Accepted Manuscript

Novel Garcinia gummi-gutta Methyl Ester (GGME) As a Potential Alternative

Feedstock for Existing unmodified DI Diesel Engine

Lingesan Subramani, M. Parthasarathy, Dhinesh Balasubramanian,

KrishnaMoorthy Ramalingam

PII: S0960-1481(18)30286-6

DOI: 10.1016/j.renene.2018.02.134

Reference: RENE 9865

To appear in: Renewable Energy

Received Date: 11 June 2017

Revised Date: 14 February 2018

Accepted Date: 28 February 2018

Please cite this article as: Lingesan Subramani, M. Parthasarathy, Dhinesh Balasubramanian,
KrishnaMoorthy Ramalingam, Novel Garcinia gummi-gutta Methyl Ester (GGME) As a Potential
Alternative Feedstock for Existing unmodified DI Diesel Engine, Renewable Energy (2018), doi:
10.1016/j.renene.2018.02.134

This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
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 ACCEPTED MANUSCRIPT

Graphical Abstract

Methanol

Garcinia Fe3O4
Raw Garcinia gummi- Immobilization
gummi-gutta
gutta oil
seed lipase Immobilized
Transesterification
process

Diesel engine Biodiesel

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1 Novel Garcinia gummi-gutta Methyl Ester (GGME) As a

2 Potential Alternative Feedstock for Existing unmodified
3 DI Diesel Engine

4 a*Lingesan Subramani, bDr.Parthasarathy M, cDr.Dhinesh Balasubramanian,

5 dKrishnaMoorthy Ramalingam

6 a,d Research Scholar, Department of Automobile Engineering, Madras Institute of

7 Technology(MIT) Campus, Anna University, Chromepet, Chennai 600 044,
8 Tamil Nadu, India.

9 b Department of Automobile Engineering, Veltech Dr.RR & Dr.SR University,

10 Chennai, Tamil Nadu, India 600062.

11 c Department of Mechanical Engineering, Mepco Schlenk Engineering College,

12 Sivakasi, Virudhunagar, Tamil Nadu, India.

13 *b Corresponding Author: E-mail address: s.lingesan@gmail.com (Lingesan

14 Subramani); Contact Number: (+91) 9626126744.

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25 Abstract

26 The present experimental study is investigated on Kirloskar make TAF-1 model CI engine powered by
27 Garcinia gummi-gutta methyl ester (GGME) biodiesel and its blends with mineral Diesel. Biodiesel is conceived
28 from Garcinia gummi-gutta seed oil via novel immobilized lipase transesterification and achieved the higher yield
29 of 93.08% at 73 hours of reaction time. Raw GGME was blended with mineral Diesel in various proportions,
30 namely, B10, B20, B30, B40, and B100 and the GGME blends were analyzed in terms of combustion,
31 performance and emission characteristics. The results show GGME B20 blend displays lower peak pressure and
32 heat release rate (HRR) than mineral Diesel. The brake thermal efficiency (BTE) for B20 blend reveals there is a
33 slight decrement at peak load. Brake specific energy consumption of GGME blends was marginally decreased for
34 increased blend concentration and at peak load B20 blend shows minor deviation against mineral Diesel. In terms
35 of tailpipe emission, B20 blend exhibits sharp decrement for HC, CO followed by smoke emission at full load
36 condition. B20 blend produces higher NOx and CO2 emissions than mineral Diesel at peak load. The above results
37 conclude that the B20 blend of GGME showcased as a chief alternative fuel for the CI engine.
38
39 Keywords: Garcinia gummi-gutta methyl ester, Immobilized, lipase transesterification, Combustion,
40 Performance, emission
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65 1. Introduction
66
67 As per the statistical report of American Energy Information and International Energy Agency world crude
68 oil consumption - surges by 2% every year. By 2030 the world-wide energy consumption will be increased by 4%
69 leading to uncertain fuel consumption rate in every 5 years. Among all the countries the Asian continent energy
70 consumption growth was predicted up to 3.7%. In order to ameliorate global warming, it is wise to lower the
71 percentage of use of fossil fuels as much as possible [1]. Compared with fossil fuels, biodiesel seems to be the
72 best solution for solving global energy crisis [2]. Currently, renewable energy crisis and higher environmental
73 pollution necessitates the search for alternative fuel sources [3-4]. There are different methods for the production
74 of biodiesel, such as dilution, pyrolysis, micro-emulsion followed by transesterification. Among them,
75 transesterification process involves the presence of triglycerides from vegetable oil and animal fat mixed with
76 alcohol or methanol and catalyst to produce tri-hydroxy alcohol and mono-alkaline ester. Compared with fossil
77 fuel, it has viable advantages like eco-friendly nature, fuel efficiency, biodegradable nature, renewable tendency,
78 fuel portability, non-toxic, better performance, good durability and minimized tail pipe emissions [5-7]. Fueling
79 of vegetable oil in CI engine is not a recent approach. Rudolf Diesel, the inventor of compression-ignition engine,
80 in prior used peanut oil as a fuel source. At the time of World War II, again the vegetable oils were utilized in
81 emergencies [8]. Vegetable oils on higher concentration, however, have a negative impact on the engine. Some
82 of the possible negative effects, namely volatility rate, fuel viscosity and cold flow of vegetable oils can choke
83 the engine parts [9].

84 I.M. Monirul et al [10] evaluated Conduct the performance and emission test carried the single cylinder
85 diesel engine using three different biodiesels with varying fuel blends namely palm, jatropha and Calophyllum
86 inophyllum methyl esters and observe exhaust emission majorly reduced for 20% palm biodiesel blend than diesel
87 and another biodiesel blend. The Calophyllum inophyllum biodiesel blends exhibit higher heat release rate and
88 peak cylinder pressure than diesel and another biodiesel blend.

89 Sunil Kumar et al [11] analysed the suitability of petro-Diesel blended with biodiesel of Jatropha curcas
90 in varying proportions in a stationary single-cylinder four-stroke CI engine. Jatropha biodiesel was mixed with
91 mineral Diesel in 0%, 5%, 20%, 50%, 80% and 100% volume. For B20 blend, test engine performance and
92 efficiency were in par with mineral Diesel. HC, CO, and CO2 emissions were found to be lower than Diesel fuel.

93 Sathiyamoorthi et al [12] carried out an experimental investigation to analyze the raw lemongrass oil
94 mixed with petroleum-Diesel fuelled in CI engine and its fuel efficiency and tailpipe emission were analyzed.
95 They noticed that BTE and BSFC results showed the same trend as that of mineral Diesel. Both carbon monoxide
96 (CO) and smoke emission were lesser compared with mineral Diesel, but NOx and CO2 emissions were higher.
97 Overall, combustion characteristics showed higher range for raw lemongrass oil.

98 Khiari et al [13] examined the effect of Pistacia lentiscus biodiesel and blends in 4.5 kW Diesel engine
99 and its combustion, performance and emission characteristics. 5, 30, and 50% of Pistacia lentiscus biodiesel were
100 blended with petroleum Diesel and its BTE was increased by about 3% compared with raw Diesel. There was a
101 reduction observed in emission levels by 17% (particulate matter), 45% (UBHC) and 25% (CO) correspondingly
102 at full load state, although fuel consumption rate and NOx emissions increased by 10% and 4% respectively.
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103 Mallikappa et al [14] investigated the behaviour of cardanol biofuel blends in double cylinder DI Diesel
104 engine and studied its fuel efficiency and tailpipe emission. They observed that the brake power increased
105 significant at 70% engine load. Results revealed that, BSEC levels were decremented by 30% with increased BP
106 (Brake power). At higher load, thermal efficiency scored higher and emission like NOx, CO, and HC showed
107 equivalent up to 20% of fuel blend.

108 Ayatallah Gharehghani et al [15] carried out an investigation on the performance, combustion and
109 emissions parameter of the conventional CI engine for waste fish oil (WFO) biodiesel and its fuel blend mixed
110 with neat Diesel. An E6 Ricardo engine was used to perform the tests under steady state conditions and engine
111 load conditions. WFO was blended in the proportions of (B25), (B50) and (B75) by volume with Diesel. More
112 stable combustion without large cycle-to-cycle variations was found to be achieved by WFO biodiesel and its fuel
113 blends. The analysis showed that, the biodiesel had about 2.92% more gross thermal efficiency and about 1.1%
114 lower combustion loss compared with mineral Diesel fuel. CO emission for the biodiesel and its fuel mixture was
115 found to be reduced by a range of about 5.2 – 27% while significant reduction by about 11.6 – 70% occurred for
116 unburnt HC emissions. However, the more efficient combustion led to an increase of about 7.2% in CO2 emission
117 and about 1.9 – 12.8% increase in NOX emission for WFO and its blends.

118 Jayashri et al [16] conducted the test with neem biodiesel and its fuel mixture fuelled in 4-stroke DI
119 Diesel engine and its output were examined in terms of performance and emission characteristics. The blend
120 mixtures were prepared in the proportions of B10, B20, and B30 % by volume with Diesel. It is observed that,
121 B10 blend resulted in higher performance and lower emissions than the other blends and Diesel. The brake thermal
122 efficiency of B10 was found to be higher than that of Diesel. Emission levels of CO, HC, and NOX were reduced
123 by 23%, 8.5%, and 22% compared with raw Diesel fuel.

124 Kakati et al [17] carried out the production, characteristics and engine performance evaluation of Kutkura
125 fruit seed oil biodiesel. The kutkura fatty acid methyl ester biodiesel was mixed with raw Diesel by B10 and B20
126 and the results showed nominal BSFC range with mineral Diesel. Increased brake thermal efficiency and reduced
127 smoke emissions were also observed. The authors concluded that, the performance level of the engine up to 20%
128 blending of kutkura biodiesel revealed superior efficiency.

129 Sanjid et al [18] studied the outcomes of Brassica juncea methyl ester (mustard biodiesel) and its fuel
130 blends in Diesel engine by both performance and exhaust emissions. Mustard biodiesel showed superior properties
131 compared with the other conventional biodiesels. MB10 blend and MB20 blend of mustard biodiesel were
132 employed for the performance and emission tests. Both the blends, MB10 and MB20 gave 8–13% superior fuel
133 consumption rate and brake power reduced by 7 – 8% compared with Diesel. The MB blends when compared
134 with Diesel exhibited NO higher by (9-12%), HC lower by (24-42%), CO reduced by (19-40%) and finally noise
135 emission by (2-7%).Thus, the authors were able to conclude that MB10 and MB20 blends of fuel were best suited
136 to CI engine.

137 The present research work is about the newly discovered Garcinia gummi-gutta methyl ester extracted
138 from gracinia seeds, as a novel alternate biodiesel for powering the Diesel engine. Globally, none of the researcher
139 used this GGME as a fuel source for DI Diesel engine but only the oil extraction and fuel characterization could
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140 be made by some of the research persons. To conduct this experimental investigation Garcinia gummi-gutta seed
141 was obtained from Thrissur district in Kerala. In order to increase the GGME yield percentage the novel lipase
142 immobilization concept was implemented in transesterification process. Previously, GGME and its blends meet
143 the ASTM standards. Initially, Garcinia gummi-gutta methyl ester (GGME) was easily mix with mineral Diesel
144 and five fuel blends was adapted namely 10, 20, 30, 40 and 100 percent by volume basis. Moreover, the engine
145 combustion, performance and tailpipe emission were investigated for five GGME test fuels including mineral
146 Diesel then the test fuel results were compared with mineral Diesel.

147 2. Materials and methods

148 2.1 Biological background of Garcinia gummi-gutta species

149 The main significance of this assessment is to evaluate the clearer of biodiesel generation from Garcinia
150 gummi-gutta seed-based oil as an alternative resource of fuel to alleviate world fossil fuel demand. Garcinia
151 gummi-gutta is a renowned Malabar tamarind named “Kodampuli” in Malayalam belonging to the family
152 clusiaceae, and the tree population is denser in evergreen forest areas of Western Ghats, particularly from
153 Travancore region and more over it is found in Nigerian forest. Further, the other parts the tree, namely leaves,
154 bark, root, flower and sap also have more medicinal properties and they add advantage to medical field. In larger
155 context the seed extracted oil is used for ayurvedic purposes. Garcinia gummi-gutta seed oil a sustainable, more
156 feasible, non-edible, ecofriendly and novel biodiesel to play the role of the best alternative to CI engine. This
157 novel oil does not have any impact on commercial agreement as a fuel source. None of the researchers have done
158 the experiment by using Garcinia gummi-gutta fruit seed oil as a non-traditional source for CI engine. The kernel
159 of 95% mixed seeds contains larger quantity of oil, i.e., about 42% yield. There are three different modes of
160 extraction process employed to extract the oil by using kernel: Boling method, Solvent extraction method and
161 mechanical expeller method. Compared with the mechanical expeller method, the remaining two methods result
162 in lesser oil yield up to (30%).Hence, mechanical expeller method was selected to improve the oil yield from
163 Garcinia gummi-gutta seed. The test fuel properties of Garcinia gummi-gutta methyl ester was showed in Table
164 1. The physicochemical properties and chemical composition of Garcinia gummi-gutta were displayed in Table
165 2 and Table 3.

166 2.2 Garcinia gummi-gutta seed oil preparation and extraction process

167 Initially the seeds are collected at National Bureau of Plant Genetic Resource (NBPGR) zone, Thrissur
168 district, Kerala. Then they are sorted based on the size, further the seeds are directly dried in sunlight for 2-5 days.
169 After the removal of moisture content in the seeds, the seeds are roasted at 101°C for 12hr. Then, the seeds are
170 crushed to produce fine powder and the oil is extracted from the powdered seeds using mechanical expeller
171 method. By using this method, marginally higher yield is obtained up to 40% for 1 kg of Garcinia gummi-gutta
172 seed. Various properties like density, calorific value, kinematic viscosity, acid value, cetane number, water
173 content, flash point & ash content are measured based on the ASTM standards. In the present study, raw GGME
174 biodiesel is selected and it is blended with the mineral Diesel on volume basis. The oil extraction process of raw
175 gracinia is illustrated in Fig.1.

176
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177 2.3 Biodiesel production process of Garcinia gummi-gutta seed oil with immobilized nano catalyst approach

178 Transesterification process of novel Garcinia gummi-gutta seed oil was performed by lipase immobilized
179 Fe3O4 catalyst. Primarily, lipase immobilized Fe3O4 catalyst (Fe3O4 + Thermomyces lanuginosus lipase) was
180 purchased from Center for Nanoscience and Technology, Anna University Chennai, Tamil Nadu, India. In order
181 to anticipate higher biodiesel yield, the renowned approach of immobilization technique was furnished for
182 transesterification of raw Garcinia. By immobilization, chemically bind strategy outcome was created to invent
183 the novel core-shell structures alliance with Fe3O4 nanoparticle as core and enzyme catalyst as shell. To enhance
184 the catalytic activity, iron oxide magnetic nanoparticles were prepared by co-precipitation method and
185 Thermomyces lipase (TL) were immobilized into Fe3O4 nanoparticle. This reaction yields a novel enzyme
186 immobilized Fe3O4 magnetic Nano particle. Initially, transesterification reaction was done by using 150ML
187 shaking flask under 50ºC on a reciprocal shaker.

188 Equivalent amount of 10g of raw Garcinia oil was mixed with TL linked iron oxide nanoparticle and
189 three times the methanol was added to the solution up to 1.5g. Then the residual methanol content was distilled
190 off completely with the help of the evaporator at 65ºC under vacuum condition. After the evaporator process the
191 conversion of Garcinia oil to its methyl ester was reached with optimized time, temperature then the biodiesel
192 efficiency was higher by the impact of batch process. Batch process results that lipase immobilized
193 transesterification process deserves higher yields of 93.08% Garcinia gummi-gutta methyl ester at 74hr of reaction
194 time. Subsequently, the collected immobilized TL was used with fresh substrate material for each cycle. Then
195 the stability of immobilized TL was analyzed by using batch transesterification of Garcinia oil with methanol
196 solution.

197 2.4 Test Engine Set-up

198 To analyze the combustion, performance and emission parameters of GGMS, experiments were
199 conducted in single cylinder TAF-1 model: kirloskar engine. This type of test engines was preferred since it is
200 widely used in industrial, agriculture and generator applications. It is an air-cooled engine, coupled with eddy
201 current dynamometer along with electrical resistance besides a dynamometer controller. The rated power and
202 constant speed of this engine is 5.2 kW at 1500rpm. Five gas analyzers QRO-402 model and QROTECH Co Ltd.,
203 Korea make analyzer were used to measure the concentration of tailpipe emissions, namely CO, CO2, NOx and
204 HC. Smoke emission was examined by an AVL 437 C smoke opacimeter. Highly equipped flow meter was
205 employed to measure the flow rate in every 20S. A piezo-electric pressure transducer of 7063-A model and kistler
206 make was installed to observe the cylinder pressure; to evaluate the pressure versus crank angle a flywheel was
207 linked with crank angle encoder that was fitted on the flywheel. A combustion analyzer (SeS) was installed. Since
208 the necessity of the analyzer, the encoder and charge amplifier kistler instruments AG, Switzerland make to host
209 the input signals from the test engine is illustrated in Fig 2. The test engine specification is illustrated in Table 4.

210 2.5 Uncertainty analysis

211 The uncertainty and error analysis are significant to ascertain the positive agreement in the experimental
212 measurements, various performance parameters and errors. By using the Holman principle of uncertainty
213 propagation [19], the analysis on certainty was made. So many factors like the test elevation, calibration,
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214 environment factor, reading, relative state, device selection and finally observation of uncertainties and errors.
215 The calculated uncertainty of various devices along with parameter is listed in Table 5 and Table 6. The value of
216 total uncertainty is derived as shown below:

217 Total uncertainty of the experiment

218 = U load 2  U BTE 2  UUBHC 2  U NOx 2  U CO 2  U Smoke 2  U Pressure 2

219 = + 1.491%

220 3. Results and Discussion

221 3.1 Brake thermal efficiency

222 The thermal efficiency was focused as a most eminent performance characteristic for the test engine. In
223 general, it is defined as the combination of net indicated thermal efficiency and mechanical efficiency. Violability,
224 BTE of the Diesel engine is an independent variable to shorten heating value and BSFC of the test fuel. Fig 3
225 shows the variation of Brake Thermal Efficiency (BTE) for mineral Diesel and GGME- Diesel blends. In general,
226 BTE is influenced by distinct fuel characteristics like calorific value, oxygen content, cetane index and kinematic
227 viscosity. From the plot, it is observed that mineral Diesel fuel exhibits highest level of BTE throughout the engine
228 load spectrum followed by B10, B20, B30, B40 and B100 blends. It was inferred that, higher percentage of
229 GGME in Diesel fuel led to marginal drop in the thermal efficiency which occurred due to higher viscosity of the
230 fuel influenced inferior air entrainment and fuel spray which strongly affected the combustion process in the test
231 engine. In addition, lesser energy content of the biodiesel also influenced in the combustion. B10 blend exhibited
232 better results compared with the other blends due to air-fuel interaction, atomization of fuel, lower viscosity and
233 higher vaporization phase. The overall BTE trend revealed, up to 75% load condition. In terms of performance
234 B20 blend was similar to B10 blend; however, at 100% load, BTE dropped by 2.31% comparatively. From the
235 observation, it was found that BTE was higher for mineral Diesel (30.69%), followed by B10 (28.99%), B20
236 (28.32%), B30 (27.09%), B40 (26.87%), and B100 (25.68%) comparatively. For all the GGME–Diesel and B100
237 blends, BTE was lower than mineral Diesel fuel. Similar agreements were exhibited for various biodiesel blends
238 [20-25]. There are some possible reasons for lower BTE followed by higher BSEC due to the effect of lesser
239 indicated work, higher pumping and friction losses. At higher loads, these losses were eliminated therefore higher
240 indicated work with higher fuel constraint.

241 3.2 Brake Specific Energy Consumption

242 BSEC validates the quantum of energy taken from the input test fuel on the basis of shaft power acquired
243 by the test engine. In general, cylinder wall temperature of the test engine is increased; correspondingly energy
244 consumption will decrease with increase in power output for the complete test fuel blends. Fig.4 shows Brake
245 Specific Energy Consumption (BSEC) with respect to applied brake power for all the GGME biodiesels and
246 mineral Diesel. Compared with B100, B10 indicates descent energy consumption about 25.29% and 15.46% at
247 lower load and higher load conditions respectively. This is due to fuel viscosity and calorific value of B10 mixture
248 and it seems to be closer to mineral Diesel. It is also observed that BSEC decreases with increase in load condition
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249 due to minimal heating value, higher mass flow, and viscosity of the biodiesel. B100 blend shows higher BSEC
250 of 33.15 MJ/kWh and 14.91 MJ/kWh at part load and full load conditions respectively. At peak load condition
251 signify BSEC of B100 is nearly 22.07 % higher than that of mineral Diesel. This could be the reason of enhanced
252 BTE followed by lesser ignition delay period. This is in agreement with previous findings with various biodiesels
253 [20-23]. In addition, greater density of GGME yields higher fuel discharge for identical movement of plunger
254 associated with the fuel pump. This might be the reason for higher BSEC attainment for GGME blend.

255 3.3 Cylinder pressure rise

256 During the compression operation in CI engines, the highest cylinder pressure was advanced by the test
257 fuel and it mainly depends on the fast burning rate of the test fuel that occurs during the premixed combustion
258 phase. Cylinder pressure plays a significant role in probing the combustion characteristics. The key factors that
259 are involved in manipulating the cylinder pressure variation includes air-fuel reaction rate, cetane index and
260 viscosity, increasing ID, larger fuel accumulation in Premixed Combustion Phase (PCP), faster combustion rate
261 and higher peak pressure. Fig.5 shows the plot of in-cylinder pressure (bar) versus crank angle (degree) at variable
262 peak load spectrum. It is observed that, the cylinder pressure subjected to entire GGME- Diesel blend reveals
263 lower pressure range than that of mineral Diesel fuel, elsewhere higher percentage of blend results in significant
264 drop in the trend. Among all the blends, B100 results in lower peak pressure, while higher peak pressure is noticed
265 for mineral Diesel. This is, perhaps due to poor evaporation rate, which is the result of lower calorific value, higher
266 density and poor atomization of GGME blends [26-27]. It might be influences in vaporization and fuel-air mixing.
267 Finally, cylinder pressure for all the GGME blends exhibits declined range in compared with mineral diesel fuel.
268 This is because of Garcinia gummi-gutta methyl ester fuel properties and its blends results in higher cetane number
269 is compared with mineral diesel fuel. So, due to this reason ignition delay of the biodiesel was lowered followed
270 by lessened fuel accumulation during the combustion stroke.

271 3.4 Heat release rate variation

272 The model is shown in equation 1

dQn   dV   1 dP 
273  P  V   Qlw . (1)
d   -1 d    -1 d 

274

dQn
275 Where, = Net heat release rate (J/ºCA), V=Instantaneous volume in (m3), θ = Crank angle in degree, γ =
d
• •
276 Ratio in specific heats in Cp/Cv(KJ/kgK), P = Instantaneous pressure in (N/m2). The variables Q lw . Q lw and

dQn
277 = Blow by loss, γ = Temperature are assessed by Rakopoulas [28]. The gross HRR is consider as
d

dQg dQn dQlw

278 = + (2)
dθ dθ dθ
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dQlw
279 In the above equation is related to sum of heat transfer rate to combustion walls [29]. By using some
d
280 correlation associated with the first law of thermodynamics, model equation is being used to calculate the HRR
281 at every crank angle. Fig 6 exhibits the plot of heat release rate (HRR) of GGME blends with regard to crank
282 angle. From the plot it was noticed that the influence of GGME and its various blending ratios does not have
283 consistent HRR trend throughout the crank angle. On account of higher fuel vaporization phase was occurred
284 during the ignition delay period. At initial stage combustion HRR peaks has negative value for all the test fuel
285 blends. However, the combustion started, the HRR peak shows positive value and precedes a similar trend for DI
286 Diesel engine. This was inferred by simultaneous process of premixed and diffusion combustion phase. Lower
287 HRR prevails due to minimal calorific value, higher cetane number and shortened ignition delay [30]. It is also
288 occurring due to the influence of unsaturated fatty acid that leads to aerosolized biodiesel into small nuclei leading
289 to larger spray angle compared with mineral Diesel. By equate with mineral Diesel HRR for biodiesel blends
290 shows B10 (9.77%), B20 (10.25%), B30 (17.32%), B40 (18.12%) and finally B100 (18.47%) respectively.
291 Meanwhile, during the diffusion burring phase of GGME-Diesel blends inferred higher in range with mineral
292 Diesel. This could be attributed to excess O2 content followed by increased heating value in the fuel [31]. It is also
293 observed that during the diffusion combustion phase, the HRR of B20 and B40 were found to be higher than
294 mineral diesel fuel. This could be attributed to earlier start of injection followed by lowered peak HRR and more
295 diffusion burning. Heat release rate of B10 blend stays closer to Diesel due to its calorific value and it is almost
296 nearer to mineral Diesel.

297 4. Unburned hydrocarbon (UBHC)

298 The level of completeness in fuel combustion can be indicated by unburned hydrocarbon emission
299 UBHC; is a direct indication of incomplete combustion while CO is an indirect source. Generally, HC emissions
300 are less when fueled with biodiesel blends because of higher cetane index and oxygen content [32-38]. Some
301 intensity results even showed HC reduction up to 65% in comparison with Diesel [33-34, 39]. With increasing
302 percentage of biodiesel [36] and increasing chain length [37, 42], HC emission was found to reduce when the
303 amount of oxygen content and cetane number increased, delay period was reduced which caused increase in the
304 percentage of fuel accumulation in the combustion chamber followed by lesser fuel loss, improved rate of
305 combustion and lesser quenching loss resulting in lowered HC emissions [40-42]. The plot of UBHC (ppm)
306 against brake power (kW) is shown in Fig 7. For increasing concentration of mineral Diesel, B10, B20, B30 and
307 B40 blends results marginal increment in the UBHC emission was observed at part and full load spectrum. This
308 could be due to the existence of oxygen molecules in the B100 fuel blend yields, enhanced combustion followed
309 by lesser UBHC formation. Further, oxygen content of GGME enhances certain favorable effects, namely post-
310 flame oxidation, superior flame speed and higher air-fuel mixing rate. The influence of fuel-rich regions revealed
311 improved oxidation of unburned UBHC, thereby reducing UBHC emission. At peak load spectrum, higher UBHC
312 was noticed for mineral Diesel (66.1 ppm), B10 (60.98 ppm), B20 (59.9 ppm), B30 (59.2 ppm), B40 (58.1 ppm)
313 and finally B100 (56.8 ppm) accordingly. Higher levels of UBHC emission were attributed to higher viscosity,
314 density, poor atomization of the fuel blends. By evaluate with mineral Diesel, all the GGME blends causes adverse
315 effect on the declined range of UBHC emission; as a result of integrated reaction of higher cetane number and
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316 higher-cylinder pressure. Thus, higher cetane number of the fuel liberate lessened burning delay period thereby
317 improving the combustion followed by lowered UBHC formation.

318 4.1 Carbon monoxide (CO)

319 Whenever there is deficit oxygen for transforming the carbon to carbon dioxide, the hydrocarbon
320 molecule does not get combusted completely resulting in tangible carbon content ending up as carbon monoxide.
321 In addition, various discrepancies like local rich regions, poor mixing and partial combustion act as a CO
322 formation resource. CO emissions were found to reduce with increasing chain length [41, 42] increasing cetane
323 number [43], engine speed [44]. When the amount of oxygen increases, these discrepancies can be overcome by
324 complete combustion and lesser CO formation can be achieved [35, 43]. Fig.8 depicts the carbon monoxide
325 emission versus brake power for all the fuel GGME Diesel blends. The data shown in figure 8, for increasing fuel
326 blend at decrement and increment engine loads has negligible issue on the carbon monoxide emission as a result
327 of higher lean mixing rate followed by deficit air [45, 46]. This event was attributed to O2 molecules in the test
328 fuel promoting the combustion of CO in higher extent [47]. Normally, BSFC is compensated by higher oxygen
329 content that facilitates higher homogenous mixture which in turn forms less fuel – rich zones, leading to complete
330 combustion. In addition, higher cetane index of the fuel yields, shorter ignition delay resulting in improved
331 combustion. For B20 blend CO emission was ultimately lower due to saturated level and increased carbon chain
332 length. By inspecting the various ranges of different fuels, mineral Diesel and B10 have higher value at peak load.

333 4.2 Carbon dioxide (CO2)

334 Carbon dioxide is an elementary source of GHG (Green House Gas) emission which is a commodity of
335 complete combustion of a HC fuel (Combination effect of both CO2 and H2O leads to complete combustion
336 process). CO2 is a very essential gas for plants and trees for their growth and photo-synthesis. When a bio-fuel is
337 combusted, the CO2 that is emitted into the atmosphere is simply re-circulated and do not add to the atmosphere,
338 whereas combustion of fossil fuels releases carbon atoms that were stored in subterranean region and CO2 gets
339 added up into the atmosphere [48]. Biodiesel fuel combustion emits higher CO2 due to higher O2 content and
340 relative lower C/H ratio. Some studies on the contrary were also reported where the biodiesel combustion lowered
341 the CO2 emission in comparison to Diesel fuel combustion [49-50]. Fig.9 portrays the CO2 emission versus applied
342 brake power for all the test fuels. The plot shows that increasing concentration of GGME blends cause higher CO2
343 emission for the entire engine load spectrum. At peak load condition, it was noticed that CO2 emission was higher
344 for B100 (3.99%) followed by B40 (3.89%), B30 (3.77%), B20 (3.8%) and B10 (3.7%) in comparison with
345 mineral Diesel (3.51%). The influence of O2 content in the fuel facilitates complete combustion of the fuel.
346 Moreover, increased ppm of CO2 emission might be nullified by the natural sources through the plantation of the
347 biodiesel species in the earth. Earlier combustion, lower heating value, higher expansion and more reaction time
348 for converting CO to CO2 are all the possible parameters resulting in higher CO2 emission formation.

349 4.3 Nitrogen oxides (NOx)

350 CI engines are prone to NOx formation tendency since they operate at higher excess air ratios. Oxides of
351 nitrogen are composed of nitrogen dioxide (NO2) and nitrogen oxide (NO). Production of NOx chiefly depends
352 on O2 reactions, cylinder temperature and equivalence ratio [51]. Higher cetane indexed fuel reduces the
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353 possibility of pre-mixed combustion phase by deteriorated delay period followed by lower NOx formation [52-
354 53]. The various reasons associated with higher NOx emissions are (i) lowered radiation heat transfer, (ii) higher
355 adiabatic flame temperature (iii) faster burning rate and (iv) availability of inbuilt excess oxygen [54]. Fig.10
356 displays the variation of Nitrogen oxide (NOx) with respect to brake power for all the GGME-Diesel blends. For
357 the entire load spectrum, increased concentration of blends reveals higher NOx emission and reaches their highest
358 level at peak load. This could be the reason for Zeldovic mechanism, higher peak pressure, greater In-cylinder
359 temperature, availability of oxygen [55] and may be due to lower cetane rated fuel followed by rich air/fuel ratio.
360 The variation at part load and full load conditions displays higher NOx emission signifying the availability of rich
361 core region revealing that excess fuel was supplied by the injector. Thus, consistent higher temperature prevails
362 because of oxygen enrichment in the blends [56]. These are the feasible factors for higher NOx emission for
363 GGME – Diesel blends. Meanwhile, B100 and B40 blend shows higher NOx emission due to combined effect of
364 higher combustion rate owned by rapid combustion. The optimized B20 blend reveals 15.93% lowered NOx
365 emission against B100 blend.

366 4.4 Smoke opacity

367 Smoke emission from the CI engine depends mainly on engine load because with increasing engine load,
368 air-fuel ratio reduces as a result of more fuel taking part in combustion which overall contributes to the overall
369 pressure of more rich mixture zones and higher diffusion burning causing excess smoke [57]. Factors like high
370 density and high viscosity tend to increase the smoke emissions, especially at higher engine loads, where reaction
371 time is less and fuel accumulation is more [58]. There is always a trade-off existing between NOx and smoke
372 emissions being lower and is vice-versa. This is because temperature, air-fuel mixing, fuel atomization, diffusion
373 combustion and ignition delay play “repulsion effect” between NOx and smoke emission. Fig.11 shows the
374 variation of smoke opacity with brake power for all the test fuel blends. From the plot, it was cleared that, in
375 comparison with diesel, lowered smoke emissions were observed for higher GGME blend ratios at entire engine
376 load spectrum. In thus, at peak load higher smoke emission was acquired for mineral Diesel followed by B10
377 (72.8 HSU), B20 (71.85 HSU), B30 (69.15 HSU), B40 (62.85 HSU) and the lowest smoke is observed in case of
378 B100 (60.7 HSU). This indicates lower stoichiometric ratio at peak load condition, higher percentage of fuel in
379 the combustion chamber which in turn gives greater unburned fuels in the tailpipe emission [59]. Moreover, higher
380 smoke opacity is owing to numerous parameters like mismatched injection, worn, clogged, lack of injection timing
381 and injection pressure and some fault arising in fuel and air filters. This also can be attributed to lowered flame
382 temperature and poor mixing rates of the biodiesel besides the presence of aromatic component, lower ignition
383 delay and higher soot oxidation [60]. On the contrary, at peak load the smoke produced by B40(62.85 HSU) and
384 B100(60.7 HSU) blends were marginally lower in comparison with mineral Diesel signifying the influence of
385 better combustion, higher oxygen presence, and lower volatility of the fuel [61].

386 Conclusion:

387 The current article presented a novel approach of lipase-based catalyst immobilized transesterification
388 process. The prime objective of this experimental research work is to investigate the combustion, performance
389 and tailpipe emission characteristics of a single cylinder, kirloskar make TAF-1 model, four strokes, and air-
390 cooled DI Diesel engine fueled with Gracinia-gummi gutta biodiesel and with other fuel blends. Various physical
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391 and chemical properties of GGME blends were tested with ASTM standard methods. The following conclusions
392 were drawn based on the experimental results as follows:

393  Garcinia gummi-gutta seed oil was extracted by mechanical expeller and transesterification reaction was
394 performed with novel lipase enzyme linked bio-catalyst reaction and it yields 93.08% of GGME at 74hr
395 of reaction time.
396  In terms of engine performance raw GGME and its blends displayed lower BTE trend and B20 exhibits
397 28.32% decreasing in BTE in comparison with mineral Diesel fuel and for BSEC B20 blend shows minor
398 deviation against mineral Diesel at peak load.
399  Raw GGME and its blends caused lower trend in cylinder pressure and HRR owing to poor evaporation,
400 lower CV followed by lack of atomization which results in shortened ID and period.
401  Raw GGME and its blends lowered the CO emission because of its higher lean mixture and improved
402 O2 content. Lower UBHC and smoke opacity were observed for GGME-Diesel blends due to lower
403 ignition delay period, higher O2 presence followed by complete combustion of the test fuel. The tailpipe
404 emission level of NOx and CO2 were comparatively higher than mineral Diesel fuel owing to higher
405 temperature prevails inside the cylinder and early combustion.
406  Finally, B20 blend found to be exhibiting a trend closer to mineral Diesel trend, which was a good sign
407 for DI Diesel engine at 1500 rpm.

408 Based on the above evidences, Garcinia gummi-gutta seed oil was found to be a potentially powerful
409 biodiesel feedstock for DI Diesel engine. Thus, GGME blend B20 (80% Diesel+ 20% biodiesel) showcased as a
410 chief alternative fuel profile for Diesel engine in the research field.

411 Acknowledgement

412 The authors express their gratitude to the University Grants Commission (UGC) for providing financial
413 grant for this research work. The corresponding authors also would like to thank the Head of the Department and
414 the staff members of Automobile Engineering Department, MIT campus, Anna University, Chennai, for lending
415 support during experimentation and the Centre for Nanotechnology, Anna University for helping in the process
416 of characterization of nanoparticles.

417

418

419

420

421

422

423

424
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425 Abbreviation

CI Compression Ignition

CO Carbon monoxide

NOx Oxides of Nitrogen

CO2 Carbon dioxide

HC Hydro Carbon

BSEC Brake Specific Energy Consumption

BTE Brake Thermal Efficiency

GGME Gracinia gummi-gutta Methyl Ester

ASTM American Society for Testing and Materials

HRR Heat Release Rate

UBHC Unburned Hydrocarbon

H2O Water

HSU Hartridge Smoke Units

O2 Oxygen

CA Crank Angle

426

427 Symbols and Nomenclature

v Instantaneous heat release rate, N/m2

P Instantaneous cylinder volume

θ Crank angle in degree

 Specific heat in ratio (Cp/Cv), KJ/kgK

• Blow-by loss
Q lw

dQg Gross heat release rate

dθ
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dQn Net heat release rate

dθ

dQlw Combustion chamber walls heat release

dθ rate

428

429

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List of figure captions

Fig 1 Oil extraction process of raw GG oil from Garcinia tree seed of (a) Gracinia Tree (b) Younger Gracinia fruit (c) Younger
Gracinia seed (d) Ripe Gracinia fruit (e) Ripe Gracinia seed (f) Gracinia seed collection (g) Dried seed (h) Mechanical
Expeller (i) Gracinia seed oil

Fig 2 Experimental kirloskar engine setup for GGME investigation

Fig 3 Variation of Brake Thermal Efficiency (BTE) with regard to Brake power for various GGME fuel blends

Fig 4 Variation of Brake Specific Energy Consumption (BSEC) with regard to Brake power for various GGME fuel blends

Fig 5 Variation of cylinder pressure with regard to crank angle for various GGME fuel blends

Fig 6 Variation of heat release rate with regard to crank angle for various GGME fuel blends

Fig 7 Variation of UBHC with regards to brake power for various GGME fuel blends

Fig 8 Variation of Carbon monoxide with regards to brake power for various GGME fuel blends

Fig 9 Variation of carbon dioxide with regards to brake power for various GGME fuel blends

Fig 10 Variation of oxides of nitrogen with regards to brake power for various GGME fuel blends

Fig 11 Variation of smoke opacity with regards to brake power for various GGME fuel blends

Fig.1 Oil extraction process of Raw Garcinia gummi-gutta oil from Garcinia tree seed of (a) Gracinia Tree
(b) Younger Gracinia fruit (c) Younger Gracinia seed (d) Ripe Gracinia fruit (e) Ripe Gracinia seed (f) Gracinia
seed collection (g) Dried seed (h) Mechanical Expeller (i) Gracinia seed oil
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Fig. 2 Experimental kirloskar engine setup for GGME investigation

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Fig. 3 Variation of Brake Thermal Efficiency (BTE) with regard to Brake power for various GGME fuel blends
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Fig. 4 Variation of Brake Specific Energy Consumption (BSEC) with regard to Brake power for various GGME
fuel blends
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Fig. 5 Variation of cylinder pressure with regard to crank angle for various GGME fuel blends
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Fig. 6 Variation of heat release rate with regard to crank angle for various GGME fuel blends
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Fig.7 Variation of UBHC with regards to brake power for various GGME fuel blends
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Fig.8 Variation of Carbon monoxide with regards to brake power for various GGME fuel blends
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Fig.9 Variation of carbon dioxide with regards to brake power for various GGME fuel blends
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Fig.10 Variation of oxides of nitrogen with regards to brake power for various GGME fuel blends
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Fig.11 Variation of smoke opacity with regards to brake power for various GGME fuel blends
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Highlights

 Raw Garcinia gummi-gutta seed oil was extracted by mechanical expeller and achieved the higher yield
of 93.08% at 73 hours of reaction time.
 Transesterification was done by novel lipase enzyme linked biocatalyst reaction.

 Raw GGME and its blends displayed lower BTE and higher BSEC at peak load condition in comparison
with mineral Diesel.

 Raw GGME obtained lower trend for In-cylinder pressure and Heat Release Rate (HRR) in comparison
with mineral Diesel.

 Higher CO2, UBHC, NOx, and smoke opacity along with lowered CO emission were observed for raw
GGME and its blends at peak load condition.
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List of Various Table Caption

Table 1 Properties of Garcinia Gummi-gutta methyl ester

Table 2 Physicochemical properties of raw Garcinia Gummi-gutta seed oil

Table 3 Chemical composition of Garcinia Gummi-gutta seed oil

Table 4 Kirolskar engine specification

Table 5 Uncertainty of various measuring instruments

Table 6 Uncertainty of different measuring parameters

Table1

Properties of Garcinia Gummi-gutta methyl ester

Sl.No Test Fuel Properties Units Diesel B10 B20 B30 B40 GGME

B100

1. Density @ 15°C g/cm3 0.830 0.871 0.863 0.861 0.847 0.878

2. Viscosity @ 40°C mm2/s 3.2 4.62 4.51 4.33 4.15 4.83

3. Flash point °C 70.0 93.6 90.7 88.4 85.6 96.2

4. Cetane Number - 46 51.2 50.7 50.3 49.5 52

5. Higher heating value MJ/Kg 43.82 40.52 40.81 41.28 41.61 40.28

6. Ash Content % 0.01 0.026 0.025 0.023 0.021 0.03

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Table 2

Physicochemical properties of raw Garcinia Gummi-gutta seed oil

Sl.No Component GG seed oil

1 Color Pale yellow

2 Specific gravity 0.89

3 Refractive Index 1.462

4 Acid Value (mg NaOH/g) 5.04

5 Saponification value (mg KOH/g) 145.36

6 Free fatty acid (%) as oleic acid 11.50

7 Iodine value (g/100 g) 131.0

8 Peroxide value (meq/g) 3.73

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Table 3

Chemical composition of Garcinia Gummi-gutta seed oil

Sl.No Fatty acid Fatty acid Fatty acid Carbon EI Mol. Pubchem IUPAC name Class of
methyl ratio mass(m/z) Formula compound
number CID/CAS
ester

1. 10,13- Myristic 27.285:50 14:0 270(M+),2 C17H 34O2 267650-23-7 Tetradecanoic Saturated
trimethyl acid 42,227,143 acid,10,13-
myristate ,74 dimethyl-, methyl
ester

2. Methyl Linoleic 1.54:50 18:2 294(M+),2 C19H34O2 900336-44-2 Methyl 10-trans, Poly-
linoleate 64,234,109 unsaturated
acid 12-cis-
,67
octadecadienoate

3. Methyl Oleic acid 19.51:50 18:1 296(M+),2 C19H36O2 900336-41-6 Methyl 13- Mono-
oleate 66,223,83, octadecenoate unsaturated
55

4. 16 Margaric 1.055:50 17:0 298(M+),2 C19H38O2 900336-38-6 Methyl 16- Saturated

dimethyl 25,241,143 methyl-
acid
margarate ,87 heptadecanoate

5. Methyl Arachidic 0.61:50 20:0 326(M+),2 C21H42O2 1120-28-1 Methyl Saturated

83,269,227 eicosanoate
arachidate acid
,74
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Table 4

Kirolskar engine specification

Make Kirolskar TAF-1

Type Four stroke, single cylinder DI diesel engine

Cooling type Air Cooled

Bore 86.6 mm

Stroke 112 mm

Compression ratio 17.6:1

Rated power and Rated 5.2 kW at 1500 rpm

Speed

Injection timing 23deg before TDC

Nozzle 0.3mm and 1 nozzle

Piston geometry Hemispherical

Swept volume 662 cc

Angle of fuel spray 120 deg

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Table 5

Uncertainty analysis of various measuring instruments

Sl.no Measured instrument Percentage

uncertainty (%)

1. EGT 0.17

2. Smoke Meter 1.01

3. Pressure transducer 0.28

4. Tachometer 0.40

5. Manometer 1.7

6. Stopwatch 0.4

Table 6

Uncertainty for different measuring parameters

Sl.No Measured parameters Parentage

uncertainty (%)

1. Load 0.3

2. BTE 1

3. UBHC 0.2

4. NOx 0.1

5. CO 0.2

6. Smoke 0.21

7. Pressure 1