069.53 cm-1 and 874.86 cm-1 could be attributed for carbonate stretching and bending vibration. The spectra also show the peaks at 718 cm-1 and 576.84 cm-1, which are characteristics of KeO and CaOe stretching vibrations. The chemical composition of the recovered OPA catalyst after 5th cycle, investigated via EDX analysis (SI, Fig. S5B), shows a significant loss of K, Ca and O wt. %, from 14.67 %, 40.86 % and 7.34 % to 11.95 %, 34.64 % and 6.10 %, respectively. Due to the slight loss of major catalytic components, such as K, Ca and O, the conversion of soybean oil decreased to 85 % after 5th cycle.
FAME (Fig. 8) was performed by varying the catalyst amount from 2 wt. % to 13 wt. % with 1:6 oil:methanol ratio at RT. When catalyst loading was 2 wt. % the conversion was 76.5 %. Increasing the catalyst loading to 7 wt. %, about 98 % conversion of oil to FAME was found. Further increase in catalyst loading, a decrease in the conversion of oil was observed. This might be due to the initiation of saponification reaction at higher catalyst loadings, which also makes the reaction mixture more viscous, resulting in severe mass transfer limitations (Pathak et al., 2018; Hsiao et al., 2011). Thus, the conversion of oil decreases at higher catalyst loadings and therefore, 7 wt. % is the optimal catalyst loading for achieving high conversion of soybean oil to FAME. 3.3.2. Influence of methanol:oil ratio The significant effect of oil:methanol ranging from 1:3 to 1:12 on the production of FAME (Fig. 9) was investigated with catalyst loading of 7 wt.%, 7 h reaction time and at ambient temperature. 1:3 of oil:methanol ratio gives only 74 % conversion of FAME. While, 1:6 of oil:methanol ratio drastically increases the conversion of FAME to 98 %. Further increase in the oil:methanol ratio upto 1:12; it is expected to exponentially increase the conversion of FAME. However, the conversion decreased to 96 % for 1:12 oil:methanol molar ratio since increase in the amount of methanol will drive the reaction to backward direction to form monoglyceride and diglyceride as the transesterification is a reversible reaction (Laskar et al., 2018a). Thus, 1:6 oil:methanol molar ratio is the optimized condition for the maximum conversion of soybean oil to FAME. 3.3.3. Influence of reaction time on conversion of soybean oil to FAME The influence of reaction time on biodiesel production was also investigated by performing the reaction for different time-period at optimized conditions (Fig. 10). It was observed that after 7 h it gives 98 % conversion of biodiesel. 3.4. Comparison of other reported heterogeneous catalysts with the present catalyst
4. Conclusions
Several literatures were reported on the production of FAME from soybean oil using heterogeneous catalysts. Comparison of reported heterogeneous catalysts with the present catalyst is shown in Table 6. CaO–MoO3–SBA-15 (Xie and Zhao, 2014), CaO/Al2O3 (Pasupulety et al., 2013), WO3/SnO2 (Xie and Wang, 2013) etc., showed very good stability and high conversion of soybean oil to FAME, but they have some drawbacks such as preparation of these catalyst require toxic chemicals, complex chemical process and high cost. However, several heterogeneous catalysts, such as chicken manure (Maneerung et al., 2016), egg shell (Wei et al., 2009), waste carbide slag (Li et al., 2015), snail shell (Laskar et al., 2018a) etc., can be prepared from natural waste which can reduce the total cost of the FAME production. Unfortunately, preparation of these catalyst requires high calcination temperature and longer time, which limits their wide applications in industrial scale. Recently, (Pathak et al. (2018) reported the use of a banana species Musa acuminata peel ash catalyst for the preparation of FAME from soybean oil at room temperature. Despite the high activity of the catalyst, the catalyst shows only 52 % conversion after the 4th
In conclusion, we for the first time reported the application of orange peel ash (OPA) as a raw heterogeneous catalyst for sustainable production of biodiesel via transesterification of soybean oil at room temperature. The mesoporous structure and the high BET surface area of the OPA (605.60 m2/g) enhanced its catalytic activity towards transesterification reaction. Potassium and calcium in the form of their oxides are the major components present in the catalyst, which makes the catalyst highly basic. Owing to heterogeneity and basic nature, OPA catalyst can potentially replace conventionally used homogeneous basic catalysts for biodiesel production. Moreover, the catalyst was used for biodiesel production without any functionalization or post-modification. Our catalyst has the advantages of being renewable, non-toxic, biodegradable, safe to handle and carbon neutral. Although the burning of orange peel produces carbon dioxide, it is considered ‘carbon neutral’ as orange trees absorb carbon dioxide during its whole life cycle. Hence, our catalyst has a huge impact on conserving the environment as compared to chemically synthesized catalysts which are often highly toxic, polluting, unstable and largely non-biodegradable. In addition, 6
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 6. 1H NMR of soybean oil (A) and FAME (B).
scale. The authors declare the following financial interests/personal relationships which may be considered as potential competing interests:
owing to its wide availability at low cost, the application of bio-waste materials as a catalyst source not only complements the potential recycling the natural waste resources but also reduce the total cost and negative environmental impact of biodiesel production for industrial 7
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Fig. 7. GC–MS spectrum of FAME. Table 4 Components present in the resultant FAME along with their percentage weight and retention time (R.T.). Entry
R.T.
Name of components
Corresponding acids
Amount (%)
1 2 3 4 5 6
18.05 20.13 21.44 24 24.36 27.05
Methyl Methyl Methyl Methyl Methyl Methyl
C16:0 C18:1 C18:2 C20:1 C20:0 C22:0
11.63 25.32 54.34 1.27 2.56 4.88
palmitate oleate linoleate cis-11-eicosenoate eicosenoate docosanoate
Table 5 Physico-chemical properties of soybean oil and soybean oil biodiesel. Properties
ASTM test method
ASTM limits for biodiesel
Soybean oil
Soybean oil biodiesel
Kinematic viscosity (cst at 40 °C) Flash point (°C) Cetane number Cloud point (°C) Pour point(°C) Density (g cm−3) Calorific Value (MJ/kg)
D 445
1.90-6
32.6
5.88
D 93 D 6890 D 2500 D 97 D 1448–1972 D240
< 93 ≥47 −3 to 12 −15 to 6 0.86-0.900 37.27
317 37.9 −9 12 0.93 39.6
146 51 2 −0.2 0.86 38.2
Fig. 9. Influence of oil:methanol molar ratio for the transesterification of soybean oil to biodiesel. Reaction conditions: catalyst loading of 7 wt. %, reaction time of 7 h and room temperature.
Fig. 10. Influence of reaction time for the transesterification of soybean oil to biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, catalyst loading of 7 wt. % and RT. Fig. 8. Influence of catalyst loading for the transesterification of soybean oil to biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, Catalyst loading of 7 wt. % and RT.
Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. 8
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Table 6 Comparison of other reported heterogeneous catalysts with the present catalyst. Entry
Catalyst
Methanol/oil molar ratio
Catalyst amount (wt. %)
Temperature (°C)
Time (h)
Conversion (%)
Reference
1 2 3 4 5 6 7 8 9 10
CaO–MoO3–SBA-15 CaO/Al2O3 WO3/SnO2 Chicken manure Egg shell Waste carbide slag Duck egg shell Snail shells Banana peel ash Orange peel ash
50:1 9:1 30:1 15:1 9:1 9:1 10:1 6:1 6:1 6:1
6 3 5 7.5 3 1 10 3 7 7
63 150 110 65 65 65 60 RT RT RT
50 3 5 3 3 0.5 1.2 7 4 7
83.2 90 79.2 90 95 91.3 94.6 100 98.95 98
(Xie and Zhao, 2014) (Pasupulety et al., 2013) (Xie and Wang, 2013) (Maneerung et al., 2016) (Wei et al., 2009) (Li et al., 2015) (Yin et al., 2016) (Laskar et al., 2018a) (Pathak et al., 2018) Present work
8, 355–357. https://doi.org/10.1016/j.wasman.2018.07.022. Kulkarni, M.G., Dalai, A.K., Bakshi, N.N., 2006. Utilization of green seed canola oil for biodiesel production. J. Chem. Technol. Biotechnol. 81, 1886–1893. https://doi.org/ 10.1002/jctb.1621. Kralova, I., Sjöblom, J., 2010. Biofuels–renewable energy sources: a review. J. Dispersion Sci. Technol. 31, 409–425. https://doi.org/10.1080/01932690903119674. Maeda, Y., Thanh, L.T., Imamura, K., Izutani, K., Okitsu, K., Van Boi, L., Lan, P.N., Tuan, N.C., Yoo, Y.E., Takenaka, N., 2011. New technology for the production of biodiesel fuel. Green Chem. 13, 1124–1128. https://doi.org/10.1039/C1GC15049A. Ong, H.C., Mahlia, T.M.I., Masjuki, H.H., Norhasyima, R.S., 2011. Comparison of palm oil, jatropha curcas and calophyllum inophyllum for biodiesel: a review. Renew. Sust. Energy Rev. 15, 3501–3515. https://doi.org/10.1016/j.rser.2011.05.005. Agarwal, A.K., Das, L.M., 2001. Biodiesel development and characterization for use as a fuel in compression ignition engines. J. Eng Gas Turb Power. 123, 440–447. https:// doi.org/10.1115/1.1364522. Ma, Y., Gao, Z., Wang, Q., Liu, Y., 2018. Biodiesels from microbial oils: opportunity and challenges. Bioresour. Technol. Rep. 263, 631–641. https://doi.org/10.1016/j. biortech.2018.05.028. Likozar, B., Pohar, A., Levec, J., 2016. Transesterification of oil to biodiesel in a continuous tubular reactor with static mixers: modelling reaction minetics, mass transfer, scale-up and optimization considering fatty acid composition. Fuel Process. Technol. 142, 326–336. https://doi.org/10.1016/j.fuproc.2015.10.035. Likozar, B., Levec, J., 2014. Effect of process conditions on equilibrium, reaction kinetics and mass transfer for triglyceride transesterification to biodiesel: experimental and modeling based on fatty acid composition. Fuel Process. Technol. 122, 30–41. https://doi.org/10.1016/j.fuproc.2014.01.017. Mardhiah, H.H., Ong, H.C., Masjuki, H.H., Lim, S., Lee, H.V., 2017. A review on latest developments and future prospects of heterogeneous catalyst in biodiesel production from non-edible oils. Renew. Sust. Energy Rev. 67, 1225–1236. https://doi.org/10. 1016/j.rser.2016.09.036. Sharma, Y.C., Singh, B., Korstad, J., 2011. latest developments on application of heterogenous basic catalysts for an efficient and eco friendly synthesis of biodiesel: A Review. Fuel 90, 1309–1324. https://doi.org/10.1016/j.fuel.2010.10.015. Kumar, D., Ali, A., 2013. Transesterification of low-quality triglycerides over a zn/cao heterogeneous catalyst: kinetics and reusability studies. Energy Fuels 27, 3758–3768. https://doi.org/10.1021/ef400594t. Xie, W., Zhao, L., 2013. Production of biodiesel by transesterification of soybean oil using calcium supported tin oxides as heterogeneous catalysts. Energy Convers. Manage. 76, 55–62. https://doi.org/10.1016/j.enconman.2013.07.027. Lee, H.V., Juan, J.C., Taufiq-Yap, Y.H., 2015. Preparation and application of binary acid–base cao–la2o3 catalyst for biodiesel production. Renew Energy 74, 124–132. https://doi.org/10.1016/j.renene.2014.07.017. Xie, W., Han, Y., Tai, S., 2017. Biodiesel production using biguanide-functionalized hydroxyapatite-encapsulated-γ-fe2o3 nanoparticles. Fuel 210, 83–90. https://doi.org/ 10.1016/j.fuel.2017.08.054. Correia, L.M., Saboya, R.M.A., Campelo, N.S., Cecilia, J.A., Rodrguez-Castelln, E., Cavalcante, C.L., Vieira, R.S., 2014. Characterization of calcium oxide catalysts from natural sources and their application in the transesterification of sunflower oil. Bioresour. Technol. 151, 207–213. https://doi.org/10.1016/j.biortech.2013.10.046. Sudarsanam, P., Zhong, R., den Bosch, S.V., Coman, S.M., Parvulescu, V.I., Sels, B.F., 2018. Functionalised heterogeneous catalysts for sustainable biomass valorisation. Chem. Soc. Rev. 47, 8349–8402. https://doi.org/10.1039/C8CS00410B. Shan, R., Lu, L., Shi, Y., Yuan, H., Shi, J., 2018. Catalysts from renewable resources for biodiesel production. Energ convers. Manage. 178, 277–289. https://doi.org/10. 1016/j.enconman.2018.10.032. Vadery, V., Narayanan, B.N., Ramakrishnan, R.M., Cherikkallinmel, S.K., Sugunan, S., Narayanan, D.P., Sasidharan, S., 2014. Room temperature production of jatropha biodiesel over coconut husk ash. Energy 70, 588–594. https://doi.org/10.1016/j. energy.2014.04.045. Ezebor, F., Khairuddean, M., Abdullah, A.Z., Boey, P.L., 2014. Oil palm trunk and sugarcane bagasse derived heterogeneous acid catalysts for production of fatty acid methyl esters. Energy 70, 493–503. https://doi.org/10.1016/j.energy.2014.04.024. Sharma, M., Khan, A.A., Puri, S.K., Tuli, D.K., 2012. Wood ash as a potential heterogeneous catalyst for biodiesel synthesis. Biomass Bioenergy 41, 94–106. https://doi. org/10.1016/j.biombioe.2012.02.017. Zhao, C., Yang, L., Xing, S., Luo, W., Wang, Z., Lv, P., 2018. Biodiesel production by a highly effective renewable catalyst from pyrolytic rice husk. J. Clean. Prod. 199,
Fig. 11. Reusability of the catalyst for the transesterification of soybean oil to biodiesel. Reaction conditions: 6:1 of methanol:oil ratio, catalyst loading of 7 wt.%, reaction time of 7 h and RT.
Acknowledgements Financial support from the SERB (Grant No. SB/FT/CS-103/2013 and SB/EMEQ-076/2014), New Delhi is acknowledged. We acknowledge MHRD andDST, India for providing fund to BC. We also thank SAIF-NEHU, CSIR-NEIST, IIT-Roorkee, IIT-Bombay, IASST Guwahati and Assam University for analysis. Appendix A. Supplementary data Supplementary material related to this article can be found, in the online version, at doi:https://doi.org/10.1016/j.indcrop.2019.111911. References Sahaym, U., Norton, M.G., 2008. Advances in the application of nanotechnology in enabling a hydrogen economy. J. Mater. Sci. 43, 5395–5429. https://doi.org/10.1007/ s10853-008-2749-0. Putla, S., Peeters, E., Makshina, E., Parvulescu, V., Sels, B., 2019. Advances in porous and nanoscale catalysts for viable biomass conversion. Chem. Soc. Rev. 48, 2366–2421. https://doi.org/10.1039/c8cs00452h. Agarwal, A.K., 2007. Biofuels (alcohols and biodiesel) applications as fuels for internal combustion engines. Prog. Energy Combust. Sci. 33, 233271–233275. https://doi. org/10.1016/j.pecs.2006.08.003. Ambursa, M.M., Ali, T.H., Voon, L.H., Sudarsanam, P., Bhargava, S.K., Hamid, S.B.A., 2016. Hydrodeoxygenation of dibenzofuran to bicyclic hydrocarbons using bimetallic cu–ni catalysts supported on metal oxides. Fuel 180, 767–776. https://doi.org/10. 1016/j.fuel.2016.04.045. Caliskan, H., 2017. Environmental and enviroeconomic researches on diesel engines with diesel and biodiesel. Fuels. J. Clean. Prod. 154, 125–129. https://doi.org/10.1016/j. jclepro.2017.03.168. Panwar, N.L., Kaushik, S.C., Kothari, S., 2011. Role of renewable energy sources in environmental protection: a review. Renew. Sust. Energy Rev. 15, 1513–1524. https:// doi.org/10.1016/j.rser.2010.11.037. Kumar, A., Gupta, R., Rathod, V.K., 2018. Waste cooking oil and waste chicken eggshells derived solid base catalyst for the biodiesel production: optimization and kinetics. Waste Manag. 79, 169–178. https://doi.org/10.1016/j.wasman.2018.07.022. Gilbert, R., Perl, A., 2008. Book review: rob konings, hugo priemus and peter nijkamp (2008) the future of intermodal freight transport operations, design and policy. EJTIR
9
Industrial Crops & Products xxx (xxxx) xxxx
B. Changmai, et al.
Laskar, I.B., Rajkumari, K., Gupta, R., Chatterjee, S., Paul, B., Rokhum, L., 2018a. Waste Snail shell derived heterogeneous catalyst for biodiesel production by the transesterification of soybean oil. RSC Adv. 8, 20131–20142. https://doi.org/10.1039/ C8RA02397B. Chatterjee, S., Dhanurdhar, Rokhum, L., 2017. Extraction of a cardanol based liquid biofuel from waste natural resource and decarboxylation using a silver-based catalyst. Renew. Sust. Energy Rev. 72, 560–564. https://doi.org/10.1016/j.rser.2017.01.035. Laskar, I.B., Rajkumari, K., Gupta, R., Rokhum, L., 2018b. Acid-functionalized mesoporous polymer-catalyzed acetalization of glycerol to solketal, a potential fuel additive under solvent-free conditions. Energy Fuel. https://doi.org/10.1021/acs. energyfuels.8b02948. Chouhan, A.P.S., Sarma, A.K., 2013. Biodiesel production from jatropha curcas l. Oil using lemna perpusilla torrey ash as heterogeneous catalyst. Biomass Bioenergy 55, 386–389. https://doi.org/10.1016/j.biombioe.2013.02.009. Hsiao, M.C., Lin, C.C., Chang, Y.H., 2011. Microwave irradiation-assisted transesterification of soybean oil to biodiesel catalyzed by nanopowder calcium oxide. Fuel 90, 1963–1967. https://doi.org/10.1016/j.fuel.2011.01.004. Xie, W., Zhao, L., 2014. Heterogeneous CaO–MoO3–SBA-15 catalysts for biodiesel production from soybean oil. Energy Conv. Manag. 79, 34–42. https://doi.org/10.1016/ j.enconman.2013.11.041. Pasupulety, N., Gunda, K., Liu, Y., Rempel, G.L., Ng, F.T.T., 2013. Production of biodiesel from soybean oil on CaO/Al2O3 solid base catalysts. Appl. Catal. A Gen. 452, 189–202. https://doi.org/10.1016/j.apcata.2012.10.006. Xie, W., Wang, Tao, 2013. Biodiesel production from soybean oil transesterification using tin oxide-supported WO3 catalysts. Fuel Process Tech. 109, 150–155. https://doi.org/ 10.1016/j.fuproc.2012.09.053. Maneerung, T., Kawi, S., Dai, Y., Wang, C.H., 2016. Sustainable biodiesel production via transesterification of waste cooking oil by using CaO catalysts prepared from chicken manure. Energy Convers. Manage. 123, 487–497. https://doi.org/10.1016/j. enconman.2016.06.071. Wei, Z., Xu, C., Li, B., 2009. Application of waste eggshell as low-cost solid catalyst for biodiesel production. Bioresour. Technol. 100, 2883–2885. Li, F.J., Li, H.Q., Wang, L.G., Cao, Y., 2015. Waste carbide slag as a solid base catalyst for effective synthesis of biodiesel via transesterification of soybean oil with methanol. Fuel Process Tech. 131, 421–429. https://doi.org/10.1016/j.fuproc.2014.12.018. Yin, X., Duan, X., You, Q., Dai, C., Tan, Z., Zhu, X., 2016. Biodiesel production from soybean oil deodorizer distillate using calcined duck eggshell as catalyst. Energy Con Manag. 112, 199–207. https://doi.org/10.1016/j.enconman.2016.01.026.
772–780. https://doi.org/10.1016/j.jclepro.2018.07.242. Betiku, E., Akintunde, A.M., Ojumu, T.V., 2016. Banana peels as a biobase catalyst for fatty acid methyl esters production using Napoleon’s plume (bauhinia monandra) seed oil: a process Parameters Optimization Study. Energy 103, 797–806. https://doi. org/10.1016/j.energy.2016.02.138. Betiku, E., Ajala, S.O., 2014. Modeling and optimization of thevetia peruviana (yellow oleander) oil biodiesel synthesis via musa paradisiacal (plantain) peels as heterogeneous base catalyst: a case of artificial neural network vs. Response surface methodology. Ind. Crops Prod. 53, 314–322. https://doi.org/10.1016/j.indcrop. 2013.12.046. Gohain, M., Devi, A., Deka, D., 2017. Musa Balbisiana colla peel as highly effective renewable heterogeneous base catalyst for biodiesel production. Ind. Crops Prod. 109, 8–18. https://doi.org/10.1016/j.indcrop.2017.08.006. Pathak, G., Das, D., Rajkumari, K., Rokhum, L., 2018. Exploiting waste: towards a sustainable production of biodiesel using Musa acuminata peel ash as a heterogeneous catalyst. Green Chem. 20, 2365–2373. https://doi.org/10.1039/C8GC00071A. Li, X., Tang, Y., Caoa, X., Lua, D., Luoa, F., Shao, W., 2008. Preparation and evaluation of Orange peel cellulose adsorbents for effective removal of cadmium, zinc, cobalt and nickel. Colloid Surf.A 317, 512–521. https://doi.org/10.1016/j.colsurfa.2007.11. 031. Chutia, M., Bhuyan, P.D., Pathak, M.G., Sarma, T.C., Boruah, P., 2009. Antifungal activity and chemical composition of citrus reticulata blanco essential oil against phytopathogens from north east india. LWT - Food Sci. Technol. 42, 777–780. https://doi. org/10.1016/j.lwt.2008.09.015. Biswas, B.K., Inoue, J., Inoue, K., Ghimire, K.N., Harada, H., Ohto, K., Kawakita, H., 2008. Adsorptive removal of As (V) and As (III) from water by a Zr (IV)-loaded Orange waste gel. J. Hazard. Mater. 154, 1066–1074. https://doi.org/10.1016/j.jhazmat. 2007.11.030. Santos, C.M., Dweck, J., Viotto, R.S., Rosa, A.H., de Morais, L.C., 2015. Application of Orange peel waste in the production of solid biofuels and biosorbents. Bioresour. Technol. 196, 469–479. https://doi.org/10.1016/j.biortech.2015.07.114. Rajkumari, K., Kalita, J., Das, D., Rokhum, L., 2017. Magnetic Fe3O4@silica sulfuric acid nanoparticles promoted regioselective protection/deprotection of alcohols with dihydropyran under solvent-free conditions. RSC Adv. 7, 56559–56565. https://doi. org/10.1039/C7RA12458A. Das, D., Pathak, G., Rokhum, L., 2016. Polymer supported DMAP: an easily recyclable organocatalyst for highly atom-economical Henry reaction under solvent-free conditions. RSC Adv. 6, 104154–104163. https://doi.org/10.1039/C6RA23696K.
10