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BiodieselproductionusingCalophylluminophyllum(Tamanu)seedoilanditscompatibilitytestinaCIengine

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Biodiesel production using Calophylluminophyllum (Tamanu) seed oil and its compatibilitytest in a CI engine

K. Dinesh, A. Tamilvanan, S. Vaishnavi, M. Gopinath & K.S. Raj Mohan

To cite this article: K. Dinesh, A. Tamilvanan, S. Vaishnavi, M. Gopinath & K.S. Raj Mohan(2016): Biodiesel production using Calophyllum inophyllum (Tamanu) seed oil and itscompatibility test in a CI engine, Biofuels, DOI: 10.1080/17597269.2016.1187543

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Biodiesel production using Calophyllum inophyllum (Tamanu) seed oil and itscompatibility test in a CI engine

K. Dinesh a,b, A. Tamilvananb, S. Vaishnavic, M. Gopinath a and K.S. Raj Mohan a

aDepartment of Chemical Engineering, College of Engineering Studies, University of Petroleum and Energy Studies, P.O. Bidholi Via-PremNagar, 248007 Dehradun, India; bDepartment of Mechanical Engineering, Kongu Engineering College, Erode, India; cDepartment ofBiotechnology, Karpaga Vinayaga College of Engg., and Tech., Chennai, India

ARTICLE HISTORYReceived 11 February 2016Accepted 9 April 2016

ABSTRACTTamanu-based biodiesel can be used as a non-conventional fuel blended with conventionalfuel in a compression ignition engine without any need for modification in engine design. Thethree main processes involved in production of biodiesel are removal of OH group by H2SO4

(acid) and KOH (base), and removal of soapy water. The molar ratios tried in this process were4:1 to 10:1 and the yield was maximum at 6:1 (86.15%). In this present study, production ofbiodiesel from Tamanu oilseeds, its performance analysis and emission characteristics in a CIengine were extensively studied. Prepared Tamanu-based biodiesel was used in a four-stroke CIengine and performance analysis was done. The blend proportions used in the diesel enginewere 10�40 wt.% biodiesel (B10, B20, B30 and B40). Analysis of emissions such as NOX, CO, andHC from a CI engine has shown that the biodiesel blends produced fewer emissions than thatof commercial diesel. Results revealed that there is a substantial reduction of emissions and anincrease in performance of the biodiesel blends tested. Moreover, the amounts of toxicpollutants emitted from the biodiesel blends are significantly less when compared tocommercial diesel.

KEYWORDSBiodiesel; CI engine;emission; glycerol; Tamanuoil

Introduction

Worldwide energy demand is on the rise due to expan-sion of the industrial base, output in the developingcountries and ever increasing population. The world’senergy demands for the past two centuries has reliedheavily on conventional fuels, more than 90% of whichis consumed by energy generation and transportation.There is an increased restriction on the release of CO2,CO, NOX and S- containing residues because it is wellknown that they are responsible for global warming.[1]Fossil fuels consumption in India is increasing everyday. The price of petroleum and diesel is also increas-ing along with crude oil-based products. To meet thedemand in India the focus on non-conventional fuelshas increased.

Most transport vehicles run on petrol or diesel andthey emit CO2 leading to global warming and green-house gases which affect climate change. There is con-cern that at the present consumption rate of crude oil,crude reserves will be depleted in a few decades.[2]There is a need for alternative fuels which can replacediesel fuels in vehicles without demanding much changein engine design. This need has led to an increased inter-est in alternative and renewable resources to meet theenergy demands of the future. Exploration of biomass asan energy source to produce liquid fuels has been onefocus, and one such biomass source is oil seed crops. Oils

of seed crops have long been considered as alternativefuel. However oil obtained from the seed crops has anup to 10 times higher viscosity than diesel fuel, as well asan offensive odor in the exhaust, which limits their directapplication in engines because they damage parts andreduce engine life.[3]

This problem has been addressed by converting theoils into esters by transesterification with various alco-hols. Transesterified oils are called biodiesel with refer-ence to their fuel properties being similar to that ofdiesel.[4] Biodiesel is one of the most promising alter-natives to fossil fuels. Biodiesel, produced from severalsources, when tested in conventional engines haveshowed promising results of a significant decrease inemissions of CO, unburned HC, and particulate matterthus showing that biodiesel is environmentallyfriendly.[5] Biodiesel has no sulfur content or aromaticswhich eliminates the presence of SOX in emissions. Theoffensive exhaust odor of biodiesel was arrested byblending it with diesel in appropriate proportionswhich required no modification of the engine.[6] Sincebiodiesel is less flammable than diesel, it is a safe alter-native to diesel in mining operations which are proneto fire accidents. Commercial production of biodieselmay lead to a reduction in the expenditure on crudeoil imports and it may contribute to sustainable eco-nomic growth in India.[7]

CONTACT K.S. Raj Mohan ksrajmohan@ddn.upes.ac.in

© 2016 Informa UK Limited, trading as Taylor & Francis Group

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Biobutanol derived using the sources used to pro-duce bioethanol was tested in an engine after blendingit with diesel and performance and emission analysishas been widely reported in the literature.[4,8] Thusthe motivation to develop biodiesel blends is itsdecreased viscosity, reduced offensive odor, reducedenvironmental pollution, increased agricultural prod-ucts economy, and conservation of diesel, coupledwith the possibility of job opportunities.[9]

Biodiesel can be produced either from consumableoil or non-consumable oil. Edible oils such as palm oil,soya bean,[8] sunflower oil,[10] rapeseed oils,[11]canola,[12] safflower [13] and cotton oil have beenused in CI engines successfully. Due to the high popu-lation in India, using edible oils for fuel purposes willnot help the food industry. Hence it is wise to use non-edible oil for biodiesel applications. Some of the non-edible oils used as a substitute for petrol and diesel areHonge (Pongamia pinnata),[14] Jatropha (Jatrophacurcas),[15,16,17,18,19,20,21] Mahua (Madhuca indica),[22], Honne (Calophyllum inophyllum Linn),[14,23,24Brassica carinata [25] and Tamanu (Calophylluminophyllum seed oil).[19,26]

Esterified biodiesel offers various advantages overdiesel. Esterified biodiesel is reported to have less vis-cosity, higher oxygen content, lower density and is richin monoglyceride compounds. The raw oil contains tri-glyceride compound which is a long chain fatty acid.The chemical formula for the triglyceride is C55H98O6.After esterification the biodiesel contain monoglycer-ide which is C9H14O9. Most non-edible oils contain oleicacid, a well-known fatty acid, as a major component. Adecrease of oleic acid content in the oil depends onthe type of catalyst used (acid or base) in the esterifica-tion process. A FFA content of 2.38% was used for acidand base esterification process using H2SO4 or Potas-sium Hydroxide (4.76 mg KOH/g) during the biodieselproduction.[27]

Various studies have demonstrated that problemsarise when the oil is directly used in the engine withoutesterification. Hence it is necessary to identify an opti-mum esterification method to enable application ofbiodiesel for commercial applications. Non-edibleplants such as Calophyllum inophyllum (commonlyknown as Tamanu or Punnai) found in southern Asia,the centralized pacific region and Australia, is culti-vated widely in the tropical region. It is known as anornamental flower and can grow to 8�20 m producinga round, green drupe fruit of 2�4 cm diameter. Theripe fruit is yellow or brownish color (Figure 1). Theseed of these fruits can be extracted using a mechani-cal press with a yield of oil in the range 80�85% andthe waste produced in the biodiesel production can beused in biogas production. Thus Tamanu as a rawmaterial for biodiesel is a wise choice among the vari-ous sources. Hence, in this present investigation, bio-diesel production by transesterification methods using

Tamanu seeds was studied. The characteristics of bio-diesel such as the stability, properties of fuel and char-acteristics of emission in a CI engine performance forvarious blends are discussed.

Esterification is necessary to make biodiesel suitablefor testing in a diesel engine. We used H2SO4 and KOHfor the optimization of the biodiesel by using the molarratio. The yield of biodiesel was calculated as reportedin the literature.[27]

Material and methods

LR grade chemicals of potassium hydroxide, petroleumether, ethanol, phenolphthalein, Hanus solution, potas-sium iodide, starch, and sodium thiosulfate was pur-chased from Ranchem, India. All chemicals were driedin an oven at 608C for two hours prior to usage. Concen-trated hydrochloric acid and sulfuric acid were procuredfrom Merck and diluted to required concentrationsusing distilled water. Methanol was purchased from theScientific Instrument Company, Erode. Distilled waterwas used for washing and preparation of reagents. Theapparatus used in the study are a high precision bal-ance (Wensar company). Fuel properties were deter-mined using ASTM apparatus, cleaveland apparatusflash point and fire point, Redwood viscometer andBomb calorimeter (Arham scientific company, India),magnetic stirrer and 500 ml two-necked round-bottomflask (Zexter Lab Solution). Saponification, iodine andfree fatty acid (FFA) were determined according to thestandard iteration process reported in the literature.[27]The raw oil was extracted from Calophyllum inophyllum(commonly known as Punnai or Tamanu) and subjectedto various tests to determine its FFA, acid value, flashpoint, fire point, density, saponification value, Iodine

Figure 1. Pictorial representation of (a) green seeds of Calo-phyllum inophyllum (Tamanu), (b) dried seeds of Tamanu, (c)mechanical extractor and (d) extracted Tamanu oil.

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value, and Cetane number. ASTM standard of accordingto which the tests were performed are mentioned inTable 2. The raw oil was subjected to an acid esterifica-tion process in which H2SO4 and methanol were usedas a catalyst and reactant respectively. The base transes-terification was also used to reduce the oleic content inthe raw oil wherein potassium hydroxide and methanolwere used as a catalyst and reactant. The recovery ofmethanol was performed using ASTM distillation pro-cess (D6751). The prepared biodiesel was blended withthe diesel fuel and used in the engine. Commercial die-sel was purchased from IOCL retail bunk.

Methods

Oil from the seed was extracted through an oil pressmill and the oleic acid test for the raw oil was 18.09%.Acid and base esterification process was carried out.The preliminary studies were conducted to determinethe maximum yield of the biodiesel by varying themolar ratio of CH3OH to raw oil ratio such as 4:1, 6:1,8:1, 9:1 and the yield was 82%, 86.15%, 81% and 75%respectively. The optimum ratio was determined andthe same was utilized for the biodiesel production inbulk quantity. The synthesis of biodiesel is shown inFigure 2.

Acid esterification processThe raw oil with high FFA which contains triglyceridecompounds was converted to diglyceride by acid esterifi-cation. The catalyst used was H2SO4 and methanol asreactant. The temperature in this reaction was main-tained at 55�608C and two hours of continuous heatingin the 500 ml two-necked round-bottom flask. A mag-netic stirrer was used for stirring the product. The catalystand methanol are taken in the correct ratio for acid ester-ification. In this study, an oil and methanol ratio of 2:1and 1% catalyst were used. First the oil was heated for20 minutes after which the catalyst and methanol wereadded to the raw oil. The mixture was heated for twohours after which it was allowed to cool to room temper-ature, poured in the separating funnel, and left for8�10 hours to obtain a clear separation of the ester andthe excess methanol with impurities. The base transes-terification product was found in the bottom layer andtop layer was excess methanol with impurities. At thisstage the excess methanol formed was taken for metha-nol recovery by distillation process.

Base transesterification processThe bottom layer of the acid esterification was taken ina 500 ml round-bottom flask and heated for 20minutes. Potassium hydroxide catalyst and methanol

Figure 2. Synthesis of biodiesel.

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as a reactant were added. After 20 minutes the catalystand reactant were added to the product of the acidesterification. If the acid esterification product con-tained 110 ml of ester, then eight pellets of KOH cata-lyst and 52 ml of methanol reactant were used. Then itwas heated for 90 minutes in the flask. If the catalystconcentration is in excess then the product formedmay be sticky or a precipitation may form; if the cata-lyst concentration is too low, then a change in the layerseparation may occur. The heated oil was poured intothe separating funnel for gravity separation and left for8�10 hours. The glycerol was obtained in the bottomlayer and the ester was found in the top layer. This isdue to the reduction in the oleic acid in the oil. Since abase catalyst was used in the transesterification, theremay be soap formation in the ester product. To reducethe soap formation in the ester, a water wash was car-ried out.

Water washThe ester formed in the base transesterification wastaken in a 25 liter container and a water wash was car-ried out until the pH of the washed water was main-tained as that of distilled water. The ester product waswell mixed with the water through the bubbling for-mation in the container. The ester product was washedand then soap formation in the water can be used forthe various purposes. The washed ester product wastaken and heated to the desired temperature to reducethe moisture content in the biodiesel. As a result, purebiodiesel was obtained.

The synthesized biodiesel was blended with com-mercial diesel fuel such as B10, B20, B30 and B40. Theblended samples were used in the Kirloskar engineshown in Figure 3 and performance tests (mechanicalefficiency [ME], brake thermal efficiency [BTE] and spe-cific fuel consumption [SFC]) were carried out. Tests

were performed by varying the load by monitoring inthe load indicator; as a result of increase in the load,the dynamometer fluctuates. In addition, SFC (kg/s),BTE (%), ME (%) and exhaust gas emissions (CO, HC,NOx) were measured with instrumentation for everyload. The readings were obtained using IC enginesoftware.

Results and discussion

Biodiesel production from Tamanu oil bytransesterification

From the preliminary studies with different CH3OHTamanu oil ratio, the maximum yield was obtainedwhen the molar ratio was 6:1. The yield was 86.15%when the ratio was 6:1 and hence the same ratio wasinferred to be the best composition to achieve maxi-mum yield and the same was used for the synthesis ofbiodiesel.

Fuel properties of biodiesel blends

Table 1 shows the determined properties of synthe-sized biodiesel blended with commercial diesel fuelssuch as B10, B20, B30 and B40. The results of the ICengine, i.e., the raw oil and biodiesel fuel, are com-pared in Table 2.

Performance analysis in compression engine

Emissions were measured using Gas Analyzer AVL-444and Smoke Meter AVL-437C.

Specific fuel consumptionFigure 4(a) illustrates that the specific fuel consump-tion for B10 at full load is the lowest in comparison tothe other blends. It signifies that more energy is

Figure 3. Pictorial representation of single cylinder four-stroke Kirloskar CI engine (cylinder diameter 87.5 mm, stroke length110 mm, connecting rod length 234 mm, orifice diameter 20 mm, dynamometer arm length 185 mm, power 3.5 kW, speed1500 rpm, compression ratio 12:1 to 18:1, injection point variation 0�25oBTDC).

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produced with the B10 blend in comparison to otherblends. Our results are in accordance with the earlierstudies in a different engine using Tamanu oil whichalso reported that B10 has lower specific fuel consump-tion when compared to the other blends.[28] Lowerblend favors the atomization of the fuel whereashigher blends have higher viscosity which results inpoor atomization. Biodiesel may not require enginemodification up to B20, however higher blends mayneed some minor modifications. Thus the blended bio-diesel with diesel (B10) showed their maximum engineload requires less fuel consumption and it showshigher performance in comparison to other blends.Also B10 blend does not require any modification ofthe engine which makes it suitable for application incommercial engines.

Brake thermal efficiencyFigure 4(b) illustrates the change in BTE with respect toengine load. It was observed that a maximum BTE of38% was achieved at full load with B10 and this maybe due to the low friction losses when compared tothe other blend ratios. A decrease in BTE was observedfor the other blends due to higher friction losses. BTEfor B10 is 13% higher than that of diesel which was25% at full load when tested under identical condi-tions. Biodiesel does not require any lubricant oilwhereas commercial diesel requires lubrication oil. Ourresults are in contrast with an earlier report using Tam-anu oil which showed that B40 has the highest BTEcompared with other blends.[28] B40 blends needmodification in the engine which limits the practicalapplications whereas our biodiesel which showed max-imum BTE at B10 requires no change in the enginethereby saving the cost involved in the enginemodification.

Mechanical efficiencyThe ratio of the brake power produced by the engineto the engine indicated power referred to as ME wasdetermined for various engine loads. Figure 4(c) illus-trates the change in ME with respect to engine load. It

Table 1. Results of parameters determined for synthesized bio-fuel and its comparison with raw oil and commercial diesel.

ParametersASTM

standards Raw oil Biodiesel Diesel

Acid value (mg KOH/g) D 664 36.12 2.35 �Free Fatty Acid (%) D 5555 18.09 1.18 �Density (kg/m3) D 4052 905.6 766.4 830Viscosity (cSt) @ roomtemperature

D 445 � 4.02 2.68

Calorific value (MJ/kg) D 4809 � 37.7 43.06Saponification value D 5558 394.4 108.4 �Iodine value D 1959 5.0 10.23 �Cetane number D 613 58.99 63 53Flash point (8C) D 6450 228 143 110Fire point (8C) D 6450 247 155 80

Table 2. Results of parameters determined for the synthesizedbiofuel and its blends.Parameters Diesel Biodiesel B10 B20 B30 B40

Density (kg/m3) 832 766.4 851 855.1 857.9 867.9Viscosity (cSt) 2.68 4.02 3.55 3.61 3.98 4.25Flash point (8C) 49 143 77.5 79.5 82.5 83.5Cetane number 45 63 52.4 53.9 55.8 56.7Calorific value (MJ/kg) 43.06 37.7 42.53 41.50 40.47 40.16

Figure 4. Effect of percentage load on (a) specific fuel con-sumption (kg/s), (b) brake thermal efficiency and (c) mechani-cal efficiency.

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was observed that a maximum ME of 66% wasachieved at full load with B20 when compared to theother blends. The brake power produced in the engineis high and friction losses are low in the B20 blend. Ourresults are in accordance with the earlier study whichreported B20 has the highest ME when compared toother blends.[28]

Emission analysis in the compression engine

HydrocarbonsUnburned hydrocarbons (HC) in the emissions are dueto incomplete combustion in the engine. The higherthe biodiesel in the blend, then the higher the oxygencontent in the fuel. This promotes combustion andthereby reduces unburned HC in the emissions. Asshown in Figure 5(a), the unburned HC for B30 is lowerwhen compared to the other blend ratios. As the loadincreases, the HC emissions reduce due to the com-plete combustion of the hydrocarbon fuel in theengine and the results are in accordance with thosepreviously reported by Agarwal and Agarwal usingJatropha blends [20] and Arun using Tamanu oils.[28]

Nitrogen oxideBecause of the high combustion temperature and highpressure in the cylinder, NOx formation occurs. Some-times, prior to ignition in the engine NOx formationwas reported.[28] Biodiesel contains a lower sulfur con-tent which produces less NOx emission. Figure 5(b)illustrates the change in nitrogen oxide with respect toengine load. It was noted that the nitrogen oxide forB10 was 1262 ppm at full load which is lower whencompared to the other blends. An earlier study showsthat B20 (1400 ppm) has lower NOx emission and B20of our NOx emission was 1360 ppm.[28]

Carbon monoxideFigure 5(c) illustrates the change in carbon monoxidewith respect to engine load. It was observed that thecarbon monoxide for B10 (313 ppm) at full load is lowerwhen compared to the other blends. An earlier studyshows B20 (320 ppm) has lower CO emission in theexhaust gas.[28] CO emission is lower due to the higheroxygen content in the biodiesel blend. CO emissionmust reduce when the blend increases in the biodiesel.These improper curves are due to the different spraypattern in the engine and viscosity in the biodiesel.

Conclusion

Tamanu biodiesel has emissions generally close to die-sel like HC and some lower than the diesel like CO andNOx. The study shows that B10 has better efficiencyand emissions are also reduced when compared to theother blend properties. Properties of B10 are shown inTable 3 and heat value is higher when compared to the

Figure 5. Effect of percentage load on (a) hydrocarbon in emis-sion gas, (b) nitrogen oxides (ppm) in emission gas, (c) carbonmonoxide in emission gas.

Table 3. Properties of blend B20 which showed optimumperformance in a CI engine.Parameters B10

Density (kg/m3) 851Viscosity (cSt) 3.55Flash Point (8C) 77.5Cetane number 52.4Calorific value (MJ/kg) 42.53

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other blends. Efficiency is high in the B10 blend Tamanuoil as the oxygen content excess which is inbuilt andreduces emissions such as HC, CO and NOX. Tamanu oilcan be a good substitute for diesel in renewable appli-cations. To enhance the combustion properties andemission control in the IC engine are basic criteria forthe future scope in the Tamanu based biodiesel produc-tion. It may be achieved by introducing a foreign mate-rial into the biodiesel.

Acknowledgments

We thank R & D division, UPES, Dehradun, for funding a partof this project through RISE-2015. We thank petroleum prod-uct testing laboratory, UPES, for use of the facilities.

Disclosure statement

No potential conflict of interest was reported by the authors.

ORCID

K. Dinesh http://orcid.org/0000-0001-6164-0405M. Gopinath http://orcid.org/0000-0001-6867-0076K.S. Raj Mohan http://orcid.org/0000-0002-9682-1836

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t 22:

23 1

3 Ju

ne 2

016