Biodiesel production from Calophyllum inophyllum oil a potential non-edible feedstock: An overview

Accepted Manuscript Biodiesel production from Calophyllum inophyllum oil a potential non-edible feedstock: An overview

A. Arumugam, V. Ponnusami PII:

S0960-1481(18)30856-5

DOI:

10.1016/j.renene.2018.07.059

Reference:

RENE 10333

To appear in:

Renewable Energy

Received Date:

16 March 2018

Accepted Date:

14 July 2018

Please cite this article as: A. Arumugam, V. Ponnusami, Biodiesel production from Calophyllum inophyllum oil a potential non-edible feedstock: An overview, Renewable Energy (2018), doi: 10.1016/j.renene.2018.07.059

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ACCEPTED MANUSCRIPT Title Biodiesel production from Calophyllum inophyllum oil a potential nonedible feedstock: An overview Authors’ names and affiliations: Dr. A. Arumugam, School of Chemical & Biotechnology, SASTRA University, Thirumalaisamudram, Thanjavur, India. 613 401 Phone: +91 4362 264101 Fax: +91 4362 264120 Email: [email protected]. Dr. V. Ponnusami School of Chemical & Biotechnology, SASTRA University, Thirumalaisamudram, Thanjavur, India. 613 401 Phone: +91 4362 264101 Fax: +91 4362 264120 Email: [email protected].

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1

Biodiesel production from Calophyllum inophyllum oil a potential

2

non-edible feedstock: An overview

3

A. Arumugam*, V. Ponnusami

4

School of Chemical & Biotechnology, SASTRA University, Thirumalaisamudram, Thanjavur, India.

5

ABSTRACT

6

Utilizing renewable feedstock for the production of alternate fuels is a challenging task. The

7

need for finding a new fuel is gaining importance owing to rapid depletion of fossil-fuel

8

resources and fluctuating crude oil price. Alternate fuel must also be environmental friendly,

9

cheap, technically acceptable and abundant. Biodiesel, eco-friendly alternative liquid fuel, are

10

fatty acid alkyl esters produced by chemical or lipase-catalyzed transesterification of fats or oils.

11

It has both economic and environmental benefits in addition to its renewable origin. Feedstocks

12

such as animal fats and vegetable oils play a vital role in biodiesel production. The demand for

13

biodiesel production from non-comestible oil is growing steadily as there are restrictions on the

14

conversion of edible oils into fuels. Hence, researchers are looking for promising newer sources

15

of non-comestible oil which can sustain biodiesel production and use. These attributes have

16

contributed to growing interest on biodiesel production from Calophyllum inophyllum oil. This

17

study focuses on a promising newer source of non-comestible oil which can sustain biodiesel

18

growth. Various technological options available for the conversion of C. inophyllum oil into

19

biodiesel, their strengths and weaknesses are highlighted. Also, engine performance of the C.

20

inophyllym biodiesel blends is also reviewed.

*

Corresponding author: Dr. A. Arumugam, SASTRA University. Email: [email protected]

1

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Keywords: Calophyllum inophyllum oil, Biodiesel, Transesterification methods, Scientometric

22

analysis.

23

1 INTRODUCTION

24

Focus on alternative fuels is growing in the recent past owing to ever increasing demand for fuels

25

and depleting fossil fuel resources. Furthermore, use of fossil fuels has given rise to several

26

environmental concerns such as global climate change, air quality and volatility in the fossil fuel.

27

For sustainable development, use of economically viable alternative fuels is necessary. Thus,

28

there is a growing interest in alternative fuels such as biodiesel [1].

29

Biodiesel, a promising alternative fuel for transport and mechanized agriculture sectors,

30

is a renewable, green and nontoxic fuel. Biodiesel is a long chain fatty acid methyl ester (FAME)

31

obtained by either transesterification of triglycerides (TAG) or esterification of free fatty acids

32

(FFAs) [2, 3]. Particularly, use of non- comestible vegetable oils as biodiesel feedstock has

33

gained interest of researchers in the recent past [4].

34

Some of the non - comestible feedstocks used for biodiesel production include: jatropha

35

(Jatropha

curcas L.) [5], Karanja (Pongamia pinnata) [6], Mahua (Madhuca indica) [7] and

36

Castor (Ricinus communis L.) etc. [8]. Among the non-comestible charging stocks, C.

37

inophyllum and Jatropha curcas seeds posses’ relatively high oil content (Table 1).

38

Aza et al., 2005 [9] inspected the fatty acid composition of vegetable oils from 75 plant

39

species. Out of this 75, 26 plant species were identified as a potential feedstock for biodiesel

40

production. This includes C.inophyllum. As the properties of C. inophyllum oil is closely

41

matching with that of the diesel fuel, yield of biodiesel is usually very high. Thus, during the past 2

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42

few years, biodiesel production from C. inophyllum oil has gained the attention of the

43

researchers. A brief scientometric analysis of biodiesel production from C. inophyllum oil

44

discussed below, clearly reveals this.

45

Table 1

46

Non-edible sources and oil content for biodiesel production. Non-edible feedstock

Oil content (wt %)

Calophyllum Inophyllum L.

65-75

Jatropha curcas L.

40-60

Ricinus communis (castor)

45-50

Sapindus Mukorossi Gaertp (Soapnut)

45-50

Hevea brasiliensis (Rubber)

40-50

Madhuca indica (Mahua)

35-50

Pongamia pinnata (Karanja)

30-50

Azadirachta indica (Neem)

25-45

Ceiba pentandra

24-40

47

SCOPUS database search with keywords “Calophyllum inophyllum and biodiesel” fetched

48

110 results (between 2005 and 2017) on 27-09-2017. Research articles, conference proceedings,

49

reviews, and books chapter shared 88%, 12%, 5% and 2% of the publication respectively. There

50

has been a steady increase in number of publications over the period, (Figure. 1) particularly

51

over the period 2011 – 2017 [10]. These publications were reported from 11 different countries

52

(Figure. 1). A major contribution was from India (38 %) followed by Malaysia (23%), Indonesia 3

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(12%) and Australia (8%). Availability of C. inophyllum trees in these countries favor the choice

54

of

the

oil

as

a

potential

charging

4

stock

for

biodiesel

production

[11].

Paper number (%)

30

The distribution of the papers by the publication year

25 20 15 10 5

2005 2006 2007 2008 2009 2010 2011 2012 2013 2014 2015 2016 2017

0

The most publishing countries (%)

14 4

38

8 12

55 56 57

23

India Malaysia Indonesia Australia Nigeria Others

Geographic distribution Abundance

Figure. 1. Geographic Distribution of Calophyllum inophyllum Linn, Countries that published about Calophyllum inophyllum as a source of biodiesel feedstock during the period of 2005–2018. 5

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In this review, we discuss the nature of the tree, its origin, seed oil content, oil composition,

59

and various methods of transesterification reported in the recent literature.

60

2 Calophyllum inophyllum

61

The systematic position of C.inophyllum Linn is given in Table 2. C. inophyllum is a

62

genus of evergreen tree commonly found along the coastal region of eastern Africa,

63

Madagascar, Papua New Guinea, India, Northern Australia, and tropical America along the

64

east and west coast of Peninsula, the islands of the Pacific Ocean, Melanesia and Polynesia,

65

and tropics of Asia, mainly in the Indo-Malaysian region and Ceylon [12]. In India, they are

66

found along the shorelines of Maharashtra, Karnataka, Kerala, Tamil Nadu, Andhra Pradesh,

67

Orissa, Andaman and Arunachal Pradesh [13]. There are about seven species of Calophyllum

68

in India. Among them, while some of the species are ornamental the others are used for

69

timber. It is said that the Polynesian settlers who migrated from South Pacific regions brought

70

the species from north to Hawaii [14].

71

Figure 1 shows the geographic distribution and abundance of C.inophyllum [15].

72

The height of matured C.inophyllum tree is typically around 18 m. It has wide spreading

73

branches and dense leaves at top (Figure. 2). When cut and wounded, its trunk exposes a

74

reddish-brown hardwood which always exudes pellucid resins. It is generally seen without

75

buttresses and it has twisted or leaning bole with a maximum of 150 cm diameter. The outer

76

bark is seen shallowly and vertically fissured with pale grey and fawn in color [16]. Pink to

77

red laminated fibrous, soft and thick inner bark which turns brownish when exposed is

78

present. Twigs are 4-angled and rounded and terminal bud plump with 4–9 mm long. The

79

leaves of C.inophyllum are usually 3-8 inches in length and have a blunt tip. They are large

80

shiny and stiff leaves. The leaves are oppositely arranged and have parallel venation from a

81

prominently raised yellow-green midrib to the leaf margin. The flowers are white and waxy 6

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and possess typically 4-8 petals. They also have stamens of golden yellow color, which have

83

a pleasant odor and small in size (about 1 inch wide). The flowers are found hanging from a

84

long stalk because of pink pistils growing in clusters of a dozen. The dark green background

85

given by the leaves make the small flowers sparkle like stars as it begins to open early

86

morning (at around 3 – 4 am) and are wide open at sunrise [17]. Various pollinating insects

87

get attracted towards them because of its delightful fragrance. The fruits typically 2 inches

88

long. It commonly found in the regions where the average annual rainfall is in the range of

89

1000-5000 and it is also found at ground as well as mountains usually less than 200 m

90

height. It is indeed a coastal species that is often seen in sandy beaches and rarely seen along

91

river margins further inland. They can withstand strong winds, salt spray, sea water, back

92

water tables and strong tidal waves as they grow along the coasts whereas they cannot

93

tolerate frost and fire [18].

94

Table 2

95

Systematic position of Calophyllum inophyllum Linn

Kingdom

Plantae (Plants)

Subkingdom

Tracheobionta (Vascular plants)

Superdivision

Spermatophyta (Seed plants)

Division

Magnoliophyta (Flowering plants)

Class

Magnoliopsida (Dicotyledons)

Subclass

Dilleniidae

Order

Theales

Family

Clusiaceae (Mangosteen family)

Genus

Calophyllum L

Species

Calophyllum inophyllum L (Alexandrian laurel) 7

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C. inophyllum oil is composed of free fatty acids, glycerides, sterols, terpenoids,

98

steroids, calophyllolids, inophyllolids and calophyllic acid. The oil possesses properties

99

nearly equivalent to that of petroleum diesel and meets various engine combustion parameters

100

such as heat release, ignition delay, peak pressure and time of occurrence of peak pressure

101

[18]. The Physical and chemical properties of C. inophyllum oil is reported in Table 3. The

102

fatty acid composition of C. inophyllum oil (%) is given in Table 4. The fatty acid

103

composition of the C. inophyllum oil revealed the presence of palmitic, steric, oleic, linoleic

104

acids as the major constituent [20].

105

3 Calophyllum inophyllum Biodiesel

106 107

The idea of using biodiesel is not a new one. Literature reports indicate that Rudolph

108

Diesel, in 1911, was the first one to use vegetable oil to run the diesel engine [21]. If the

109

properties closely match with that of the petroleum crude derived diesel for a raw vegetable

110

oil, then that vegetable oil can be used without blending in diesel engine [22]. However,

111

engine failure due to high fuel viscosity, more carbon deposits, injector coking, oil ring

112

sticking etc. will occur due to the usage of raw vegetable oils in engines. Some of the issues

113

highlighted above can be solved by reducing the viscosity of vegetable oils and this can be

114

achieved by following four techniques: dilution [23], micro-emulsification [24], pyrolysis

115

[25], and transesterification [26]. Transesterification is considered to be the best among them.

116

Various transesterification methods are in practice for the conversion of vegetable oil into

117

biodiesel. In the following section, we discuss those methods, their merits, and demerits [27].

118 119 8

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Table. 3

123

Physical and chemical properties of Calophyllum inophyllum oil Aspect 16°C-20 °C

liquid and crystallization of resins

Aspect 25°C

Liquid

Odor

slightly & characteristic

Colour

Green

Specific gravity 25°C

0.91 – 0.96 Kg/l

Refractive index 20°C 1.463 – 1.495 Solubility in water

Immiscible

Solubility in oils

Miscible

Solubility in ethanol

partly miscible (resins)

kinematic viscosity

39 cSt

flash point

210 °C

fire point

118 °C

cloud point

-2.5 ± 1 °C

Pour point

-8±1 °C

Acid value

6- 75 mg of KOH/ gm of oil

Free fatty acid (%)

4 - 29.66

Saponification value

230

iodine value

97

Calorific value

38743- 41.397 MJ/kg

Oil content (%)

75

pH at 26°C

4.60 ± 5.0

Carbon residue (wt%)

0.85 ± 0.05

Ash (wt.%)

0.04 ± 0.05

124

9

125

Table 4

126

Fatty acid composition of C. inophyllum oil (%)

Fatty acid

Molecular formula

Chemical structure

Systematic name

Palmitic acid

C16:0

CH3(CH2)14COOH

Hexadecanoic

12.0- 20.0

Stearic acid

C18:0

CH3(CH2)16COOH

Octadecanoic

6.1- 19.2

Oleic acid

C18:1

CH3(CH2)7CH=CH(CH2)7COOH

cis-9- Octadecenoic

28.2- 42.0

Linoleic acid

C18:2

CH3(CH2)4CH=CHCH2CH=CH(CH2)7 COOH

cis-9-cis-12-Octadecadienoic

25.0- 38.0

Linolenic acid

C18:3

CH3CH2CH=CHCH2 CH=CHCH2CH=CH(CH2)7COOH

9,12,15-Octadecatrienoic acid

0.2- 4.0

10

wt %

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(a) Calophyllum inophyllum Linn tree.

(b) Leaf

(c) Tree with fruits

(d) Fruit changes color when it ripens

128

Figure 2. Calophyllum inophyllum Linn

129 11

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130

3.1 Transesterification

131

Transesterification is the method that is used generally to obtain biodiesel from vegetable

132

oil. Different transesterification methods commonly used for conversion of vegetable oil into

133

biodiesel are shown in the Figure. 3. As stated earlier, transesterification is the most effective

134

method for biodiesel production. Transesterification is the reaction between glycerides with

135

short-chain alcohols and is comprised of three series reaction steps, wherein triglycerides are

136

broken down to diglycerides, monoglycerides and finally to glycerol sequentially [28, 29]. In

137

each step, one mole of the ester is produced per mole of alcohol consumed. During this process,

138

the organic group (R”) of the ester is interchanged with that of an alcohol (R’) (Figure 4).

Biodiesel from Calophyllum inophyllum oil

Transesterification

Non-catalytic method

Supercritical methanol

Dilution

Pyrolysis

Microemulsion

Catalytic method

Homogenous catalyst

Alkaline Catalysts

Heterogeneous catalyst

Acid catalysts

Whole cell

139 12

Lipase catalyzed

Alkali metal oxides

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140

Figure 3. Methods for biodiesel production from Calophyllum inophyllum oil

141

Alcohol to oil molar ratio, Alcohol type, free fatty acid content, water content, temperature,

142

reaction time and catalyst type are the various parameters that influence the reaction performance

143

[30, 31]. Since alcohol plays a major role in the conversion of triglycerides, alcoholysis is the

144

other name commonly used for transesterification. Although it contains a series of reversible

145

reactions, it is low cost and simple. Triglycerides in oil turn gradually into glycerol from di and

146

monoglycerides upon the action of oil in the presence of a catalyst and during this process

147

alcohol is formed [32]. This glycerol has a great demand in cosmetic industries. Alcohols like

148

methanol, ethanol, propanol, butanol and amyl alcohol are used in this procedure [33].

149

Transesterification processes are broadly classified into two types: Non-catalytic and

150

Catalytic method. Among them, catalytic method is further classified into heterogeneous and

151

homogeneous methods. Alkaline catalysts such as NaOH and acid catalysts such as H2SO4 are

152

examples of homogeneous catalysts, and enzymes, especially lipases are among heterogeneous

153

catalysts.

154 155 156 157

O || CH2 - O - C – R1

O ||  / H  / Enzyme CH - O - C – R11 + 3 CH3OH OH    CH - OH O || CH2 - O - C – R111 Triglyceride

158 159

CH3 – OOR1

CH2 - OH

Methanol

+

CH2 - OH

CH3 – OOR111

Glycerol

Methyl ester

O H-O–C -R Fatty acid

CH3 –OOR11

O +

CH3OH Methanol





/ H / Enzyme OH   

13

Figure 4. Biodiesel production reaction scheme.

H3C – O – C ˗ R methyl esters

+ H2O Water

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160 161

162

3.1.1 Catalytic methods

163

3.1.1.1 Homogeneous catalysts

164

Acid catalyst transesterification and alkaline catalyst transesterification are two important

165

conventionally used transesterification methods for the biodiesel production. In Acid catalyst

166

transesterification usually sulphuric acid, hydrochloric acid, and sulfonic acids are the very

167

commonly used catalysts for acid transesterification. The catalyst is not directly applied to react

168

on oil, instead, the acid is dissolved in the alcohol and the mixture is vigorously blended with a

169

stirrer. This acid-alcohol mixture is then pumped into the biodiesel reactor that contains crude

170

oil. The acid donates protons to the carbonyl group and forms a strong electrophile that catalyzes

171

the reaction. A tetrahedral intermediate is produced by nucleophilic attack on alcohol molecule.

172

The carboxylic acid formation is facilitated by the existence of water in the reaction. Formation

173

of carboxylic acid leads to a reduction in yield of FAAE (Fatty acid alkyl ester) [29]. Alkaline

174

catalyst transesterification, also known as base catalyzed transesterification, is the most

175

commonly used process for the production of biodiesel. Potassium hydroxide (KOH), Sodium

176

hydroxide (NaOH) and solution of sodium methoxide (NaOCH3) and potassium methoxide

177

(KOCH3) are some of the strongest bases used for treating oil. Active catalysts, such as alkaline

178

metal alkaloids are capable of catalyzing the reaction at the atmospheric pressure and low

179

temperature, which leads to high conversion rate. Generally, alkaline transesterification of

180

vegetable oil seems to be faster and less corrosive than acid transesterification method [32]

181

(Figure 5).

14

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182

Vasanthakumar et al, 2011[34] developed two-step pretreatment for the conversion of C.

183

inophyllum oil to biodiesel. Acid-catalyzed esterification catalyzed by b-zeolite modified with

184

phosphoric acid and KOH catalyzed transesterification was used. Response surface methodology

185

was used to optimize the process parameter for the acid esterification. Biodiesel produced by this

186

process was tested for its fuel properties.

187

Sathyaselvabala et al, 2012 utilized sulfated zirconia an efficient catalyst for esterification

188

of pinnai oil free fatty acid. A reduction in free fatty acid from 44 to 2 mg KOH/g of oil at

189

optimized process parameter temperature 63.2 °C, methanol/oil ratio 12, and catalyst amount

190

0.5% was obtained [35]. The produced biodiesel was analyzed and compared to ASTM standard

191

and the properties were within the limits.

192

Ong et al, 2014 [36] synthesized biodiesel from crude C. inophyllum oil in a four stage

193

(degumming, esterification, neutralization and base catalyzed transesterification) process. They

194

obtained a yield of 98.82 % under optimum methanol to oil molar ratio (value), which was

195

catalyzed by 1 wt% NaOH at 50 °C for 2 h. The diesel fuel showed good performance in engine

196

test of 10 % blend with diesel fuel and compared with ASTM biodiesel standard.

197

Chavan et al, 2013 [37] focused on the collection of seeds and oil extraction, and then

198

proceeded for biodiesel production. A molar ratio of 8:1, 1.2 wt% KOH, temperature 65°C, and

199

reaction time 1.5 h was used to produce biodiesel and the parameters tested as per ASTM 6751

200

standards. The physicochemical parameters showed that C. inophyllum works well as a charging

201

stock for biodiesel production.

15

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202

Venkanna et al, 2009 developed a three-stage transesterification process that consist of acid

203

esterification followed by transesterification and post-treatment. The effect of catalyst

204

concentration, alcohol to oil molar ratio, temperature and reaction time were optimized for

205

biodiesel production [38].

206

16

Esterification

207 208

Catalyst reuse

Transesterification

Alcohol

Evaporator

209 210 Hydrocyclone

211 212

Oil

Fatty acid alkyl esters

213 H2O

214 215 216

Alcohol

Washing

Acid/ Alkali/ Biocatalyst/ Heterogeneous catalyst

Acid/ Base

Crude Glycerol

217

Drying

218 219 220 221 222 223 224

Aci d

Pure glycerol

Acidification

Biodiesel

Figure. 5. Process flow diagram of conventional Acid/ Alkali/ Biocatalyst/ Heterogeneous catalyst in transesterification process for biodiesel production. 17

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225

3.1.1.2 Heterogeneous catalysts

226

Transesterification reactions using the heterogeneous catalysts the catalyst can be

227

recovered and reused. The separation and purification are simplified because the production of

228

the waste stream is reduced. Non-corrosive catalysts are used. Heterogeneous catalyst can be

229

either by base or acid [39]. Various types of basic solids have been used and these can be

230

categorized into ion-exchanged zeolites [40], alkaline earth oxides and hydroxides [41],

231

supported metal salts or ions and heterogenized organic bases [42]. Alkaline earth metal oxides

232

are better and stronger bases as compared to their hydroxides. Among them calcium oxide is

233

recognized as a most efficient catalyst due to its high trans-esterification activity, availability,

234

low cost and less toxicity [43, 44] (Figure 5 ).

235

Muthukumaran et al. 2015 produced biodiesel from C. inophyllum and tested in a diesel

236

engine. To bring down the production cost raw fly ash, a waste material was exploited as a cheap

237

catalyst, for the cracking process instead of the commonly used zeolite catalyst. Biodiesel

238

produced from C. inophyllum was blended with petroleum diesel with different proportion was

239

tested in a diesel engine. The brake thermal efficiency (BTE) of the engine for 25% biodiesel

240

(25% cracked C. inophyllum oil and 75% diesel) was closer to diesel but decreased for higher

241

blends while NOX emission decreased for all blends. It was also found that hydrocarbon; carbon

242

monoxide and smoke emissions were comparable for biodiesel blend with diesel [45].

243

Dawodu et al, 2014 [46] used the solid acid catalyst derived from cellulose a renewable

244

biomass and obtained about 99% conversion of methyl ester at 180°C in 4 h with 15:1 methanol

245

to oil molar ratio and 5 wt% catalyst. The high catalytic stability observed in the study showed

246

the solid acid catalysis can be a suitable alternative. Even after 5 cycles of reuse the catalyst

247

retained around 82.5 % of the original activity. 18

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248

Ayodele et al, 2014 used pyrolyzed microcrystalline cellulose as a precursor for

249

polycyclic aromatic carbon which is capable of binding SO3H groups when subjected to

250

sulfonation. The biodiesel yield of 99% at an optimum condition of 15:1 methanol to oil molar

251

ratio, 5 wt% catalyst loading, a reaction temperature of 180°C and a reaction time of 4 h was

252

obtained [47].

253

Rismawati Rasyid et al, 2015 converting C. inophyllum kernel oil into a liquid fuel by

254

making use of the hydro-cracking process catalyzed by non-sulfide CoMo catalysts under

255

controlled temperature up to 350°C and a pressure up to 30 bar. The catalysts (CoMo) used in

256

the study were produced by 10 wt. % loading of molybdenum and cobalt solutions over different

257

support materials such as. γ-Al2O3, SiO2, and γ -Al2O3-SiO2 by impregnating. It is determined

258

from the study that non-sulfide catalysts (CoMo) have performed efficiently in converting C.

259

inophyllum kernel oils into liquid fuels such as gas oil, kerosene, and gasoline via the process of

260

hydro-cracking. The CoMo/ γ -Al2O3 catalyst generated higher conversion than CoMo/SiO2 and

261

CoMo/ γ-Al2O3-SiO2. The fuel produce was 17.31% kerosene, 25.63% gasoline and 38.59% gas

262

oil. The liquid fuels derived in this study do not comprise of a sulfur compound and thus can be

263

classified as environment-friendly fuels [48].

264

Marso et al 2017, Classic transesterification of feedstock with high free fatty acid

265

content are usually done through acid or base catalyzed reactions. Base-catalyzed reactions have

266

become unfavorable over the years due to the formation of cationic salts of the fatty acid (cation

267

from the base) in a process called saponification, which decreases of the overall yield of the

268

biodiesel eventually obtained. Acid-catalyzed pre-esterification of fatty acids may decrease the

269

FFA content to insignificant levels but are still plagued by the subsequent separation process and

270

the possibility of oxidation of the raw materials. The study illustrates potential application of 19

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271

trivalent metal ion (Al3+, Fe3+) doped graphene oxide composites as a solid-state acid catalyst in

272

the esterification of stearic acid, as well as in the reduction of FFA concentration in C.

273

inophyllum oil. The composite was characterized by FTIR and AAS spectroscopy, X-ray

274

diffraction and SEM-EDX methods, while the surface acidity was measured by the Hammett

275

indicator method. It was found that there was a 92.72% conversion of stearic acid, as well as a

276

95.37% reduction in the FFA levels in the C. inophyllum oil. The optimal reaction condition was

277

determined to be at 10:1 molar ratio of methanol to FFA with 8% of the catalytic dose at 65oC

278

for 3 hours. The catalyst was re-used for more than four cycles of FFA conversion reactions

279

without any adverse waste formation. The activation energy for the catalyzed esterification

280

reaction was substantially lower when (23.67 kJ mol/1) than analogous reactions which were

281

previously published [58].

282

3.1.2 Biological methods

283

3.1.2.1 Enzymatic transesterification

284

In comparison with the chemical method, biodiesel production catalyzed by the enzyme

285

is more preferred due to its advantages like mild operating conditions, toleration of moisture

286

content in oil, less consumption of energy, non-toxicity and environmental friendliness. Enzymes

287

including lipase are usually expensive. High cost and low stability reduce its applicability in

288

commercial scale. To overcome this problem, immobilized lipase was used for the biodiesel

289

production [49]. The recovery, recycling, and reusability of the enzymes are enhanced by

290

immobilization. Immobilization of enzymes on inert supports initiates the continuous operation

291

and reduces the biodiesel production cost-effectively [50] (Figure 5). Arumugam et al, 2013

292

used immobilized lipase for the production of biodiesel. The immobilization matrix was

293

synthesized from a low cast silica precursor.A biodiesel yield of 96.4 % was obtained under 20

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294

optimized conditions The reusability studies of immobilized lipase on SBA-15 was studied [51].

295

Arumugam et al, 2013 used amine-functionalized mesoporous silica as the immobilization

296

support for lipase enzyme for the transesterification of crude C. inophyllum oil. The percentage

297

yield of fatty acid methyl ester 94 % was obtained under optimized conditions: For processing

298

2 g of C. inophyllum oil: lipase immobilized on amine-functionalized SBA-15- 125 mg,

299

methanol/oil molar ratio- 6:1, water—15 % v/v and temperature - 35 °C. The reusability study

300

had shown the long-term stability of lipase activity for methanolysis (10 cycles) [52].

301

3.1.2.2 Whole-cell Biocatalysts

302

Whole cells capable of producing intracellular lipase can be immobilized and used for

303

biodiesel production. Cost of using the whole cell is much lower compared with to that of

304

immobilized enzymes [53]. A. Arumugam et al, 2014 produced biodiesel by using R. oryzae

305

cells immobilized on reticulated polyurethane foam. Under optimized conditions, 92% FAME

306

yield was achieved during batch transesterification [54].

307

3.2 Supercritical methanolysis

308

An alternative catalytic-free called supercritical methanolysis can be used for vegetable

309

oil transesterification (Figure 6). Alcohol under supercritical conditions i.e at temperature and

310

pressure above critical point is used in this method. The quality of fuel and concerns regarding

311

the environment are maintained. Washing steps and alkaline water treatments for catalyst

312

removal from the product are not required in this method [55]. Using supercritical conditions for

313

production of biodiesel requires higher alcohol to oil ratio, increased pressures and temperatures

314

are used in the reaction to obtain desired conversions. Usage of higher energy for the process

315

results in increased costs. Sometimes, the reaction conversion gets reduced due to the reaction of

316

glycerol with other components and due to the degradation of FFA esters [56]. 21

ACCEPTED MANUSCRIPT

317

Neha Lamba et al, 2017 Non-catalyzed synthesis of biodiesel (fatty acid methyl esters)

318

from C. inophyllum, an inedible crop using different supercritical fluids, such as methanol

319

(MeOH), methyl tert-butyl ether (MTBE), methyl acetate (MeOAc) and dimethyl carbonate

320

(DMC). The operation conditions were 523-673K at 30MPa with reaction times ranging from 3

321

min to 3 h at a molar ratio of 40:1. Within 30 mins, atleast 80% conversion was achieved with

322

MeOH and DMC at 623K, 60% conversion with MeOAc and 70% conversion with MTBE, each

323

operated at 673K. Rate constants were derived by using pseudo-first-order kinetics and the

324

activation energy was found to be highest for EMeOH, followed by EDMC, EMeOAc, and

325

EMTBE [37].

326

4 Physico-chemical properties of Calophyllum inophyllum biodiesel

327 328

The following thermo-physical properties are estimated by standard ASTM methods and

329

tabulated in Table 5.

330

Flash point is the minimum temperature that is required by the fuel to get ignited when exposed

331

to an ignition source is referred to as its flash point temperature. Flash point generally has a

332

reverse effect on the fuel’s volatility. Lower the flash point higher the risk of fire hazard. The

333

flash point has a significant effect on deciding the fire hazard [59]. The flash point for the

334

biodiesel produced by C. inophyllum was reported to be 136 - 179ºC which is much higher than

335

conventional diesel fuel. The higher flash point of the C. inophyllum biodiesel indicates that the

336

flammability hazard is much less than that of the diesel [60, 61].

22

337 338

Methanol for reuse

Glycerin

339 340

Flash

341

Column

342

Feed preparation Degumming

343

Vacuum Flash Column

Supercritical reactor

Vacuum distillation

344 345 346

Feed stock

347 348 Decanter

349 350 351 352

Figure 6. Biodiesel production processes with supercritical methanol.

23

Biodiesel Unconverted oil

353

Table. 5

354

Fuel quality of biodiesel from Calophyllum inophyllum oil

Properties of biodiesel

C.inophyllum

Jatropha

Density (kg/m3) at 15°C

868±5

879

883

866

Flash point (°C)

138±3

135

212

3.15±0.4

5.56

69±3

Kin.viscosity at 40 °C (cSt) Cetane number Acid value (mg KOH/g of oil) Cloud point (°C) Water and sediments (%) vol. max) Calorific value (MJ/Kg)

P. pinnata Mahua biodiesel C. pentandra

ASTM methods

Petroleum diesel

876.9

D5002-94 (860-900)

830±3

208

156.5

D93 (130)

56±1

4.66

4.98

4.16

D91 (-3 to 12)

-8±1

51.9

57

51.2

57.2

D445 (1.9 to 6)

3.12±0.5

0.29±0.1

0.4

0.17

0.41

0.38

D613 (49)

-

16±3

2.7

6

16

3

D664 (0.8 max)

-

0.0028

0.03

0.005

0.04

0.045

D2709 (0.30 max)

0.15±0.05

43.28±2.2

36.5

36.12

37

30.97

355 24

44.80-43.40

ACCEPTED MANUSCRIPT

356

Cloud point is one of the important parameters that describe the cold flow behavior of biodiesel.

357

The usage of biodiesel is limited by its response at lower temperatures. Suitable precautions must

358

be taken to monitor the operation of the engine using while using biodiesel [62]. The cloud point

359

of biodiesel obtained from C. inophyllum oil (10-21°C) was much higher than the corresponding

360

other biodiesel obtained from other vegetable oil [63]. Higher cloud point may cause cold start

361

problems in a diesel engine, particularly in cold climate countries. However, this could be

362

prevented by using additives, preheating before injection etc. M. M. Islam et al., 2016 studied the

363

effect of the addition of polymethyl acrylate on the cold flow properties on C. inophyllum

364

biodiesel (B20). There was a good improvement in the cold flow properties by the addition of

365

0.03 wt% polymethyl acrylate. The enhanced fuel properties were due to change in the rate of

366

crystal precipitation and aggression of blend was modified by the addition of additives [64].

367

The Cetane number is a key parameter to estimate the ignition quality of diesel during

368

combustion ignition. Another essential parameter, the ignition delay time, that is measured when

369

the diesel fuel is released into the combustion chamber is evaluated by the CN. This indicates

370

that high ignition delay corresponds to a lower CN value [65]. When this occurs, a phenomenon

371

called diesel knocking takes place and the fuel exhibits an increase in the amount of gaseous and

372

particulate exhaust emissions (PM) which generally takes place due to incomplete combustion.

373

This is also accompanied by greater engine deposits. Similar to the previous case the value is

374

higher for biodiesel when compared with petroleum diesel [66]. The cetane number of biodiesel

375

derived from C. inophyllum oil (69±3) was higher than that of the biodiesels’ from several other

376

vegetable oils listed in Table 5. This could be attributed to the higher saturated acid content of

377

C. inophyllum oil compared to other vegetable oils.

25

ACCEPTED MANUSCRIPT

378

A higher calorific value of the befoul leads to enhanced performance [67]. The calorific value of

379

the diesel derived from C. inophyllum is (38-46 MJ/kg) higher when compared with other

380

biodiesel fuels but, lower than that of petroleum diesel. Table 5 shows that the calorific values of

381

C.inophyllum, Jatropha, P. pinnata, Mahua and C. pentandra are 43.28 MJ/kg, 36.5MJ/kg,

382

36.12, 37 and 30.97 MJ/ kg respectively. These values are closely matching with that of

383

petroleum diesel. G. Knothe, 2005 reported that the Calorific value increases with the fatty acid

384

chain length and degree of saturation [68]. In C. inophyllum oil 35 % of the fatty acids were

385

saturated and therefore would readily release their heat content during combustion. Whereas

386

other oils only 5-10% of their fatty acid composition is saturated. Therefore, C. inophyllum

387

biodiesel gives better engine performance compared to other biodiesel fuels [69].

388

Presence of water may lead to hydrolysis of biodiesel which is not desirable as it leads to

389

degradation of fuel properties. When oxidative instability occurs, the fuel water content elevates

390

with the time of storage, which is regulated by the peroxidation chain reaction mechanism.

391

Primary oxidation products like hyperperoxides and conjugated dienes are produced due to the

392

breakdown of unsaturated fatty acids. This is detrimental to fuel characteristics like heating

393

value, flash point, and cetane index. The moisture content in liquid fuel initiates the growth of

394

microbes and quickens the rusting of metallic engine components. Therefore, decreasing the

395

moisture content to the lowest possible level in the liquid fuel is necessary to retain the desired

396

fuel characteristics [69].

397

The water and residue are present in two forms, dissolved water or droplets of water in

398

suspension. It is considered that water does not solubilize biodiesel but, biodiesel absorbs more

399

water than diesel fuel. The presence of water in biodiesel decreases the heat of combustion and

400

causes rusting of parts like fuel tubes, injector pumps, fuel pumps, Sediment could consist of rust 26

ACCEPTED MANUSCRIPT

401

particles in suspension and dirt or it may be formed from the fuel as components which are not

402

soluble, formed during the oxidation of the fuel. The water and sediment content of methyl esters

403

of C. inophyllum was found to be 0.0028-0.0045 [70]. C. inophyllum oil and Biodiesel produced

404

are shown in Figure 7.

405

5. Performance and emission characteristics of biodiesel obtained

406

from Calophyllum inophyllum oil.

407

Biodiesel has many desirable characteristics such as high biodegradability, non-toxicity, free of

408

aromatic compounds, renewability, low SOx content, higher cetane number and high flash point

409

that ultimately results in better performance. Presence of oxygen in biodiesel improves the

410

combustion efficiency. Carbon monoxide, hydrocarbons, and particulate emission are

411

comparatively lower and hence can be considered as a green fuel. Biodiesel blends can be used

412

in IC engines without any modification in the engine design. The performance analysis of C.

413

inophyllum biodiesel blend was reported in the literature were discussed in Table 6. The results

414

showed that blend of C. inophyllum biodiesel with diesel fuel is a potential alternative fuel which

415

can be used effectively in a diesel engine.

416

27

ACCEPTED MANUSCRIPT

417 418

Figure 7. Calophyllum inophyllum oil and produced Biodiesel.

419

28

420

Table 6

421

The comparison of biodiesel production from Calophyllum inophyllum oil using various process and catalyst and performance and

422

emission analysis available in the literature.

Methanol Temperature, Time, Yield to oil (Transesterification) h °C % ratio Catalysts

1 % (w/w) NaOH

6:1

60°C

0.5

85

Performance and emission characteristics

Reference

Compression ignition engine characteristics were studied on four nano- Nanthagopal, 2017 emulsion mixtures, comprising of 93% C.inophyllum biodiesel, 5% nanofluid solution and 2 % span and were compared with standard diesel and pure C. inophyllum biodiesel with the engine load acting as a variable parameter. At maximum brake power, the BTE was observed to be 5-17% higher in CIME nano-emulsions than undoped biodiesel, a consequence of the high surface area to volume ratio of the nano-particles, resulting in improved

evaporation

and

atomization.

The

emission

pollutant

compounds, CO and unburned hydrocarbons, and smoke were substantially lower for the CIME nano emulsions than both diesel and the pure biodiesel at all engine loads. NOx emission of CIME nano emulsions was lower 29

than that of pure biodiesel but was nevertheless slightly higher than stock diesel. Nanoparticle addition enhanced in-cylinder gas pressure and heat release rate over the entire range of varying engine loads. It was thus inferred that fuel combustion, emission, and engine performance parameters were positively influenced by doping of nanoparticles into the biodiesel. For both the pure biofuel and the blends, that the engine thermal efficiency was slightly lower in CIME biodiesel than in regular diesel. Emissions of CO and HC dropped with on using CIME biodiesel, but at the cost of higher NOx emissions. Smoke emissions were also lower than diesel at higher loads. Additionally, the combustion parameters were contrasted 1.5 wt% NaOH

16:1

60°C

0.5

85

against conventional diesel fuel under various loading conditions. The Ashok et al, 2017 cylinder pressure when biodiesel was used was lower than diesel, and as expected, increases with the decrease in the biodiesel concentration in the diesel blend.The peak heat release and ignition delay of CIME biodiesel were also lesser than that of the conventional diesel fuel, attributed to the high cetane number of the biodiesel.

NaOH (0.5% to 3.0%

6:1

50°C

0.5

-

The consequence of varying nozzle opening pressures on the operation Vairamuthu et al,

w/w)

(molar

characteristics of a constant speed, Direct Injection (DI) diesel engine

ratio)

when using of C. inophyllum Methyl Ester as a biofuel was studied by 30

2017 [73]

using the Artificial Neural Network (ANN) computational model. The NOP ranged from 220 bar to 250 bar and various parameters such as engine performance, exhaust gas emission and content, and the combustion characteristics of C. inophyllum biofuel. An ANN computational model was designed to predict and establish a relation between engine performance parameters [specific fuel consumption , brake thermal efficiency], emission parameters [exhaust gas temperature , unburnt hydrocarbon , CO, CO2, NOx and smoke density] when known parameters such as engine load, diesel-biofuel blend %and the NOP are entered, with correlation coefficient values between 0.98-1. Conventional BackPropagation Algorithm (to measure the individual neural error contribution for each processed batch data) and Multi-Layer Perception network (nonlinear approximate solutions for mapping the parameters between the input and output nodes) were used. Mean relative errors values were found to be between 0.46 and 5.8% and mean square errors were also insignificant. It was thus ascertained that ANN models can be used as a highly dependable and consistent tool characterizing performance and emission parameters of DI diesel engines. The optimal nozzle operating pressure for engine operation was determined to be 250 bar with unblended biodiesel. 1 % wt NaOH

9:1 molar

50 °C

2

Performance, combustion and emission characteristics when a novel anti- Ashok et al, 2017 oxidant, Ethanox, was utilized as an additive with pure C. inophyllum 31

ratio

methyl ester, while also comparing the results with a conventional antioxidant, namely butylated hydroxytoluene (BHT). Ethanox and BHT have blended with pure C. inophyllum biodiesel at 200, 500 and 1000 ppm by weight. The experiment was performed on a twin cylinder, four stroke diesel engine, operating at 1500 RPM. It was established that anti-oxidant blends had improved brake specific fuel consumption and brake thermal efficiency (5.3% increase), in comparison with pure biodiesel. Exhaust gas composition of blended biodiesels also showed lesser amounts of NOx than the neat biodiesel at all concentrations of both the additives, with reduced rates of 12.6% and 21% for 1000 ppm of Ethanox and 500 ppm of BHT respectively, compared to neat diesel. Both ethanol and BHT had similar combustion characteristics. Furthermore, anti-oxidation blending with neat biodiesel increased the exhaust gas content of CO and unburned hydrocarbons, while also having higher smoke emission at all concentrations. Higher smoke emission was found in BHT -blended fuel (500 ppm) compared to Ethanox, attributed to lack of oxygen due to the formation of hydroxyl radicals on the C4 on the ring due to inductive effects. It was thus concluded that Ethanox served as a better anti-oxidant than BHT.

32

[74]

The objective of the research was to establish the consequence of modifying the nozzle configuration, namely the number of spray holes and hole diameter from the conventional 3 holes (diameter (Ø ) =0.280mm) to NaOH (0.5% to 3.0% w/w)

6:1 (molar

4 ( Ø = 0.220 mm) and 5 (Ø = 0.240 mm) holes in a 4-stroke diesel engine 50°C

0.5

-

ratio)

using C. inophyllum methyl ester. It was concluded that modifications of the nozzle (4 and 5 holes) had a positive effect on of brake thermal

Vairamuthu et al, 2016 [75]

efficiency and specific fuel consumption, with a significant decline in emission levels when 5 holes were used, in particular, at a nozzle operating pressure of 250 bar. 1 % (w/w) KOH

25% (v/v)

70 °C

3

-

ALB showed higher kinematic viscosity and density but slightly lower Ruhul Amin, 2016 HHV than JB. On the basis of the FAC, PB showed a higher degree of saturation, whereas JB showed the highest degree of unsaturation than others. The amount of each fatty acid, the carbon chain length, and the number of double bonds were the determinant factors of the biodiesels’ physicochemical properties. A higher CN of PB compared with the other two biodiesels could be attributed to a higher content of methyl palmitate. On average, all the tested fuels reduced BP (2.8%–4.5%) and increased BSFC (8%– 15%) compared with B5 fuel. The lower BP and higher BSFC of the biodiesel blend might be the result of low HHV, high viscosity, and high density. Biodiesel blending decreased CO and HC emissions. ALB blends showed better performance than JB blends in terms of CO and HC 33

[76]

emissions. ALB blends provided lower CO emissions due to its higher degree of saturation and higher CN compared with those of JB blends. On average, the CO emission of all the tested blends decreased from 13.25% to 29%, HC emission decreased from 13.33% to 21.33%, CO2 emission increased from 1.5% to 3.9%, and NOX emissions increased from 11.33% to 19.66% compared with B5 fuel Higher injection pressures of the biodiesel had considerably reduced the brake specific fuel consumption. At 220 bars, the emission of environmentally polluting combustion by-products such as carbon 6:1 1 % (w/w) KOH

(Molar

monoxide and incompletely burnt hydrocarbon entities was significantly 60° C

0.5

lower, and the smoke opacity was much lesser, although nitrogen oxide

ratio)

concentrations linearly increased with increase in pressure and were higher

Nanthagopal, 2016 [77]

than the neat diesel emission concentration of corresponding injection pressures. Both the fuel sources showed analogous combustion characteristics, regardless of injection pressure. 1 % (w/w) NaOH

_

60 °C

2

90

Operational, combustion and emission characteristics of constant speed Vairamuthu et al, direct injection diesel engine running on blends of C. inophyllum - diesel (25%, 50% and 75% biodiesel) were analyzed and compared with conventional diesel fuel. The performance of the 25% biofuel blend showed superior performance (27.5%, over the 26.28% of diesel) and 34

2015 [78]

lowered the smoke density by 2.6% on full load, with CO emissions being 4% lower than that of diesel. However, hydrocarbon emissions were 5.37% higher in 25% blend and 25.8% higher in pure biodiesel than that of diesel. Nitrogenous oxide emissions were lower across all the blends, with 75% blend and pure biodiesel having 13.29% and 22.16% lower NOx emissions respectively. C. inophyllum oil-based methyl ester (COME) and COME-diesel blend 1.5% - 1 % KOH w/w

operated engines, the effect of compression ratio on the combustion

18-20% methanol

60°C

3

-

v/v

characteristics were surveyed. Experimentation was done at 1500 rpm fixed motor speed, full load and at varying compression ratios of 16:1, 17:1 and 18:1. The survey demonstrated that C. inophyllum oil had higher

Swarup Kumar Nayak et al, 2015 [16]

combustion time and shorter ignition delay period than conventional diesel. SBA-15/ Lipase from Aspergillus niger

Ca/SBA-15 solid base Rhizopus oryzae cells

6:1 (Molar

30°C

8

96.4

-

80°C

5

88.7

-

30°C

72

94

-

ratio) 16:1 (Molar ratio) 12:1

35

Arumugam et al, 2015 [51]

Arumugam et al. 2015[40] Arumugam et al,

immobilized within

(Molar

reticulated foams

ratio)

2015 [54]

Compression ratios are linearly proportional to the cylinder temperature, meaning higher ratios creates better vaporization conditions, and thereby, better performance, although only up to a CR of 19:1. Higher operation Methanol/ KOH (w/v): 1.3

oil (v/v) :

temperatures were also, however, implicated in higher NOx emission 53.8 °C

1.4

94

0.42

concentrations, but lower carbon monoxide and unburned hydrocarbon emissions for both the pure biofuel and the blends due to improved

Antony Miraculous et al, 2014 [79]

combustion. The designed empirical statistical model established that B30 (30% biofuel blend) had the most optimal performance and lower emissions at CR 19:1, which was validated by testing. Studied the physical and chemical properties of biodiesel-diesel blends of biodiesel 1 % (w/w) KOH

12:1

80°C

produced

from

Croton

megalocarpus,

C.

inophyllum,

Moringaoleifera, palm, and coconut. It was inferred that a fuel mixture of Atabani et al 2014

24

diesel and biodiesel enhanced the combustion characteristics, while also

[80]

having a diminished flash point and lower viscosity index than the pure diesel fuel. 1% (w/w) NaOH

9:1 (molar

50°C

2

98

The performance and emission characteristics of 10% C. inophyllum Hwai Chyuan Ong, biodiesel blend (CIB10) showed considerable improvement over pure diesel operated engines, evident from an increase in the brake thermal 36

2014 [81]

ratio)

increase by 2.30 % and a drop in fuel consumption by 3.06%.CIB50 has highest BSFC of biodiesel-diesel blend which is 621.4 g/kW h at 1500 rpm. Besides, CIB10 reduces CO and smoke opacity compared to diesel. The NOx emission was low and within acceptable limits for 10% blend of biodiesel with diesel fuel. The brake specific fuel consumption decreased with lesser concentrations of the biodiesel.

9:1 1% (w/w) KOH

(Molar

55°C

1

98.53

-

ratio)

Silitonga et al, 2014 [82]

Physico-chemical property studies on diesel- biodiesel mix were performed. The performance and emission characteristics on a 55kW, 2.5L, four-cylinder indirect injection diesel engine when using blends having 10% and 20% biodiesel concentrations were also examined. It was

6: 2 % (w/w) KOH

1(Molar ratio)

60 °C

2

ascertained that brake power requirements dropped in the range of 0.36- Abedin et al, 2014 0.76%, while the brake-specific fuel consumption increased by 2.42-3.2% on using the blends. Emission characteristics of biodiesel blends were superior to diesel (15.12-26.84% lesser CO emission and 9.26-17.04% lesser hydrocarbon emissions), while NOx emissions suffered a setback over diesel emissions (2.12-8.32% higher than in diesel).

37

[84]

Sulphonated carbon catalyst Sulfonated Microcrystalline cellulose catalyst (5 wt %)

30:1 (Molar

Olubunmi O. 180 °C

5

92

-

ratio)

[47]

15:1 (Molar

Ayodele et al, 2014

180 °C

4

99

-

ratio)

Dawodu et al, 2014 [46]

Anti-oxidant addition improved oxidative stability. The anti-oxidant addition also decreased the ignition delay, while enhancing the brake power and brake thermal efficiency, and lowering the brake specific fuel consumption than unblended biodiesel and stock diesel (admixture of BHT and MBEBP resulted in an average decrease of BSFC by 0.43% and 0.57%

6:1 1% (w/w) KOH

(molar ratio)

60°C

2

95

compared to the 30% blend). NOx emissions were substantially reduced Rizwanul Fattah et on anti-oxidant addition (5.91% and 5.27% mean reduction compared to the 30% blend on adding BHT and MBEBP respectively) although smoke opacity, CO and hydrocarbon emissions were compromised in the process, being somewhat higher than the initial blend. It was concluded that antioxidant doped 30% C. inophyllum biodiesel- diesel blend can be used as a fuel for diesel engines without any alterations in engine designs.

38

al, 2014 [83]

1 % (w/w) Sodium methoxide

7.5:1 (Molar

55 °C

5

93

-

ratio)

(molar

[85]

Calophyllum biodiesel was found to have greater thermal efficiency than

16:1 1 % (w/w) KOH

Jahirul et al, 2014

70 °C

3

-

ratio)

palm biodiesel and conventional diesel. Biodiesel from both palm and C. inophyllum had lower hydrocarbon and CO emissions than stock diesel as

Sanjid et al, 2013

well. Brake specific fuel consumption was positively influenced by increasing biofuel concentration in the blend, but the influence was however negligible at the highest idling condition. Brake thermal efficiency of the blends was found to be substantially lessened at engine operating at 1000

1 % (w/w) KOH

25% v/v methanol

RPM 10% load and 1200 RPM 12% load. Exhaust gas temperatures varied 70 °C

3

-

inversely with the biofuel concentration in both the blends. NOx levels increased with the increase in bio-fuel concentration in both the blends, being negligible at low biodiesel to diesel ratios but increased drastically at higher ratios. Emission of carbon monoxide and unburnt hydrocarbons were lesser in both blends than pure diesel, with the lowest emissions found on 20% C. inophyllum-diesel blend.

39

Ashrafur Rahman, 2013 [87]

8:1 6 % (w/w) KOH

(Molar

60°C

2

93

-

60°C

2

89

-

ratio)

8:1 1.25 % (w/w) NaOH

(Molar ratio)

Vasanthakumar et al, 2011 [34]

Venkanna et al, 2009 [35]

Fuel economy for 20%, 50% blends and neat biodiesel was found to be 180.55 g/bhp-h, 181.15 g/bhp-h and 189.97g/bhp-h respectively. Brake

6:1 1.5 % (w/w) NaOH

(Molar

65°C

2

98.4

ratio)

specific energy consumption (BSEC) was moderately lesser in the biofuel Sahoo et al. 2009 blends than stock diesel, with CB20 (20% blend) having the lowest BSEC

[88]

value at 2.59%. It was hence implied that CB20 is the optimum fuel blend among those analyzed.

9:1 1.5 % (w/w) KOH

(Molar

Sahoo et al. 2007 65°C

4

85

[89]

ratio) 423

40

ACCEPTED MANUSCRIPT

424

6 Conclusion

425 426

Calophyllum inophyllum oil appears to be an attractive alternate biodiesel feedstock in the near

427

future. Major advantages of Calophyllum inophyllum, as an alternate biodiesel feedstock are:

428

1. Properties of Calophyllum inophyllum oil very close to diesel fuel. Properties of the C.

429

inophyllum biodiesel meets ASTM standards by and large. Transesterification of C.

430

inophyllum by catalytic method produces a good yield, usually greater than 95%, making

431

it as economically attractive feedstock.

432

2. Yields more oil per hectare(The average oil yield: 5000 L/ha) compared to other plants.

433

There is no competition for the cultivatable land, as these plants grow on seashores.

434 435

3. Non-edible and cheap. The species is abundantly available in many countries as indicated in section 1. Almost available during all seasons

436

4. It is one of the clean and carbon neutral fuels

437

5. Among various methods used for biodiesel production enzymatic conversion appears to

438

be more attractive. Recent developments in advanced processes like supercritical fluid

439

methanolysis can make this oil more attractive.

440 441 442 443 444 445 41

ACCEPTED MANUSCRIPT

446 447

7 REFERENCES

448

[1] Fatiha Ouanji, Mariam Khachani, Mustapha Boualag, Mohamed Kacimi, Mahfoud Ziyad.

449

Large-scale biodiesel production from Moroccan used frying oil. I J Hydrogen Energy 2016; 41:

450

21022-21029.

451

[2] Mohammad Ali Rajaeifar, Asadolah Akram, Barat Ghobadian, Shahin Rafiee, Reinout

452

Heijungs, Meisam Tabatabaei. Environmental impact assessment of olive pomace oil biodiesel

453

production and consumption: A comparative lifecycle assessment. Energy 2016; 106:87-102.

454

[3] Nuria García-Martínez, Pedro Andreo-Martínez, Joaquín Quesada-Medina, Antonia Pérez de

455

los Ríos, Antonio Chica, Rubén Beneito-Ruiz, Juan Carratalá-Abril, Optimization of non-

456

catalytic transesterification of tobacco (Nicotiana tabacum) seed oil using supercritical methanol

457

to biodiesel production. Energ Convers Manage 2017; 131: 99-108.

458

[4] Sandra B. Glisic, Jelena M. Pajnik, Aleksandar M. Orlovic, Process and techno-economic

459

analysis of green diesel production from waste vegetable oil and the comparison with ester type

460

biodiesel production, Appl Energ 2016;170:176-185.

461

[5] Siow Hwa Teo, Umer Rashid, Yun Hin Taufiq-Yap, Biodiesel production from crude

462

Jatropha Curcas oil using calcium based mixed oxide catalysts, Fuel, 2014;136: 244-252.

463

[6] Ortiz-Martínez VM, Salar-García MJ, Palacios-Nereo FJ, Olivares-Carrillo P, Quesada-

464

Medina J, De los Ríos AP, Hernández-Fernández FJ. In-depth study of the transesterification

465

reaction of Pongamia pinnata oil for biodiesel production using catalyst-free supercritical

466

methanol process. J Supercritical Fluids 2016; 113:23-30. 42

ACCEPTED MANUSCRIPT

467

[7]. Deepesh Sonar, Soni, Dilip Sharma SL, Anmesh Srivastava, Rahul Goyal. Performance and

468

emission characteristics of a diesel engine with varying injection pressure and fuelled with raw

469

mahua oil (preheated and blends) and mahua oil methyl ester, Clean Technol Environl Pol 2015;

470

17: 1499–1511.

471

[8]. Celián Román-Figueroa, Pilar Olivares-Carrillo, Manuel Paneque, Francisco Javier Palacios-

472

Nereo, Joaquín Quesada-Medina. High-yield production of biodiesel by non-catalytic

473

supercritical methanol transesterification of crude castor oil (Ricinus communis). Energ 2016;

474

107: 165-171.

475

[9] Aza MM, Waris A, Nahar NM. Prospects and potential of fatty acid methyl esters of some

476

non-traditional seed oils for use as biodiesel in India. Biomass. Bioenerg.2005; 29: 293–302.

477

[10] Torsten Siegmeier, Detlev Möller. Mapping research at the intersection of organic farming

478

and bioenergy — A scientometric review. Renew Sust Energ Rev 2013; 25: 197-204.

479

[11] Ozcan Konur, The scientometric evaluation of the research on the algae and bio-energy.

480

Appl Energ 2011; 88: 3532-3540.

481

[12] Mosarof MH, Kalam MA, Masjuki HH, Abdullah Alabdulkarem, Ashraful AM, Arslan A,

482

Rashedul HK, Monirul IM. Optimization of performance, emission, friction and wear

483

characteristics of palm and Calophyllum inophyllum biodiesel blends. Energ Conv Manage 2016;

484

118: 119-134.

485

[13] Kadambi K.. The silviculture of Calophyllum inophyllum Linn, Indian For.1957 ;83: 559-

486

562.

43

ACCEPTED MANUSCRIPT

487

[14] Dweck AC, Meadowsy T. Tamanu (Calophyllum inophyllum) – the African, Asian,

488

Polynesian and Pacific Panacea. Int. J. Cosmetic .Sci. 2002; 24, 1-8.

489

[15] Agroforestry Data Base . World Agroforestry Centre PROSEA network, 2006

490

http://www.world agroforestry.org.

491

[16] Swarup Kumar Nayak, Santosh Kumar Nayak, Purna Chandra Mishra, Srinibas Tripathy.

492

Influence of compression ratio on combustion characteristics of a VCR engine using

493

Calophyllum inophyllum biodiesel and diesel blends. J Mech Sci Technol 2015; 29 : 4047- 4052.

494

[17] Porcher Michel H. Multi lingual multiscript plant name database- Calophyllum inophyllum

495

L.; 2005.

496

[18] Friday JB, Okano D. Calophyllum inophyllum (kamani) species profiles for Pacific Island

497

agroforestry, Traditional Tree Initiative Hawaii.2006. http//.traditionaltree.org

498

[19] Ng FSP. 1992. Manual of Forest Fruits, Seeds and Seedlings. Malayan Forest Record 1992;

499

34: 2.

500

[20] Atabani A.E, Aldara da Silva César. Calophyllum inophyllum L. – A prospective non-edible

501

biodiesel feedstock. Study of biodiesel production, properties, fatty acid composition, blending

502

and engine performance, Renew Sust Energ Rev 2014; 37: 644-655.

503

[21] Parawira W. Biodiesel production from Jatropha curcas : A review. Sci. Res. Essays. 2010;

504

5: 1796–1808.

44

ACCEPTED MANUSCRIPT

505

[22] Agarwal D, Agarwal AK. Performance and emissions characteristics of jatropha oil

506

(preheated and blends) in a direct injection compression ignition engine. Appl Therm Eng 2007;

507

27: 2314–2323.

508

[23] Misra RD, Murthy MS. Straight vegetable oils usage in a compression ignition engine—a

509

review. Renew Sust Energy Rev 2010; 14: 3005–3013.

510

[24] Attaphong C, Do L, Sabatini DA. Vegetable oil-based microemulsions using carboxylate-

511

based extended surfactants and their potential as an alternative renewable biofuel. Fuel. 2012;

512

94:606–613.

513

[25] Yin C. Microwave-assisted pyrolysis of biomass for liquid biofuels production. Bioresour.

514

Technol. 2012; 120:273–284.

515

[26] Bart JCJ, Palmeri N, Cavallaro S. Vegetable oil formulations for utilisation as biofuels.

516

Biodiesel. Sci. Technol. 2010; 4:114–129.

517

[27] Olutoye M.A, Hameed B.H. Kinetics and deactivation of a dual-site heterogeneous oxide

518

catalyst during the transesterification of crude jatropha oil with methanol. J Taibah Univ Sci

519

2016; 10:685-699.

520

[28] Miroslawa Szczesna Antczak, Aneta Kubiak, Tadeusz Antczak, Stanis1aw Bielecki.

521

Enzymatic biodiesel synthesis – Key factors affecting efficiency of the process. Renew. Energ.

522

2009; 34: 1185–1194.

45

ACCEPTED MANUSCRIPT

523

[29] Amin Talebian-Kiakalaieh, Nor Aishah Saidina Amin, Hossein Mazaheri. A review on

524

novel processes of biodiesel production from waste cooking oil. Appl Energ 2013; 104: 683–

525

710.

526

[30] Thawatchai Maneerung, Sibudjing Kawi, Chi-Hwa Wang, Biomass gasification bottom ash

527

as a source of CaO catalyst for biodiesel production via transesterification of palm oil. Energ

528

Conv Manag 2015; 92: 234-243.

529

[31] Benjamas Cheirsilp, Aran H-Kittikun, Suchart Limkatanyu. Impact of transesterification

530

mechanisms on the kinetic modelling of biodiesel production by immobilized lipase. Biochem

531

Eng J 2008; 42: 261–269.

532

[32] Ma F, Hanna MA. Biodiesel production : a review. Bioresource. Technol. 1999; 1, 70: 1–

533

15.

534

[33] Puneet Verma, M.P. Sharma, Gaurav Dwivedi. Impact of alcohol on biodiesel production

535

and properties. Renew Sustain Energ Rev 2016; 56: 319-333.

536

[37] Fatiha Ouanji, Mariam Khachani, Mustapha Boualag, Mohamed Kacimi, Mahfoud Ziyad.

537

Large-scale biodiesel production from Moroccan used frying oil. I J Hydrogen Energ 2016; 41:

538

21022-21029.

539

[34] Vasanthakumar SathyaSelvabala, Dinesh Kirupha Selvaraj, Jalagandeeswaran Kalimuthu,

540

Premkumar Manickam Periyaraman, Sivanesan Subramanian. Two-step biodiesel production

541

from Calophyllum inophyllum oil: Optimization of modified b-zeolite catalyzed pre-treatment.

542

Bioresource Technol 2011; 102: 1066–1072.

46

ACCEPTED MANUSCRIPT

543

[35] Sathyaselvabala V, Thiruvengadaravi KV, Sudhakar M, Selvaraj DK, Sivanesan S.

544

Optimization of free fatty acids reduction in Calophyllum inophyllum ( pinnai ) oil using

545

modified zirconia catalyst for biodiesel production. Asia-Pac. J. Chem. Eng. 2012; 7: 140–149.

546

[36] Hwai Chyuan Ong, Masjuki HH, Mahlia TMI, Silitonga AS, Chong WT, Talal Yusaf.

547

Engine performance and emissions using Jatropha curcas, Ceiba pentandra and Calophyllum

548

inophyllum biodiesel in a CI diesel engine. Energ. 2014; 69: 427- 445.

549

[37] Chavan SB, Kumbhar RR, Deshmukh RB. Callophyllum inophyllum Linn (“honne”) Oil, A

550

source for Biodiesel Production. Res J Sci 2013; 3: 24-31.

551

[38] Venkanna BK, Reddy CV. Bioresource Technology Biodiesel production and optimization

552

from Calophyllum inophyllum linn oil ( honne oil ) – A three stage method. Bioresource Technol

553

2009;100: 5122–5125.

554

[39] Vairamuthu G, Sundarapandian S, Kailasanathan C, Thangagiri B. Experimental

555

investigation on the effects of cerium oxide nanoparticle on Calophyllum inophyllum (Punnai)

556

biodiesel blended with diesel fuel in DI diesel engine modified by nozzle geometry. J Energ Inst

557

2016; 89: 668-682.

558

[40] Arumugam A, Ponnusami V. Optimization of recovery of silica from sugarcane leaf ash and

559

Ca/SBA-15 solid base for transesterification of Calophyllum inophyllum oil. J Sol-Gel Sci

560

Technol. 2015; 74: 132-142.

561

[41] Qing Shu, Bolun Yang, Hong Yuan, Song Qing, Gangli Zhu. Synthesis of biodiesel from

562

soybean oil and methanol catalyzed by zeolite beta modified with La3+. Catal Commun 2007; 8:

563

2159–2165. 47

ACCEPTED MANUSCRIPT

564

[42] Muhammad Farooq, Anita Ramli, Abdul Naeem. Biodiesel production from low FFA waste

565

cooking oil using heterogeneous catalyst derived from chicken bones. Renew Energ. 2015; 76:

566

362-368

567

[43] Luiz P Ramos, Claudiney S Cordeiro, Maria Aparecida F Cesar-Oliveira, Fernando

568

Wypych, Shirley Nakagaki. Applications of Heterogeneous Catalysts in the Production of

569

Biodiesel by Esterification and Transesterification. Bioenerg. Research: Adv Appl.2014; 14:

570

255–276.

571

[44] Masato Kouzu, Michito Tsunomori, Shinya Yamanaka, Jusuke Hidaka. Solid base catalysis

572

of calcium oxide for a reaction to convert vegetable oil into biodiesel. Adv. Powder Technol

573

2010; 21: 488–494.

574

[45] Muthukumaran N, Saravanan CG, Prasanna Raj Yadav S, Vallinayagam R, Vedharaj S,

575

Roberts WL. Synthesis of cracked Calophyllum inophyllum oil using fly ash catalyst for diesel

576

engine application. Fuel 2015; 155: 68-76.

577

[46] Dawodu FA, Ayodele O, Xin J, Zhang S, Yan D. Effective conversion of non-edible oil

578

with high free fatty acid into biodiesel by sulphonated carbon catalyst. Appl. Energ. 2014;

579

114:819-826.

580

[47] Olubunmi O. Ayodele, Folasegun A. Dawodu. Production of biodiesel from Calophyllum

581

inophyllum oil using a cellulose-derived catalyst. Biomass Bioenerg 2014; 70, : 239-248.

582

[48] Rismawati Rasyid, Adrianto Prihartantyo, M. Mahfud, Achmad Roesyadi. Hydrocracking of

583

Calophyllum inophyllum Oil with Non-Sulfide CoMo Catalysts. B Chem React Eng Cataly

584

2015;10 : 61-69. 48

ACCEPTED MANUSCRIPT

585

[49] Susan Hartwig Duarte, Gonzalo Lázaro del Peso Hernández, Albert Canet, Maria Dolors

586

Benaiges, Francisco Maugeri, Francisco Valero. Enzymatic biodiesel synthesis from yeast oil

587

using immobilized recombinant Rhizopus oryzae lipase. Bioresource. Technol. 2015; 183: 175-

588

180.

589

[50] Dizge N, Aydiner C, Imer DY, Bayramoglu M, Tanriseven A, Keskinler B. Biodiesel

590

production from sunflower, soybean, and waste cooking oils by transesterification using lipase

591

immobilized onto a novel microporous polymer. Bioresource Technol 2009; 100: 1983–1991.

592

[51] Arumugam A, Ponnusami V. Synthesis of SBA-15 from low cost silica precursor obtained

593

from sugarcane leaf ash and its application as a support matrix for lipase in biodiesel production.

594

J Sol-Gel Sci Technol 2013; 67:244-250.

595

[52] Arumugam A, Ponnusami V. Enzymatic transesterification of Calophyllum inophyllum oil

596

by lipase immobilized on functionalized SBA-15 synthesized from low-cost precursor. Biomass

597

Conv. Bioref. 2014; 4: 35.

598

[53] Aitao Li, Thao P.N. Ngo, Jinyong Yan, Kaiyuan Tian, Zhi Li. Whole-cell based solvent-free

599

system for one-pot production of biodiesel from waste grease. Bioresource Technol 2012; 114:

600

725-729.

601

[54] Arumugam A, Ponnusami V. Biodiesel production from Calophyllum inophyllum oil using

602

lipase producing Rhizopus oryzae cells immobilized within reticulated foams. Ren engerg 2014;

603

64: 276-282.

604

[55] Ma F, Hanna MA. Biodiesel production : a review. Bioresource. Technol. 1999; 170: 1–15.

49

ACCEPTED MANUSCRIPT

605

[56] Puneet Verma MP, Sharma, Gaurav Dwivedi. Impact of alcohol on biodiesel production and

606

properties. Renew Sustain Energ Rev 2016; 56: 319-333.

607

[57] Neha Lamba, Kaveri Gupta, Jayant M. Modak, Giridhar Madras. Biodiesel synthesis from

608

Calophyllum inophyllum oil with different supercritical fluids. Bioresource Technol, 2017; 241:

609

767-774.

610

[58] Marso TMM, Kalpage CS, Udugala-ganehenege MY. Metal modified graphene oxide

611

composite catalyst for the production of biodiesel via pre-esterification of Calophyllum

612

inophyllum oil. Fuel 2017; 199:47–64.

613

[59] Kakati J, Gogoi TK, Pakshirajan K. Production of biodiesel from Amari (Amoora Wallichii

614

King) tree seeds using optimum process parameters and its characterization. Energ Conv Manag

615

2017; 135: 281-290.

616

[60] Kaya C, Hamamci C, Baysal A. Methyl ester of peanut (Arachis hypogea L.) seed oil as a

617

potential feedstock for biodiesel production. Renew.Energ. 2009; 34:1257-1260.

618

[61] Charudatta M. Kshirsagar, Ramanathan Anand. Artificial neural network applied forecast on

619

a parametric study of Calophyllum inophyllum methyl ester-diesel engine out responses. Appl

620

Energ 2017; 189: 555-567.

621

[62] Monirul IM, Kalam MA, Masjuki HH, Zulkifli NWM, Shahir SA, Mosarof MH, Ruhul AM.

622

Influence of poly(methyl acrylate) additive on cold flow properties of coconut biodiesel blends

623

and exhaust gas emissions. Renew Energ 2017; 101: 702-712.

50

ACCEPTED MANUSCRIPT

624

[63] Yuan Xue, Zhicheng Zhao, Guangwen Xu, Xiang Lian, Chao Yang, Weina Zhao, Peng Ma,

625

Hualin Lin, Sheng Han. Effect of poly-alpha-olefin pour point depressant on cold flow properties

626

of waste cooking oil biodiesel blends. Fuel 2016;184: 110-117.

627

[64] Mohammad Monirul Islam, Masjuki Haji Hassan, Md Abul Kalam, Nurin Wahidah binti

628

Mohd Zulkifli, Md Habibullah, Mohammad Mosarof Hossain. Improvement of cold flow

629

properties of Cocos nucifera and Calophyllum inophyllum biodiesel blends using polymethyl

630

acrylate additive. J Clean Prod 2016; 137:322-329.

631

[65] Thangavel Mathimani, Tamilkolundu Senthil Kumar, Murugesan Chandrasekar,

632

Lakshmanan Uma, Dharmar Prabaharan. Assessment of fuel properties, engine performance and

633

emission characteristics of outdoor grown marine Chlorella vulgaris BDUG 91771 biodiesel.

634

Renew Energ 2017; 105: 637-646.

635

[66] Abigor RD, Uaudia PO, Foglia TA. Lipase-catalysed production of biodiesel fuel from

636

some Nigerian lauric oils. Biochem Soc T 2000; 28:979-981.

637

[67] Acharya N, Nanda P, Panda S, Acharya S. Analysis of properties and estimation of

638

optimum blending ratio of blended mahua biodiesel. Eng Sci Technol Int J 2017;20: 511-517.

639

[68] Knothe G, Steidley KR. Kinematic viscosity of biodiesel fuel components and related

640

compounds. Influence of compound structure and comparison to petrodiesel fuel components.

641

Fuel 2005, 84, 1059–65.

642

[69] Gopinath Dhamodaran, Ramesh Krishnan, Yashwanth Kutti Pochareddy, Homeshwar

643

Machgahe Pyarelal, Harish Sivasubramanian, Aditya Krishna Ganeshram. A comparative study

51

ACCEPTED MANUSCRIPT

644

of combustion, emission, and performance characteristics of rice-bran-, neem-, and cottonseed-

645

oil biodiesels with varying degree of unsaturation. Fuel 2017; 187: 296-305.

646

[70] Saravanan N, Puhan S, Nagarajan G, Vedaraman N. An experimental comparison of

647

transesterification process with different alcohols using acid catalysts. Biomass. Bioenerg. 2010;

648

34:999-1005.

649

[71] Nanthagopal K, Ashok B, Tamilarasu A, Johny A, Mohan A. Influence on the effect of zinc

650

oxide and titanium dioxide nanoparticles as an additive with Calophyllum inophyllum methyl

651

ester in a CI engine. Energ Conv Manag. 2017;146:8–19.

652

[72] Ashok B, Nanthagopal K, Jeevanantham AK, Bhowmick P, Malhotra D, Agarwal P. An

653

assessment of Calophyllum inophyllum biodiesel fuelled diesel engine characteristics using novel

654

antioxidant additives. Energ Conv Manag . 2017;148:935–43.

655

[73] Vairamuthu G, Thangagiri B, Sundarapandian S. Experimental and artificial neural network

656

based prediction of performance and emission characteristics of DI diesel engine using

657

Calophyllum inophyllum methyl ester at different nozzle opening pressure. Heat mass trans.

658

2017.

659

[74] Ashok B, Nanthagopal K, Vignesh DS. Calophyllum inophyllum methyl ester biodiesel

660

blend as an alternate fuel for diesel engine applications. Alexandria Eng J. 2017.

661

[75] Sundarapandian G, Kailasanathan S, Thangagiri CB. Experimental investigation on the

662

effects of cerium oxide nanoparticle on Calophyllum inophyllum (Punnai) biodiesel blended with

663

diesel fuel in DI diesel engine modified by nozzle geometry. J Energ Inst 2016; 89: 668-682.

52

ACCEPTED MANUSCRIPT

664

[76] Amin R, Abedin J, Rahman SMA, Bin M, Hassan H, Alabdulkarem A. Impact of fatty acid

665

composition and physicochemical properties of Jatropha and Alexandrian laurel biodiesel blends:

666

An analysis of performance and emission characteristics. J Clean Prod. 2016; 133: 1181-1189.

667

[77] Nanthagopal K, Ashok B, Thundil Karuppa Raj R. Influence of fuel injection pressures on

668

Calophyllum inophyllum methyl ester fuelled direct injection diesel engine. Energ Conv Manag,

669

2016; 116 : 165-173.

670

[78] Vairamuthu G, Sundarapandian S, Kailasanathan C, Thangagiri B. Experimental

671

investigation on the effects of cerium oxide nanoparticle on Calophyllum inophyllum (Punnai)

672

biodiesel blended with diesel fuel in DI diesel engine modified by nozzle geometry. J Energ Inst

673

2016; 89: 668-682.

674

[79] Antony Miraculas G, Bose N, Edwin Raj R. Optimization of process parameters for

675

biodiesel extraction from tamanu oil using design of experiments. J Renew Sustain Energ.

676

2014; 6.

677

[80] Atabani AE, Mofijur M, Masjuki HH, Badruddin IA, Kalam MA, Chong W.T. Effect of

678

Croton megalocarpus, Calophyllum inophyllum, Moringa oleifera, palm and coconut biodiesel–

679

diesel blending on their physico-chemical properties. Ind. Crops. Prod. 2014; 60:130–137.

680

[81] Hwai Chyuan Ong, Masjuki HH, Mahlia TMI, Silitonga AS, Chong WT, Talal Yusaf.

681

Engine performance and emissions using Jatropha curcas, Ceiba pentandra and Calophyllum

682

inophyllum biodiesel in a CI diesel engine. Energ. 2014; 69: 427- 445.

53

ACCEPTED MANUSCRIPT

683

[82] Silitonga AS, Masjuki HH, Hwai Chyuan Ong, Kusumo F, Mahlia TMI, Bahar AH. Pilot-

684

scale production and the physicochemical properties of palm and Calophyllum inophyllum

685

biodiesels and their blends. J Clean Prod. 2014; 126: 654-666.

686

[83] Rizwanul Fattah IM, Masjuki HH, Kalam MA, Wakil MA Ashraful AM, Shahir SA.

687

Experimental investigation of performance and regulated emissions of a diesel engine with

688

Calophyllum inophyllum biodiesel blends accompanied by oxidation inhibitors. Energ. Convers.

689

Manage. 2014; 83: 232–240.

690

[84] Abedin MJ, Masjuki HH, Kalam MA, Sanjid A, Ashrafur Rahman SM, Rizwanul Fattah

691

IM. Performance, emissions, and heat losses of palm and jatropha biodiesel blends in a diesel

692

engine. Ind Crops Prod 2014; 59: 96-104.

693

[85] Mohammad Jahirul I, Wenyong Koh , Richard Brown J, Wijitha Senadeera , Ian O’Hara,

694

Lalehvash Moghaddam. Biodiesel Production from Non-Edible Beauty Leaf (Calophyllum

695

inophyllum) Oil: Process Optimization Using Response Surface Methodology (RSM). Energies

696

2014; 7: 5317-5331.

697

[86] Sanjid A , Masjuki HH, Kalam MA, Ashrafur Rahman SM, Abedin MJ, Palash SM. Impact

698

of palm, mustard, waste cooking oil and Calophyllum inophyllum biofuels on performance and

699

emission of CI engine. Renew. Sust. Energ. Rev. 2013; 27: 664–682.

700

[87] Ashrafur Rahman SM, Masjuki HH, Kalam MA, Abedin MJ, Sanjid A, Sajjad H.

701

Production of palm and Calophyllum inophyllum based biodiesel and investigation of blend

702

performance and exhaust emission in an unmodified diesel engine at high idling conditions.

703

Energ Conv Manag 2013; 76 : 362-367. 54

ACCEPTED MANUSCRIPT

704

[88] Sahoo PK, Das LM, Babu MK. Comparative evaluation of performance and emission

705

characteristics of jatropha , karanja and polanga based biodiesel as fuel in a tractor engine. Fuel.

706

2009; 88:1698-1707.

707

[89] Sahoo PK, Das LM, Babu MK, Naik SN. Biodiesel development from high acid value

708

polanga seed oil and performance evaluation in a CI engine. Fuel. 2007; 86:448-454.

709

7. List of figures and tables

710

Figure. 1. Geographic Distribution of Calophyllum inophyllum Linn, Countries that published

711

about Calophyllum inophyllum as a source of biodiesel feedstock during the period of 2005–

712

2017.

713

Figure 2. Calophyllum inophyllum Linn

714

Figure 3. Methods for biodiesel production from Calophyllum inophyllum oil

715

Figure 4. Biodiesel production reaction scheme.

716

Figure. 5. Process flow diagram of conventional Acid/ Alkali/ Biocatalyst/ Heterogeneous

717

catalyst in transesterification process for biodiesel production.

718

Figure 6. Biodiesel production processes with supercritical methanol.

719

Figure 7. Calophyllum inophyllum oil and produced Biodiesel.

720

Table 1: Non-edible sources and oil content for biodiesel production.

721

Table 2: Systematic position of Calophyllum inophyllum Linn.

722

Table. 3: Physical and chemical properties of Calophyllum inophyllum oil.

723

Table 4: Fatty acid composition of C. inophyllum oil (%). 55

ACCEPTED MANUSCRIPT

724

Table. 5. Fuel quality of biodiesel from Calophyllum inophyllum oil.

725

Table 6: The comparison of biodiesel production from Calophyllum inophyllum oil using

726

various process and catalyst and performance and emission analysis available in the literature.

56

ACCEPTED MANUSCRIPT HIGHLIGHTS 1. C. inophyllum appears to be a promising feedstock due to abundantly available 2. The oil is non-edible and cheap. 3. Transesterification of C. inophyllum by catalytic method produces a good yield. 4. Properties of the C. inophyllum biodiesel meets ASTM standards by and large. 5. Among various methods used for biodiesel production enzymatic conversion appears to be more attractive