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paper text:

Transesteri�cation and Fuel Characterization of Rice Bran Oil: A Biore�nery Path Research highlights ? RBO a potential feedstock used for e�cient & cost-effective biodiesel

production. ? Heterogeneous Ni(II)-Schiff base catalyst for conversion of RBO to RBOB & reusability studied. ? FAME & petro-derived fuel properties of RBOB are similar to

conventional biodiesels. ? Extracted RBOB showed potential in vitro antimicrobial and antioxidant activities. Abstract: Highest third worldwide production of the agricultural

product namely rice causes a huge quantity of waste residues especially, rice bran concurrently with rice husk. It fabricates the residual wastes nearly of about 31.9 MMT

annually throughout the world and owing to the thermal point of view they are not easily upgradable due to high silica content. Meanwhile, rice bran after extrusion in broilers

have been used to extract oil containing free fatty acids (FFAs) (15–30%) such as

cis–9–, & cis–12–octadecadienoic and cis–9, cis–12 & cis–15–octadecatrienoic

oils. Rice bran fatty oil methyl esters are suitably converted into biodiesel for compression ignition (CI) engines via transesteri�cation path in the presence of Ni/H2

heterogeneous basic catalytical environment along with 4–methoxy–2– hydroxybenzalidene–p–toluidine promoter. Owing to certain main drawbacks like viscous and volatile

nature of the potential alternative �rst and second generation derived biofuels, there occur some troubles in their long application in CI engines, which could effectively be

minimized by such a catalytical pathway. The literature has been found a very little research on this oil as a potential substitute for petro–diesel. Finally, the produced rice bran

based biodiesel was analyzed for its appropriateness as a fuel for ignition (CI) engines. The 2 outcomes explored the characteristics for the biodiesel extracted, under the most

promising 3 circumstances are resembling those of the petro–based fuels. The observed yields are high 4 when compared to other enzymatic transesteri�cation and

homogeneous catalysis. In 5 addition, in vitro microbial and antioxidant potentialities of RBOB were tested and compared 6 with the standard controls. Alternatively, low value

by–products for the biodiesel industries 7 like glycerol were also obtained and it gave oil suitable to feed the power generators. 8 Keywords: Rice bran oil; Heterogeneous basic

catalysis; Promoter; Transesteri�cation; 9 Biodiesel characteristics. 10 1. Introduction At present, nearly 85–88 % of fossil fuel energy resources like coal, bitumen, natural gas, oil

ManuscriptBy: Gopal Krishnan

As of: Apr 29, 2019 2:26:49 AM 6,837 words - 58 matches - 25 sources

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shales and petroleum have been utilized for our primary energy consumption in socio–economic, transportation and industrialization development activities which leads to the

fast diminishing of fossil fuel in the near future [1, 2]. In addition, the usage of fossil fuel creates some problems like environmental pollution, global climate change and increase

in greenhouse gases (GHGs) [3]. Now–a–days, a number of research works have been investigated to explore an alternate to fossil fuels for the production of cheap, convenient,

eco–friendly and non–toxic alternative renewable energy fuel sources subsequent from sun, wind, geothermal, hydraulic, nuclear, hydrogen, biomass, biofuels or biodiesel etc [4].

Of which, biodiesel or bio–oil could be considered as promising green sources of energy. According to

American Society for Testing and Materials (ASTM – 6751), the

biodiesel is considered as long chain fatty oils of C14–C22 carbons. These are derived from the transesteri�cation of �rst and second generation derived oils (UCO) with ROH

(low alcohols), with or without catalysts to give high quality biodiesel alternative to petroleum– based diesel fuels. These high–quality biodiesels are used in diesel or

compression ignition engine without any modi�cation [5], to reduce the overall emission of GHGs, comprising CO2, CH4, N2O, SO2, particulate materials, water vapours, volatile

organic compounds etc [6]. Rice (Oryza sativa), a monocotyledon plant belongs to the Gramineae family, Oryzoides and Oryza glaberrima subfamily for the Asian rice and African

rice, respectively is the world’s third most signi�cant principal food cereal crops in the agrarian systems [7–9]. The rice directly provides ~ 30–45 % calories due to its richness in

nutrients like carbohydrates, vitamins, minerals and salt contents [10–13]. During the period 2017–2018, according to USDA (United States Departments of Agriculture), the world

paddy rice 3 production will be 481.04 million metric tons (MMT) with China (36 %), India (21 %), USA (15%) and Indonesia (8%) which are the leading rice producing countries.

Annually, the rice harvested world widely was > 700 million tons with grown of rice grain ~ 85–90 % around the globe [14]. The lipid contents of the rice grain have been divided

into neutral lipids (triglycerides) (75–80 %), glycolipids (5.1–6.9 %) and phospholipids (3.5–5.2 %) among them the highest quantity of neutral lipids are localized in rice bran and

its embryo. Modern rice polishing or milling technology of paddy rice yielded ~ 70 % of white rice (endosperm) with addition of some valuable by–products like 20, 8 and 2 % of

rice husk, hull / bran and tracer amount of rice germ, respectively [15, 16]. In the �rst stage of rice milling, the husk / hull is produced, due to the removal of hard and productive

shell on the rice grain [15, 16]. In the second stage of rice milling or whitening process, the outer bran layer (brownish part–rice bran) of rice kernel (endosperm) is removed by

rubbing to produce milled or polished white paddy rice. Also, various extraction practice of rice

bran (RB) to rice bran oil (RBO)

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with solvents namely; n–hexane / methanol / petroleum ether / isopropanol / butanol at low or high temperature conditions are employed. Other methods such as supercritical

�uid extraction (SFE), microwave extraction, ohmic heating with solvent free condition and enzymatic assisted extraction methods have been used. Such processes yielded only

~15–25 % of oil (low content). It is due to the variety of rice, its long–term storage and degree of modern milling or polishing processes of the paddy rice [17–19]. Rice bran (RB)

has become more attractive which is attributable to its environmental reimbursement including enrichment in local income, rural employment, cleaner or eco– friendly

environment with technologically consideration as a potential alternative petroleum– based fossil diesel or bioenergy or biodiesel sources for compression ignition (CI) engine

[20, 21]. Rice bran (RB) is a very important resource of certain high value added by–products due to high nutritional ingredient content of proteins (12–16 %), lipid or fat (14–22

%), crude or 4 dietary �ber (7–10 %), carbohydrate or starch (45–55 %), moisture (8–10 %) and ash (6–11 %) [22]. World widely annually, the production of rice bran (RB) falls in

the range of about 75 million tons. In India, nearly 125 million tons of rice is used to produce 6–7 million and (RB) one million tons of rice

bran (RB) and rice bran oil (RBO)

respectively [23]. Moreover, 40–65 % of FFAs could effectively be converted into edible purposes and only <10–20 % into crude rice bran oil (CRBO). Thus, an agricultural waste of

rice has considerable attention for the production of biodiesel which can effectively replace the petroleum–diesel energy resource in CI engines. The CRBO can be extracted with

n–hexane solvent and thereby yields 90–95 % of saponi�able matter (SM), triglycerides (81–84 %), diglycerides (2–3 %), monoglycerides (5–6 %), waxes (0.3–0.5 %), glycolipids

(0.7–1.0 %), phospholipids (1.2–1.6 %) along with unusually 4.1–4.5 % (high level) of unsaponi�able matters (UM) and this unsaponi�able matter content in ROB is very higher

than other vegetable oils [24–26]. Recently, the rice bran oil (RBO) has become more attractive among other vegetable oils because of its richness towards some value added

bioactive products and antioxidant compounds such as lipids, proteins, phytosterols, vitamins viz, B complex, E (?–tocopherol & tocotrienol), K and ?–oryzanol [27–29]. Although,

RBO is a prominent as well as high nutritional compound as it can be utilized for curing some pathological diseases as well as preventing ageing in human life by means of

chemotherapy and some other clinical �elds. Thereby, it can be suggested that this oil is appropriate for the extraction of bio–oil or biodiesel as the alternative of fossil fuel in

future [30–32]. The transformation of vegetable based oils / animal fats into biodiesel could be achieved by various procedures like transesteri�cation, cracking, blending, micro–

emulsi�cation and pyrolysis. Among them, transesteri�cation process is superior to the other methods followed. Generally, transesteri�cation process takes place within 1–6 h,

which converts the oils or fats (triglyceride contents) into glycerol (valuable by–product) and biodiesel of fatty acid alkyl ester (FAME–MeOH is used / FAEE–EtOH is used) with

the presence of short–chain MeOH / EtOH in addition to homogenous or heterogeneous catalysts (Table 1). The use of homogenous catalyzed transesteri�cation reaction (like

KOH, NaOH, HCl, H2SO4) create several problems in environment and corrosion risk. Thus, numerous investigators have reported that the making of biodiesel can be assisted in

the presence of solid phase heterogeneous base catalysis to produce signi�cantly higher quantity of biodiesel and some glycerol like byproducts [33, 34]. Huge number of

heterogeneous base catalysts like organometallic compounds, metal or mixed metal oxides, mesoporous silica Fe–MSN, Mg–Zr catalyst, etc are employed in the catalytic

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change of FFAs into FMAEs [35]. The tracer element namely nickel (Ni) is an essential nutrient and is a catalytic cofactor [35]. In addition, it is used for certain enzymatic

bioactive reactions in anaerobic microbes [36]. To our knowledge, a very little research reports, regarding the solid heterogeneous base catalyst performance of nickel and Schiff

(Ni(II)–Schiff) base chelate promoter in simultaneous esteri�cation and transesteri�cation of CRBO into RBO based biodiesel (RBOB) production under mild condition have been

elucidated. As a part of our ongoing work, [36–39] the present work deals with the production of

rice bran oil (RBO) from the rice bran

feedstock and investigates a catalytic performance of heterogeneous Ni(s)/H2(g) environment with the presence of

Ni(II)–Schiff base chelate as promoter to produce the rice bran oil

based biodiesel (RBOB) from rice bran oil (Fig. 1). The produced RBOB via heterogeneous base catalysis was characterized structurally as well as spectrally by means of

FT–IR, UV–vis., GC/Mass, 1H NMR and 13C NMR.

Furthermore, in vitro biological antioxidant potentialities of RBOB were tested.

2. Materials and methods 2.1. Materials All the chemicals used were of Analytical grade and used without any further puri�cation.

The sources of the products are obtained

from E. Merck, Sigma Aldrich, Fluka (Puriss) and S.D. Fine chemicals.

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The paddy rice was collected from local rice industry in Kanyakumari (South India). The solvents used for the entire study at different stages of this work was standardized

according to the procedures followed by Perrin et al. [40], 2.2. General synthesis

of Ni(II)–Schiff base chelate promoter The

starting material, p–toluidine was synthesized by well–known conventional method. One part of p–nitrotoluol in minimum amount of THF solvent and 10 mL aqueous solution of

NH4Cl together was taken in a RB �ask (100 mL), ethanol was added drop–by– drop to get a clear yellowish green solution, cooled below 20 oC and slowly 8 part of �ne powder

of solid Zn(II) dust into this solution was added. The resulting

reaction mixture was stirred well and then re�uxed for an hour and kept all over the

night. The formed p–toluidine was �ltered as a colored solid compound, washed using ethanol, dried at 100 oC and �nally potted in desiccators. The Schiff base ligand (HL: 4–

methoxy–2–hydroxybenzalidene–p– toluidine) was synthesized by a condensation reaction path using 20 mL hot alcoholic solution of the above synthesized p–toluidine (10

mmol) with 20 ml of 4–methoxy salicylaldehyde (10 mmol) in 1:1 stoichiometry and the formed

reaction mixture was re�uxed for 3 h and kept overnight. On standing, the

formed solid yellowish orange compound was vacuum �ltered, washed with ethanol, hot water, followed by anhydrous ether, dried at 100 oC and stored in anhydrous CaCl2

(Yield: 85 %). 10 mmol hot ethanolic (10 mL) solution of Schiff base 4–methoxy–2– hydroxybenzalidene–p–toluidine ligand (HL) was added drop–wise to 10 mmol of hot

ethanolic (10 mL) Ni(CH3COO)2 • 4H2O in 1:1 (Schiff base: Ni(II) salt) molar ratio. The resultant product was re�uxed (3 h). Additionally, aqueous NH4OH (10 mmol) was added

to make the solution alkaline (pH: 8.0) and kept overnight. The formed compound was vacuum �ltered, washed with ethanol, hot water, followed by anhydrous ether and stored in

anhydrous CaCl2 (Yield: 85 %) (Scheme 1). The yield of the isolated promoter (P) was found to be 73 %. 2.3. Extraction of CRBO from rice bran (RB) The rice bran (RB) was �rst

sieved all the way through a 12–mesh sieve (particle size) to eliminate broken rice along with some other mechanical impurities during the rice milling or polishing processes and

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then Soxhlet’s extraction method solvent with n–hexane was carried out [41]. Approximately, 15–18 % of oil with 10 % moisture containing rice bran was kept into an oven at 95–

105 oC for 2 h to remove the water and moisture content from 10 to 4 %. The dried samples were maintained at –16 to –12 oC to avoid any degradation throughout the

experiment. In 500 mL round bottom �ask, dried RB (50 g) was shaken thoroughly in absolute n–hexane (200 mL) using Soxhlet’s apparatus and then the yield was re�uxed in

support of 3–6 h. The resultant mixture comprising saponi�ed matter was acidi�ed to pH = 2 (using HCl or H2SO4) and left overnight. After the oil extraction, the resulting

contents were cooled and �ltered or centrifuged to separate CRBO which contain lofty FAMEs and the solvent n–hexane was evaporated at 50 oC and reduced pressure by

means of a rotary evaporator and then recycled (Fig. 2a). The yield of the obtained oil was found by weighing. This extraction process was repeated three times to make

stabilization. The chemical con�guration of rice bran oil is shown in Table 2 which mainly comprises C16 & C18 constitutes of unsaturated and saturated fatty acids along with

unsaponi�able matter (UM). After that, the obtained crude rice bran oil (CRBO) was re�ned, degummed and dewaxed and �nally used for the biodiesel production. 2.4.

Heterogeneous basic

Ni(II)–Schiff base chelate promoter

catalyzed transesteri�cation of CRBO Heterogeneous CRBO

transesteri�cation reaction involves Ni(II)–Schiff base chelate promoter assisted hydrotreatment process

under hydrogen (30 bar H2 pressure) environment using the

solid Ni(II) ion with absolute methanol (MeOH)

in 500 mL three–necked round bottom �ask to yield biodiesel [37]. Initially, 0.5 g (Wt. %) of the promoter (P) was taken in 20 mL absolute methanol. It was placed on the

magnetic heating mantle for 15 min to get homogenous mixture. To this solution, CRBO (25 mL) in 150 mL of absolute methanol was mixed in the molar ratio of 1:6

(CRBO:MeOH) with simultaneous addition of 0.25 g Ni(CH3COO)2 · 4H2O in 20 mL of the same methanol solution. The proposed heterogeneous catalyzed transesteri�cation of

RBO based biodiesel from CRBO is shown in Figure 2b and the detailed mechanism is shown in Figure 3a and 3b. Generally, in transesteri�cation process, the FFAs of the oil react

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with alcohol in the stoichiometric ratio 1:3 (Oil:MeOH) to form simple glycerides (esters) and glycerol. Actually, the solvent alcohol in excess quantity (1:6) is requisite to attain

the equilibrium to the product side as the reaction is reversible, to yield more ester contents. The resulting solution was stirred well at the temperature below 65 oC, to stop

methanol evaporation from the reaction mixture with continuous stirring for 2 h at 300 rpm speed. Afterwards, the resultant product from glycerol and the base catalyst layers

was separated by means of a separating funnel. Using centrifugation, the promoter was separated by means of mechanical �ltration and the solvent (MeOH) was recovered by

vacuum evaporator. Finally, FAMEs of RBOB was obtained a layer form, washed thoroughly by several times with conductivity / distilled water and lastly by means of warm water

to remove the residues of the promoter, present and the obtained rice bran oil based biodiesel (RBOB) was collected in an air–tight container of aluminium metal for further

investigation (yield: 93.5 %). 9 2.5. Instrumentation The proximate along with ultimate investigations were done, via

Elementar Vario EL III CHNS analyzer on STIC, CUSAT, India. The

Ni(II) ion in the promoter was gravimetrically estimated by means of the standard ammonium oxalate method. The various physico–chemical characterizations (density,

viscosity, speci�c gravity, calori�c value, �ash point, pour point) were carried out using standard ASTM method of rice bran oil based biodiesel from the

R.M.K. Engineering College, Chennai, Tamilnadu. The functionalities of all the

samples were veri�ed all the way through Infrared spectra, a

JASCO FT/IR–410 spectrometer in the range of

about 4000–400 cm–, using KBr pellets. Electronic (UV–vis.,) spectra (in 200–1100 nm) were recorded with absolute alcohol by a Hitachi U–2000 double beam

spectrophotometer.

Fatty acid methyl esters compositions were described by means of a GC/

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MS (coupled with

an Agilent 5975 C MSD and

7890 A GC, operational with a capillary tube poised with DB–23, 60 m × 250 µm × 0.15 µm nominal)

using ethyl heptadecanoate as internal standard solution. In addition, both the 1H NMR and 13C NMR spectra of rice barn oil fatty acid methyl esters at room temperature were

quanti�ed with biodiesel (RBOB) and were veri�ed using deuterated chloroform (CDCl3) by means of

Perkin Elmer R–32 spectrometer. TGA/DTA investigation was

carried out by applying

a heating rate of about 10 K/min on a Perkin Elmer (TGS–2 model) thermal analyzer

with dynamic N2 environment with a rate of �ow is 20 ml/min. 2.6. In vitro microbial and antioxidant screening assay studies In vitro microbial via both antibacterial and

antifungal behavior of RBOB using dimethyl sulfoxide (DMSO) medium were examined for �ve strains of three Gram–positive bacterial species viz

Bacillus subtilis, Staphylococcus saphyphiticus, & Staphylococcus aureus (Gram–positive) along with two Gram–negative bacterial species

namely Escherichia coli and Pseudomonas aeruginosa

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(Gram–negative), through the nutrient namely Muller Hinton agar. And the antifungal behavior was tested using

Aspergillus niger, Enterobacter species and Candida albicans

like three fungal strains via in the medium of potato dextrose agar. This technique is based on modi�ed well diffusion practice [42,43]. All the analyses were made in three

replicates subsequent to

all the blank petri discs were moisturized with the same solvent consequently, the inhibition zone in

mm was measured as described earlier [44,45]. The

commercially available standard drugs ampicillin and nystatin were utilized as antibacterial and antifungal controls, respectively.

Furthermore, in vitro antioxidant activities for the RBOB have also been screened at 37 ?C by means of the scavenging model, using DPPH as a free radical and ascorbic acid

(AA) as the reference based on the Blois method. The procedure for determining free radical scavenging activity was described earlier [37,44,45] and the obtained outcomes were

matched with the reference material (AA). 3. Results and discussion The produced RBO is composed of 4.1–4.5, 21.3, 40.1 and 34.1 % of unsaponi�able matter, saturated fatty

acids, mono and polyunsaturated fatty acids, respectively. Here, the heterogeneous base catalyzed transesteri�cation procedure was carried out, in which RBOB is produced by

the reaction of methanolic solution of the extracted RBO with solid Ni(CH3COO)2 · 4H2O / H2(g) environment as catalyst using Ni(II)–Schiff base promoter. The obtained

biodiesel was further characterized via GC/MS spectra. The several physico– chemical and fuel characteristics of RBO and RBOB were assessed and matched to the petro–

diesel using ASTM standard and is given in Table 3. On account of the heterogeneous this kind of promoter assisted catalysis in the production of biodiesel, the density and

corrosion inhibition nature of the produced RBOB was comparably very little when evaluated with biodiesel based from others [46,47]. The presence of free and π–electrons on

the aromatic rings with hetero atoms (N & O) provide the corrosion inhibition e�ciency to the promoter. It is further supported by the molecular size and mode of binding

interactions in between of Ni(II) ion and Schiff base ligand. 3.1. Analytical, spectral characterization of ligand with its chelate promoter The synthesised ligand (Schiff base: HL)

from 4–methoxy

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salicylaldehyde and p– toluidine with its heterogeneous Ni(II)–Schiff base

chelate were analyzed by means of different spectral methods. The heterogeneous Ni(II) catalyst shows a characteristic color with good yield. The promoter is partially soluble in

MeOH, EtOH but very in DMSO, acetonitrile & acetone and not soluble in H2O. The observed micro elemental (C, H and N) analysis and conductivity studies (10–3 mol in DMSO

medium) con�rm the molar ratio, which is 1:2 (Ni(II): Schiff base ligand) and further con�rmed via FAB–MS. The promoter [Ni(II)–(L)2 (H2O)] is having distorted octahedral

environment with mononuclear [M+2] pattern [48]. The proposed structure and electronic spectra of heterogeneous base Ni(II) chelate catalyst are shown in Figure 4a and 4b,

respectively. The various analytical studies of HL with its promoter is summarized as follows: 3.2. Schiff base ligand (HL) Yield: 85 %; m.p.: 135 oC; Color: Yellowish Orange; Mol.

for.: [C15H15NO2]; Mol. wt.: 241.29; C, 74.04 (ca. 74.67),

H, 6. 16 (ca. 6. 27), N, 5.68 (ca.

5.81); ?M (10–3 M:DMSO) = 7.45 S cm2

mol–1; FT–IR data (KBr disk) cm–1: 3253 (br, ν(–

OH):phenolic), 1634 (s, ν(C=N): azomethine), 1243 (m, ν(C–O):phenolic stretching), 1182 (m, ν(C–O):methoxy stretching); Characteristic 1H NMR peaks are (d6–DMSO, TMS, ?

ppm): 9.22 (s,

1H, –OH), 8.11 (s, 1H, –CH=N–),

3.43 (s, 3H, –OCH3), 2.55 (s, 3H, –CH3), 6.68–8.05 (d, 1H, Ar–H); Characteristic 13C NMR peaks are (d6–DMSO, TMS, ? ppm): 168.3 (–HC=N–, azomethine carbon), 163.1 (–C–

O–CH3, aromatic carbon), 158.2 (=C–OH, phenolic), 103.7 – 153.1 (– CH–, aromatic ring Carbons), 141.8 (–C–CH3, aromatic carbon), 62.2 (–OCH3, methoxy), 42.7 (–C–CH3,

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methyl); FAB–MS: (m/z) value 242.10 (13 %)

[M+1]; UV–vis., (10–3 M:DMSO): ? max (cm–1)

with ? (dm3mol–1cm–1): 39391 (172) [INCT (π – π*)] and 28668 (136) [INCT (n– π*)]. 3.3. Heterogeneous base Ni(II)–Schiff base chelate promoter Yield: 73%; m.p.: 245 oC;

Color: Pale Green; Mol. for.: [NiC30H32N2O6]; Mol. wt.: 575.28; C, 61.49 (ca. 62.63): H, 5.56 (ca. 5.61): N, 4.58 (ca. 4.87): Ni, 9.82 (ca. 10.20); ?M (10–3 M:DMSO) = 16.18 S cm2

mol–1; FT–IR data (KBr disk) cm–1 : 3385, 846, 715 (br, ν(OH2) rocking and wagging of coordinated H2O molecule), 1608 (s, ν(C=N)azomethine), 1276 (m, ν(C–O)phenolic

stretching), 1183 (m, ν(C–O)methoxy stretching), 572 [w, ν(M–N)], 447 [w, ν(M–O)]; FAB–MS: (m/z) value 577.16 (15 %) [M+2];

UV–vis., (10–3 M in DMSO): ? max (cm–1)

with ? (dm3mol–1cm–1): 36014 (205) [LMCT (M ? L)], 27261 (172) , 17594 (114), 10552 (78) [3A2g(F) → 3T2g(F)]; Lunde’s factor (g) 2.281 (2.25 for hexaaquo Ni(II) complex),

Ligand �eld factors: 10552 [10 Dq (per cm)], 1055.2 [Dq (per cm)], 879.93 [B (per cm)], 1030 [Bo (per cm); for free Ni(II) ion], 0.85 (?), 14.57 (% of ?), 151.57 [LFSE (kJ per mol)],

1.67 (v2 / v1); Geometry: Distorted octahedral environment of 3A2g as ground state and D4h symmetry; ?eff (BM): 3.08. TGA and DTA analyses of heterogeneous Ni(II)–Schiff

base chelate promoter have been studied with a temperature of ambient to 900 oC and a representative thermogram obtained is depicted in Fig. 5(a). Initially, (Ist stage), the

thermogram showed a loss in weight of 6.19 % (cal. 6.26 %) at the temperature ranges between 40–185 ?C revealing that existence of coordinated water molecules in the

promoter [49]. In the second phase, the catalyst decomposes in the range 240 oC – 420 oC with a mass loss of 45.21 % (cal. 45.41 %) corresponding to removal of

salicylaldehyde ligand moiety. After 420 oC, losses of 41.36 % (cal. 41.60 %) correspond to p–toluidine moieties occurred. NiO is the end product (> 640 oC) with a mass loss of

12.86 % (cal. 12.98 %). The obtained NiO were further established by FTIR and pXRD pattern. The pXRD investigation of the HL and its heterogeneous promoter were recorded in

the (2 ?) 0–70o range and the representative diffractogram are given in Fig. 5(b). The promoter con�rms the uniform matrix with micro crystalline (26.41 nm) nature of different

crystallite size via XRD analysis [50]. The surface morphological photographs of Schiff base and its chelate via scanning electron microscopy (SEM) are shown in Fig. 5(c) and

(d) and this study reinforces that both are homogeneous phase materials [51]. 3.4. Regeneration of heterogeneous Ni(II)–Schiff base chelate catalyst: In industrial process, many

homogeneous or heterogeneous organometallic catalysts could be applied in chemical reaction to monitor the reaction speed and reutilized in several reaction cycles with or

without regeneration but

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in the case of solid heterogeneous catalysis, Ni(II)–

Schiff base chelate catalyst can be recovered from the FAMEs (biodiesel). So, the heterogeneous catalytic transesteri�cation reaction was performed at

optimum reaction conditions [Temp = 65 oC, Oil: MeOH = 1:6; Time = 2 h; Catalyst loading = 0.5 (Wt. %); Re�uxed with stirring speed = 300 rpm] to

yield

corresponding FAMEs (biodiesel). The completion of each reaction cycle was followed by the removal of heterogeneous base Ni(II) catalyst from the biodiesel products using

centrifugation by vacuum �ltration and �nally washed with water, MeOH, EtOH, etc. Finally, the products were dried at 100 oC in oven (1 h) and left overnight and the

heterogeneous Ni(II) catalyst was reused for a new reaction cycle. Using atomic absorption spectra (AAS) and gravimetric analysis, the Ni(II) ion content in heterogenous Ni(II)–

Schiff base chelate catalyst was also measured after each transesteri�cation reaction processes. Under the experimental conditions, initially the yield of FAMEs was 93.5 %,

however after successive reuse of heterogeneous Ni(II) catalyst, the yield of FAMEs decreased gradually (93.5 to 89.4 % for �rst four cycles), after �fth reaction cycle (Fig. 6), the

yield was reduced to 72 % which indicate that the heterogeneous Ni(II) catalyst is not suitable for further reaction cycle. Remarkably, Mazaheri et al [52] suggested that the

transesteri�cation of rice bran oil by heterogenous calcium oxide (CaO) nanocatalyst produced from calcined, hydrated as well as dehydrated shells of Chicoreus brunneus

(Adusta murex) on transesteri�cation (0.4 wt. %) at 1100 oC, 30:1 MeOH:RBO yielded 93 % of FAME by means of subsequent �ve transesteri�cation reactions under optimum

experimental process but, afterwards the sixth transesteri�cation, the yield of FAME was reduced to 85 %. In addition, Choi et al [53] studied the in situ lipase–catalysed

transesteri�cation of rice bran without the presence of any additional catalyst. It was observed that under the optimum conditions (40 oC, 1:6 molar ratio) the yield obtained is

around 83.4 % FAME after 12 days of the reaction but after 15 days the yield was reduced to 12 %. 3.5. Properties of RBOB as a fuel: 3.5.1. FAMEs analysis by GC/MS The

fractional composition of FAMEs was recognized by GC/MS spectrometry. In rice bran oil (RBO) there are seven essential FFAs namely palmitic, stearic, myristic, oleic, gadoleic,

linoleic and ?–linolenic oils, among them oleic (47.6 %), linoleic (34.0 %) and palmitic (19.1 %) oils are predominating in composition. The percentage yield of FAMEs product

after the heterogeneous base Ni(II)–Schiff base chelate transesteri�cation reaction was recognized by GC/MS analysis (after the separation of glycerol layer) and it was found to

be 93.5 %. From the observed GC/MS spectral peaks with respective retention time (RT). Table 3 shows that the presence of dissimilar FAMEs (saturated and unsaturated) in the

(RBOB). The total saturated, monounsaturated and polyunsaturated fatty acid methyl ester (FAME) contents found in rice bran oil based biodiesel (RBOB) are 23.17 ± 0.06 %,

40.95 ± 0.04 % and 29.38 ± 0.08 % respectively, out of which methyl palmitate (20.24 %), methyl oleate (40.20 %), methyl linoleate (28.13 %) predominate and are similar to the

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previously obtained results [53–56]. Moreover, the bio–sorption of Ni(II) metal ion in RBO during transesteri�cation process was examined by the ultimate analysis. Moreover, the

richness in the oleic oil (47.60 %) and its methyl oleate (40.20 %) content in the rice bran shows remarkable lubricity properties i.e., the rice bran oil and its biodiesel can act as

good lubricant base [57]. The obtained rice bran oil based biodiesel (RBOB) product of heterogeneous base Ni(II)–Schiff base chelate catalytic transesteri�cation process was

taking considerations into some speci�cations for the diesel engines. The different properties of the obtained RBO along with its biodiesel products are density, viscosity, �ash

point, cetane index, acid value, calori�c values, oxidative stability and were compared with diesel standard [56]. The biodiesel properties of rice bran oil are within the limits

prescribed ASTM D751–02, EN 14214 and ARE standards. Moreover, these values are merely comparable to some other reports [54–58]. Their low moisture content (0.0029 % w

/w) results in good yield of biodiesel. The higher density and viscosity of rice bran oil (922 kg/m3 and 28.14 mm2/s at 40 oC) are due to molecular composition, chemical

structure, long carbon chain with saturated and unsaturated double bonds of the RBO and those properties were reduced substantially after heterogeneous Ni(II)–Schiff base

chelate catalytic transesteri�cation process. It yields corresponding biodiesel (RBOB) with very low density and viscosity (876 kg/m3 and 4.46 mm2/s at 40 oC) and these values

are very comparable to the standard fuel speci�cations. The observed low density and viscosity values of RBOB are due to a drop off in the BSFC and 16 raise in the e�ciency of

the engines [37]. The examined �ash and �re points are very signi�cant among the ignition properties of a fuel when exposed to �ame as well as these properties may be

considered during storage. The observed values for �ash and �re points of RBO and RBOB were high and the values are 265 & 213 oC and 335 & 198 oC respectively, it clearly

indicates that the RBOB is a safer one on application, storage and transport purpose [59]. According to the fuel standard speci�cations, the percentage of water (H2O), sulfur (S)

ae well as carbon residue (C) of rice bran oil and its biodiesel are well agreed with the fuel standards limit but beyond the limits of the above parameters may affect the engine

performance, �lter blocking, corrosion by the injected components and severe environmental impacts (exhaust gases from combustion systems) [60]. The observed copper pipe

corrosion (3 h, 50 oC) values of rice barn oil and its biodiesel are very close to the fuels standard. Moreover, the fuel qualities were affected by air oxidation process, light (h?) and

temperature (?). The oxidative stability (at 110 oC) parameter is playing a vital role in fuel quality. The oxidative stability index values 3.28 h and 3.65 h for rice bran oil and its

biodiesel (RBOB), respectively are signi�cantly higher than the standard limit (3 h minimum) which implies that the RBO and RBOB showed better air stability owing to the

existence of a natural phytochemical / antioxidant namely; ?– oryzanol and also stored for extensive periods under elevated temperature and normal atmospheric conditions

[61]. The observed acid values of RBO and RBOB obey the fuel standards but the presence of long carbon chain length (C16–C20) of the RBO that shows a higher acid value (in

mg KOH / g: 0.42) than its biodiesel (0.37), because of the liberation of FFAs from the RBO during the heterogenous Ni(II)–Schiff base transesteri�cation process or oxidation of

RBO [62]. The calori�c or heating values of diesel, rice bran oil and its biodiesel (RBOB) are 44.23, 41.35 and 42.21 MJ/kg, respectively. It clearly demonstrates that the low value

for the RBOB is attributable to the existence of heteronuclear O2 within the molecular structure and also the obtained biodiesel has more than 85 % of its value of diesel fuel.

Moreover, the existence of oxygen in RBOB (11.25 % w/w) is higher than rice bran oil and diesel fuel standards which clearly show that, the biodiesel is assembled up of oxygen

molecules with polar bonds (strong bond) with signi�cant polarity that may reduce the evaporative tendency [63]. The observed cetane index values of rice bran oil and its RBOB

exceeds the fuel standards which indicated the biodiesel produces similar combustion properties in CI engines. The total and free glycerol content in both rice bran oil (RBO) and

its biodiesel (RBOB) are signi�cantly lower than the limits of fuel standards which clearly indicates an e�cient heterogeneous Ni(II)–Schiff base chelate catalytic

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1

transesteri�cation process (higher yield of biodiesel) and washing operations, under the experimental conditions [64]. 3.6. Spectral characterization of RBOB The electronic

absorption (UV–vis.,) spectra within the range of 200–500nm in DMSO medium for both the RBO and its RBOB were recorded at ambient temperature and the respective

spectrum obtained is shown in Fig.7. The presence of lipid soluble pigments in rice bran oil and its RBOB show a visible absorption peaks below 420–450 nm which was due to

the INCT (n –π*) band assignment however, in the ultra violet (UV) region it showed only one broad band centered at 320–335 nm (31250–29851 cm–1 with ????285?????dm3

mol– 1/cm??due to INCT (π–π*) assignment which is responsible to the presence of esters and glycerides present in RBO and RBOB. Rice bran oil based biodiesel (RBOB)

showed a characteristic strong absorption peaks at 1175, 1454, 1725 and 3450–3475 cm–1 ascribed to ??ester (C–O), ?methylester (?CH2?C??), νester (–C=O) and ?ole�n (=CH)

stretching frequency, respectively [65] which is not existing in the RBO which indicates the conversion into biodiesel has been completed using heterogeneous Ni(II)–Schiff base

chelate catalytic transesteri�cation process. The 1H NMR spectra of biodiesel (in d6–DMSO medium, TMS, ?) show some signi�cant signals in ppm: 0.71–0.78 for terminal –

CH3 protons, 1.15–1.21 for (– CH2–) protons, 1.87–1.96 for α protons to the –CO–of –CH2–CO– groups [66]. 13C NMR signals assignment of rice bran oil based biodiesel

(RBOB) also indicated the existence of methylene carbons at 25.7–29.2 ppm, ole�nic carbons at 126.5–130.4 ppm and carbonyl carbons at 172.4–176.5 ppm. Moreover, 13C

NMR spectra of the petro–derived diesel showed peaks at 20.1–38.5 ppm, correspond to non–benzanoid hydrocarbons. The thermogravimetric (TGA) analysis of RBO and RBOB

are depicted in Fig. 8. The thermogram clearly indicated that the RBOB show remarkable thermal stability than corresponding rice bran oil. The RBO and RBOB perform equal

from 220–250 oC, afterwards the RBO degrades quicker than its biodiesel. 3.7. In vitro microbial activities of RBOB with its oil (RBO) Modi�ed well diffusion agar method were

used to screen

in vitro microbial activities of rice bran oil (RBO) and its biodiesel

(RBOB) against some microorganisms in DMSO medium at 24, 48 and 72 h, respectively. The diameter of the zone of inhibition (in mm) values in favor of each microbe were

measured and correlated with ampicillin and nystatin, the standard drugs for standard for antibacterial and antifungal respectively and their biological activities diagram at 72 h is

shown in Figure 9. The obtained results clearly exhibited that the Gram–positive bacteria exhibited higher antimicrobial activities than Gram–negative bacteria [64] which is due

to the existence of outer thin layer of lipid plasma membrane as it possesses lipopolysaccharide and lipoprotein chain moieties in Gram– negative bacteria and this outer

membrane act as a barrier to antibodies. As a result, this lipid membrane is most likely a main site for antimicrobial components and they exhibit an improved membranic

piercing ability. Based on the Tweedy’s chelation coupled Overtone’s concept [67–69], the rice bran oil (RBO) showed higher activities than its biodiesel (RBOB). According to

Overton’s concept, the lipid membrane layers that surround the cell walls allow to traverse only lipid soluble materials because of liposolubility properties, which control the

biological activities. The selected microorganisms viz

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1

1

1

Bacillus subtilis, Staphylococcus saphyphiticus, Escherichia coli, Aspergillus niger and Enterobacter species

displayed enhanced in vitro biological activities as well as the observed inhibition zone value (in mm) follows the order as: Control (C) >

rice bran oil (RBOB) >rice bran oil based biodiesel

(RBOB). 3.8. In vitro DPPH scavenging

activities of rice bran oil with its biodiesel

(RBOB) The DPPH assay method was utilized towards the investigation for the antioxidant activities of rice bran oil (RBO) at room temperature and its biodiesel (RBOB) at various

(10–50 μM) concentrations. The % of RS activity value is given as the average of 3 replicates and also compared with the positive or reference ascorbic acid (AA) control. A

representative in vitro antioxidant activity is shown in Figure 10. Generally, the rice bran and its by– products acts as excellent antioxidants due to the presence of some natural

phytochemical components like ?–oryzanol, phytic acid, tocotrienols, tocopherol and vitamins (A & E), which induce to control the free radical (R•) production within the cells [70].

Moreover, the presence of phytic acid in rice bran may act to downfall iron–driven steps in carcinogenesis and reduce the colon tumor formation [71,72]. In chemical analytical

techniques, the DPPH radical (R•) is utilized for �nding the percentage of free radical scavenging activity (% RS). The results clearly indicated that rice bran oil has higher

activities but lower than ascorbic acid (AA) and the % of RS values

follow the order: Control (AA) > rice bran oil

(RBO) > rice bran based biodiesel (RBOB). From the above results, it has been concluded that the presence of predominant fraction of ?–oryzanol (natural phytochemical) in rice

bran oil possesses excellent antioxidant activities and also show that rice bran products could be employed as notable agents in chemotherapy �elds for curing pathological

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2

20

1

diseases due to oxidative stress and preventing ageing of human life progress. 4. Conclusions It has been concluded that the heterogeneous base Ni(II)–Schiff base chelate

promoter catalysis via two step catalytic transesteri�cation of RBO leads to the production of low density as well as low viscous biodiesel by the extraction path and is cost–

effective. The analyzed petro–derived fuel properties of RBOB and their fatty oil pro�le are analogous to those of the other conventional biodiesels. Furthermore, we have

recommended the extracted biodiesel to be utilized the same as a power source for both the medium and heavy–duty vehicles since they emit low CO and HCs when compared

to petro–derived fuels. In addition, the outcomes con�rm that the RBO is a potential feedstock used for e�cient and cost– effective biodiesel production and show potential bio–

activities viz in vitro microbial activities. The

additions of antioxidants are very effective for the destruction of oxidative stability, but rice bran oil based biodiesel extraction, using Ni(II)–

Schiff base chelate assisted catalyzed hydrotreatment process, there is no necessitation to add any antioxidants.

Moreover, this reaction path yields higher FAMEs than single/direct stage transesteri�cation path and this process with quality of the product yielded are depending on the

presence of the existing fatty oil pro�le in the RBO. Figure captions: Scheme 1 General route

for the synthesis of Ni(II) – Schiff base chelate

promoter Fig. 1. General schematic process for the conversion of raw material into biodiesel in the presence of heterogeneous base catalyst. Fig. 2 (a) Proposed general

schematic diagram of

extraction of rice bran oil (RBO) from rice bran

(RB); (b) Proposed general schematic diagram of

heterogeneous base catalyzed transesteri�cation of rice bran oil

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2

18

2

2

Fig. 3 (a) General transesteri�cation process; (b) Mechanism of heterogeneous base catalyst transesteri�cation process

in the presence of Ni(II)–Schiff base chelate promoter

Fig. 4 (a) Proposed structure of heterogeneous catalyst;

(b) Electronic spectra of Schiff base and its heterogenous base Ni(II) chelate

catalyst

in DMSO (10–3 M) medium at room temperature.

Fig. 5 (a) Thermogravimetric pictogram of heterogeneous Ni(II)–Schiff base catalyst; (b) Powder X–ray diffraction patterns;

(c) SEM photographs of Schiff base; (d) Ni(II)– Schiff base chelate catalyst . Fig

6. Fatty acid methyl ester (FAME) conversion yield using heterogeneous

Ni(II)–Schiff base chelate catalyst regeneration in

a reaction cycle analysis. Fig. 7. UV–vis., spectra of

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6

1

2

15

4

rice bran oil and its biodiesel (RBOB) in

DMSO medium Fig. 8. Thermogravimetric (TGA)

analysis of rice bran oil and its biodiesel

(RBOB) Fig. 9.

In vitro biological activities of rice bran oil (RBO) and its biodiesel

(RBOB)

at 72 h by well diffusion agar method.

Fig. 10.

In vitro antioxidant activities of rice bran oil (RBO)

and its biodiesel (RBOB)

with control by DPPH free radical scavenging assay method at different concentrations (10–50 μM).

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6

Table captions: Table 1:

Transesteri�cation of rice bran oil in the presence of

various types of catalysts used for the production of biodiesel under dissimilar reaction conditions Table 2: Composition of

free fatty acids (FFAs) content in rice bran oil

(ROB) Table 3 Weight percentage composition of

fatty acid methyl esters (FAMEs) in rice bran oil based biodiesel

(RBOB) 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15

16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 1 2 3 4 5 6 7 8 9

10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23

24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16

17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10

11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24

25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17

18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 1 1 2 5 6 7

8 10 11 12 13 14 15 17 18 19 20 21 22

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