Active Razor Shell CaO Catalyst Synthesis for Jatropha...

Research ArticleActive Razor Shell CaO Catalyst Synthesis for Jatropha MethylEster Production via Optimized Two-Step Transesterification

A N R Reddy1 A A Saleh1 M S Islam2 and S Hamdan1

1Department of Mechanical and Manufacturing Engineering Faculty of Engineering Universiti Malaysia Sarawak94300 Kota Samarahan Sarawak Malaysia2Department of Chemistry Bangladesh Army University of Engineering amp Technology Qadirabad CantonmentNatore 6431 Bangladesh

Correspondence should be addressed to A N R Reddy amarnadhagmailcom

Received 26 December 2016 Revised 23 February 2017 Accepted 7 March 2017 Published 12 April 2017

Academic Editor Arghya Narayan Banerjee

Copyright copy 2017 A N R Reddy et alThis is an open access article distributed under the Creative Commons Attribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Calcium based catalysts have been studied as promising heterogeneous catalysts for production of methyl esters via transesteri-fication however a few were explored on catalyst synthesis with high surface area less particle size and Ca leaching analysis Inthis work an active Razor shell CaO with crystalline size of 872 nm 119878BET of 9263m2g pore diameters of 37311 nm and porevolume of 0613 ccg was synthesized by a green technique ldquocalcination-hydro aeration-dehydrationrdquo Spectrographic techniquesTGADTA FTIR SEM XRD BETampBJH and PSA were employed for characterization and surface morphology of CaO Two-steptransesterification of Jatropha curcas oil was performed to evaluate CaO catalytic activity A five-factor-five-level two-block halffactorial central composite design based response surface method was employed for experimental analysis and optimization ofJatropha methyl ester (JME) yield The regression model adequacy ascertained thru coefficient of determination (1198772 9581) AJME yield of 9880 was noted at 119862 (310 wt)119872 (5424molmol) 119879 (12787min)119867 (5131∘C) and 119877 (612 rpm) The amountof Ca leached to JME during 1st and 4th reuse cycles was 143 ppm plusmn 011 and 425 ppm plusmn 021 respectively Higher leaching of Ca667 ppm plusmn 109 was found from the 5th reuse cycle due to higher dispersion of Ca2+ consequently JME yield reduces to 7640The JME fuel properties were studied according to biodiesel standards EN 14214 and comply to use as green biodiesel

1 Introduction

The sustainability ldquostrengthening the mechanisms for redis-tribution from the present to the futurerdquo has become a mottoof all nations around the world for promoting intrinsicscientific research methodologies into agriculture materialsenergy economy and even urban planning [1] Despitemultiphase research in energy rising global warming andair pollution issues instigated by fossil fuel combustionbesides limited petroleum fuel reserves have led to researchfor sustainable renewable energy sources Fatty acid methylester (FAME) commercially known as biodiesels intro-duced in the 1980s as a sustainable fuel energy resourcefor reducing greenhouse emissions [2] FAME comprisesmonoalkyl ester of long fatty acids typically produced bythe transesterification of biologically produced feedstockssuch as vegetable oil (VO) animal fats and microalgae oilsin the presence of methyl alcohol (MeOH) and a suitable

catalyst [3 4] Transesterification reaction is a combinationof three sequential catalyzed reactions (1)ndash(3) in whichtriglycerides (TG) of a VO were transformed to diglycerides(DG) and monoglyceride (MG) and finally as glycerol andmethyl ester (ME) known as biodiesel [5] Jatropha curcasLinnaeus an euphorbia family member has attained theresearcherrsquos attention as one of the best suited nonedible VOfeedstock types due to its agromedical tangible interests aswell as pro human food cycle nature for biodiesel fuel (BF)production via transesterification [4] Acid or base catalyzedtransesterification of VO was largely reported in literatureand also concluded on the use of heterogeneous catalysts forsustainable BF production [6 7]

TG +MeoHCatalystlarr997888997888997888997888rarr DG +ME (1)

DG +MeoHCatalystlarr997888997888997888997888rarr MG +ME (2)

HindawiJournal of ChemistryVolume 2017 Article ID 1489218 20 pageshttpsdoiorg10115520171489218

2 Journal of Chemistry

MG +MeoHCatalystlarr997888997888997888997888rarr Glycerol +ME (3)

Catalytic activity of a solid catalyst is highly influencedby its surface area and particle size distribution [8 9]Moreover rate of a reaction among the reactants significantlyaccelerates with lower particle catalysts since it improvesthe diffusion forces over catalyst particle surfaces and bettermass flow channels [8 10] In addition this phenomenonensures higher reaction rate through availability of largenumber of active reactant molecules that need a minimalactivation energy Calcium based catalysts demonstrate keypromising characteristics that include higher basicity lessersolubility better reusability low costs and easy availabilityA large number of studies have been devoted to investigatebiodiesel applications of pure or mixed calcium catalysts[11ndash15] Buasri et al [10] produced biodiesel from palm oilusing CaO catalyst which synthesized various seashells thatincludemussel cockle and scallop and reported surface areas(119878BET) of 8991m

2g 5987m2g and 7496m2g respectivelyShan et al [16] studied Ca-based heterogeneous catalystperspectives synthesized using rich waste materials suchas bones mollusk shells egg shells and industrial wastesbesides catalytic activity and biodiesel applications of calciumcatalysts prospects and challenges were discussed Mohamedet al [17] derived CaO from cockle shell by calcinationat 850∘C while Nurdin [18] derived CaO catalyst fromPaphia undulata shell wastes through calcination at 680∘C fortransesterification of Jatropha curcas oil (JCO) and Rubber oilto biodiesel Choudhury et al [11] Teo et al [12] and Taufiq-Yap et al [13] investigated the transesterification of JCO usingCaO of 119878BET 7114m2g 92 plusmn 080m2g and 95m2g andobtained a biodiesel of 8936 90 and 85 respectivelywhile Margaretha et al [19] experimented with Pomacea spshells produced CaO with pore volume of 004 ccg and 119878BETof 17m2g for transesterification palm oil to biodiesel Tan etal [14] investigated the transesterification kinetics of wastecooking oil to biodiesel using CaO catalyst synthesized fromostrich and chicken-eggshells besides their 119878BET of 710m2gand 546m2g respectively Islam et al [20] synthesizednano-CaCO3 with particle of 20 plusmn 5 nm diameter fromcockle shells by grinding mechanically in the presence ofdodecyl dimethyl betaine De Sousa et al [21] investigatedtransesterification kinetics of soybean oil using commercialCaO egg shell CaO carb shell CaO 119878BE of 09m2g 43m2gand 40m2g and particle size of 56 nm 184 nm and 74 nmrespectively

The significant transesterification reaction parametersthat influence JME yield include catalyst loading methanolto oil ratio reaction time heating temperature and thestirring rpm [22ndash26] Many researchers explored optimalparametric sufficiency over their minimum and maximumlevelsThe intrinsic impact of a parameter and their potentialinteractions to achieve the optimal FAME yield was investi-gated using the response surface methodology (RSM) as anoptimization and statistical analysis tool [11 22 27] RSMwas widely adopted based on three designs of CCD CCRD[22 27] and Box-Behnken design [11] for optimal FAMEVicente et al [28] testified over two factors temperature

(20∘Cndash75∘C) and catalyst concentration (02ndash18 wt) usingsunflower oil in the presence of various homogeneous andheterogeneous catalysts Goyal et al [23] reported the impactof four reaction parameters including the methanol-oil ratioreaction timeNaOHcatalyst concentration and temperatureover transesterification of JCO A CCD based four-factor-five-level was utilized to analyze the parametric impact on theFAME yield An optimal FAME field of 983 was reportedat 11 1molar ratio 1 wt catalyst 54∘C temperature and110min of reaction time while Dhingra et al investigatedKaranja [29] and Jatropha [30] biodiesels production opti-mization by considering five reaction parameters using theRSM coupled with GA [29] Many studies reported that thechoice of reaction parameters directly contributes in biodieselconversion process and influences FAME yield Also it isnoted that reaction parameters both stirring speed andreaction time were less studied

The literature studies emphasize suitability of calcium cat-alyst for biodiesel production via transesterification Besideshigher surface area large pores and lesser particle size of acatalyst enhance their catalytic efficacy of transesterificationreaction [11ndash15] Ensis arcuatus has been commonly foundto be fishery food source in the sandy coastal locations ofPacific and Antarctic areas and regionally referred to asRazor clams The study reports of Kanakaraju et al [31]Akmar and Rahim [32] and Hossen et al [33] demonstratepotential of Razor clams marine life and abundance in thestate of Sarawak as well as in the west Malaysian provincesThe previous works on synthesis of calcium catalysts arevery limited and have been focused on increasing catalystsurface area and lowering the particle size from naturallyavailable renewable wastes such as aquatic seashells [1820 21 34ndash38] However according to the best of ourbroad literature survey no work has reported on activatedCaO nanocatalyst synthesis using Razor shells Moreovera very scant work was accounted on the study on kinet-ics of transesterification reaction parameters that includecatalyst loading methanol to oil ratio heating tempera-ture stirring speed and reaction time which need to beundertaken

In this study CaO of high surface area and pores as wellas lower particle size was synthesized from a seashell so asto result in an activated heterogeneous catalyst Besides thedirect and interaction impacts of five reaction parameterson the FAME yield were proposed to be investigated overJCO two-step transesterification process Activated CaO wassynthesized using locally available seashell species Razorshells A laboratory scale experimental protocol ldquocalcination-hydro aeration-dehydrationrdquo was developed for Razor shellCaO synthesis besides structural and morphological char-acteristics were analyzed The transesterification reactionkinetics was studied by employing a CCD based on the five-factor-five-level two-block half factorial RSM model JMEproduction optimization protocol using active Razor shellCaO catalyst is shown in ldquoScheme 1rdquo The catalyst stabilityreusability and leaching were investigated The synthesizedJME fuel properties were tested according to the biodieselstandards EN14214

Journal of Chemistry 3

(1)

(2)

(3)(4)

(5)

(6)

(7)

Razor shell

Calcination-hydro aeration-dehydration

Active Razor shell CaO

RSM-CCD model

Two-steptransesterification

Jatrophacurcas oil MeOH

(gt99)

JMEyield 9880

70

60

50

40

301 2 3 4 5

M

C

Contour plot of JME versus M C

Scheme 1 Jatropha methyl ester production optimization using active Razor shell CaO catalyst

2 Material and Method

The Jatropha curcas seeds were obtained from a Jatrophafarm Wahaba Sdn Bhd situated in Sarawak MalaysiaJatropha curcas oil (JCO)was extractedmechanically using anoil expelling machine from their dried seeds The crude JCOwas used as extractedwithout any processing like purificationor refining JCO fatty acid profile was determined by the gaschromatography and the results are as indicated in Table 6The acid value (A) and saponification value (S) of JCOwere measured as 2946mgKOHg and 21004mgKOHgrespectively by utilizing a standard procedure [39] Themolecular weight (119872) of JCO was resulted as 932 gmol bythe equation119872 = (561times1000times3)(SVminusAV) [39] Laboratorygrade chemicals that include sulfuric acid (999) methylalcohol (gt99) potassium hydroxide (95) calcium oxide(CASNO0001305788) and double distilled deionized waterwere utilized All experiments were conducted at the EnergyLaboratory Department of Mechanical and ManufacturingEngineering Faculty of Engineering Universiti MalaysiaSarawak (UNIMAS) Malaysia

21 Preparation of Active Razor Shells CaO Catalyst Razorshells were collected from a local community market atMuara Tebas Sawarak Malaysia The CaO catalyst was syn-thesized following ldquocalcination-hydro aeration-dehydrationrdquoof the Razor shell The synthesis protocol is adopted asdescribed before by Niju et al [40 41] and modified to get afine Razor shell powder In a nutshell about 500 gm of Razor

shells was thoroughly water washed and dried overnight at105∘C in a hot air oven (IMPACT Scotland UK) [42] Thedried Razor shell was finely crushed using a heavy dutyprofessional blender (OmniBlend V imbaco Australia) andthen sieved using an 80 120583m mesh The micron-sized Razorshells powder was calcinated in a high temperature mufflefurnace (KSL-1700X-A4 MTI Corporation USA) at a targettemperature of 850∘C for 25 h At a calcine temperature of850∘C CaCO3 of Razor shell decomposes as CaO and CO2The fine CaO powder was refluxed in water for 6 h at 60∘CSimultaneously the mixture was aerated using spherical andcylindrical air stone bubbler setup fitted with a Hi-blowair pump (HAP-60 001Mpa 60w Hailea) and then themixture was allowed to settle for 2 h Continuous aerationoxygenates refluxing mixture and precipitates heavy dirtand solid particles which results in refined highly poresRazor shell CaO particles The catalyst was filtered and driedovernight at 120∘C in an oven [42] The refined Razor shellsolid powder was grounded for high grade fine catalystparticles utilizing a Planetary Ball mill (PM 400 RetschGermany) at 250 rpm for 2 h Calcination of fine Razor shellCaO was carried out for 3 h at 600∘C so as to transformhydroxides to oxide form through dehydration Accordinglyan active Razor shell CaO catalyst was synthesized followingldquocalcination-hydro aeration-dehydrationrdquo protocol

22 Characterization of Razor Shells CaO Catalyst To inves-tigate the organic structural features of Razor shell CaO cata-lyst newly synthesized CaO and lab grade CaO samples were


characterized using infrared spectrometer (Perkin Elmer 100series) over wavelengths 4000 to 280 cmminus1 Thermogravi-metric analyzer equipped with high temperature furnace(Mettler-Toledo Switzerland) was employed for thermo-gravimetric and differential thermal analysis (TGDTA) ofRazor shell catalyst Thermal analysis of samples was per-formed 35∘Cndash1000∘Cat a heating rate of 10∘Cmin and airflowof 100mlmin Razor shell CaO catalyst and lab grade CaOcrystalline features were studied employing X-ray diffraction(XRD) method (Shimadzu 6000) over 20ndash80∘C at a scanningangle of 2120579 and frequency of 2∘C per minute Scherrerrsquosequation 119863 = 09120582120573 cos 120579 was applied to calculate CaOparticle average crystalline size where ldquo119863rdquo denotes averagecrystalline size of CaO in nm 120582 equals 1542 A X-ray radi-ation wavelength ldquo120573rdquo denotes full width at half maximumintensity in radians and ldquo120579rdquo denotes Bragg angle in degreesRazor shell CaO catalyst surface morphology was analyzedwith scanning electron microscopy (SEM TM3030 HitachiJapan) The newly synthesized Razor shell CaO catalyst sur-face area pore diameter and pore volume calcined nonaer-ated CaO unclacined Razor shell and reference-CaO pow-der samples were investigated utilizing the BET (Brunauer-Emmett-Teller) and BJH (Barrett-Joyner-Halenda) proto-cols (Autosorb iQ-AG-C Quantachrome instruments USA)Both aerated and nonaerated CaO samples of Razor shellrsquosparticle size distribution were studied using particle sizedistribution analyzer (PSA 1090 004 120583mndash500120583m CILASFrance) The basic strength (H_) of Razor shell catalyst wasdetermined by employing Hammett indicators Typically asolution mixture of 1ml of Hammett indicator and 20mlof methanol was prepared and added to 25mg of catalystsample The contents were shaken well to attain homogeneityand left for 2 h to equilibrate and then catalyst color changewas noted [43] The following Hammett indicators wereutilized phenolphthalein (H_ = 82) thymolphthalein (H_ =100) 24-dinitroaniline (H_ = 150) and 4-nitroaniline (H_ =184) By adding a Hammett indicator to the catalyst sampleif it displays a change in color which infers that basicity of thecatalyst is stronger compared to the Hammett indicator usedon the contrary the catalyst sample is to be labeled as a weakerthan the probe Hammett indicator [44]

23 Jatropha Methyl Ester Production Jatropha methyl ester(JME) production was carried out by following an in-houselaboratory protocol The high free fatty acids (FFA) andmoisture contents of JCO strongly influence JME productionthrough the catalyzed transesterification reaction [45] JCOof FFA value gt 3 and moisture content gt 1 wt whichlead to saponification and oil hydrolysis besides reducing rateof biodiesel yield [46] Hence a two-step transesterificationprocess was adopted [47] The first step is acid esterificationin which FFA of JCO reduced to a suitable minimum levelfollowed by the second step which is base catalyzed trans-esterification [48] The successive steps which involved acidesterification and catalyzed transesterification are explainedin the following sections

24 Acid Esterification A digital hot plate magnetic stirrermixer (MS300-BANTE make 300∘C 2 L 220V 1250 rpm)

and a 500ml two-neck flat bottom glass reactor are attachedto a water cooled reflex condenser used for the acid ester-ification of JCO In order to improve the JCO conversionprocess and enhance the JME yield esterification was carriedout using methanol and concentrated H2SO4 as a catalyst asmentioned in (4) An amount of 100ml JCOwas preheated at110∘C for 30min to get moisture-free oil A mixture of 60(vv) methanol and 1 (vv) catalyst to JCO was preparedand added to the JCO The mixture was vigorously stirred at200 rpm and then heated to 50∘C for 1 h After the reactionthe reactant mixture was allowed to settle for 1 h and thenwashed successively thrice using double distilled deionizedwater Finally the oil portion was duly dried at 110∘C toprepare moisture-free oil As a result of acid esterificationFFA of JCO was noted all in a minimum of 1 with anesterification rate of 984 Thus the esterified JCO wassuitable for the transesterification with base catalyst [48]

RCOOH + CH3OHH

2SO

4997904997904997904997904997904rArr RCOOCH3 +H2O (4)

25 Transesterification of Esterified JCO The transesterifi-cation of the esterified JCO with newly synthesized Razorshell CaO catalyst was carried out in a 500ml three-neckflat bottom glass reactor fitted together with an overheadstirrer (IKA RW 20 Digital Dual-Range Mixer speed 60to 500240 to 2000 rpm) a sampling port and a watercooled reflex condenser A digital hot plate was employed forproviding a variable heat input as desired for the transesteri-fication reaction process The reactor experimental setup wasimmersed in a water bath to keep the uniform temperaturelevels throughout the reaction process The schematic of theexperimental setup is shown in Figure 1 A mix of methanolof 30 to 70molmol and Razor shell CaO catalyst of 1 wtto 5wt was thoroughly mixed for one hour and thentransferred to the glass reactor for each batch of experimentsThe transesterification reaction was performed over discreteoperating parameters that include heating temperature of40∘C to 60∘C stirring speed of 500 rpm to 700 rpm and areaction time of 60min to 180min These parametric rangeswere ascertained with published literature [22ndash24 49]

26 Design of Experiments for Optimal JME Yield The flowof the JME yield optimization was broadly executed infour sequential operations starting with the review exper-imental design modeling and optimization and resultsvalidation The intrinsic actions followed in each operationstage together with decision flow are shown in Figure 2In this study five significant independent transesterifica-tion reaction parameters which influenced the JME yieldinclude Razor shell CaO catalyst loading (119862) methanol tooil ratio (119872) reaction time (119879) heating temperature (119867)and the stirring rpm (119877) which have been considered for theoptimization of JME yield The effects of five significantreaction parameters together with intrinsic interactions weredevised by utilizing a central composite design (CCD) basedon the half-fractionmodel response surface statistical modelThe transesterification experimental data obtained were thenfit to a full quadratic equation as specified in (5) to analyze the


(1) Digital overhead stirrer(2) Sampling port(3) Three-neck glass reactor(4) Water bath tub

(5) Digital hot plate(6) Reflex condenser(7) Thermometer

(1)

(2)

(3)

(4)

(5)

(6)

(7)

Figure 1 Transesterification experimental setup for JME produc-tion

response variable JME yield through the response surfaceregression procedure

119884 = 1205730 +119899

sum119894=1

120573119894119896119894 +119899

sum119894=1

1205731198941198941198962119894 +sum

119899

sum119894lt119895=1

120573119894119895119896119894119896119895 + 120576 (5)

The symbolic notations of (5) are as follows ldquo119884rdquo is thepredicted response for JME yield ldquo1205730rdquo is the constantcoefficient ldquo120573119894 120573119894119894 and 120573119894119895rdquo are the regression coefficientsof intercept linear quadratic interactions 119896119894 and 119896119895 arethe coded independent process parameters and ldquo120576rdquo is theresidual of the predicted and experimental value knownas standard error The five significant parameters were setindependently within the following ranges 1 le 119862 (wt) le 530 le 119872 (molmol) le 70 60 le 119879 (min) le 180 40 le 119867(∘C) le 60 and 500 le 119877 (rpm) le 700 Considering each factorat five levels 33 base experimental reaction iterations wereconcluded from a CCD of two-block half-fraction modelwhich corresponds to sixteen cubic points six center pointsin the cube ten axial points and one center point at the axiallevel For a CCD the numerical value of alpha 120572 plusmn 2 is ameasure of the distance that keeps each of the axial designpoints from the center in evolution of the factorial levels[27] In Table 1 the actual levels of individual parameters

were tabulated representing their coded and uncoded valuesThe redundancy in datasets and results was minimized byperforming all the experiments in a random run orderThe Minitab 1621 software was employed for performingthe analysis of variance (ANOVA) of the model togetherwith CCD based response surfaces generation and JMEyield optimization A Minitab 1621 software was utilizedfor the response surface regression analysis and ANOVA ofthe designed model The regression model was presented in(5) and validation was ensured through the confirmatoryexperiments besides analysis of corresponding contour andsurface plots

27 Study of Razor Shell CaO Reusability Leaching Analysisand Transesterification with Reference Catalyst The Razorshell CaO catalyst was recovered by centrifuging the trans-esterification reactant samples at 4000 rpm for 60min Theprecipitated CaO was then washed in four sequential repeatswith 119899-hexane to remove Jatropha oil residues and thendried overnight in a forced air convection oven followed byrecalcination at 850∘C for 2 h before reuse The oil portionseparated was washed using double distilled deionized hotwater successively for four times to clear away the traces ofmethanol and catalyst from the samples followed by dryingover 110∘C in order to obtain a pure JME Furthermore allthe experiments were conducted using the variant operatingparameters to investigate their specific impact on the JMEyield The biodiesel obtained from each reusability cyclewas tested using an atomic absorption spectrometer-AAS(AA-7000 Shimadzu calcium ldquo4227 nmrdquo hollow cathodelamps as radiation source) and to measure the amount ofcalcium ions (Ca2+) concentration that leached into the JMEsamples The newly synthesized Razor shell CaO catalyticactivity was evaluated in comparison with a lab grade CaO(CASNO0001305788) Before being used the lab grade CaOcatalyst was dehydrated at 105∘C for 2 h in a hot air ovenFurther the reused Razor shell CaO catalyst surface mor-phology was analyzed using SEM (TM3030 Hitachi Japan)Five successive cycles of relative transesterification werecarried out using esterified JCO under similar experimentalconditions and standard ratios

28 Jatropha Methyl Ester Fuel Properties Analysis The spe-cific JME fuel properties that include density at 15∘C calorificvalue flash point cetane value specific gravity at 15∘C vis-cosity at 40∘C water content ash content acid value mono-glyceride diglyceride triglyceride free glycerine total estercontent and total glycerine contents were evaluated with afuel property testing equipment built on the ASTM standards(D2624 D3828) and European standards (EN 14105) such ascalorimeter fuel test kit and gas chromatograph (Shimadzu-GC-2010 Plus) fitted with a flame ionization detector FID-2010 Plus and a capillary column of size 30m times 025mm times025 120583m

3 Results and Discussion

31 Analysis of Razor Shell CaO Characteristics Thermo-gravimetric analysis (TGA) and differential thermal analysis


Literaturereview

Determine significanttransesterification reaction parameters

Parametric limitsand ranges

Assess parametersignificance

Known

No Yes

No

Yes

Expe

rimen

tal

FitnessNo

Response surface bycentral composite design

Design new setof parameters

Pilotexperimental trials

Yes

Choose model design inputsFactors (5) levels (5) blocks (2)CCD two-level factorial design (Half fraction)

JME yield prediction Experiments with predictedparametric sets (random order)

Response optimization

Data validation(pred versus exp) Fitness

No

Yes

Confirmatory experiments withoptimal range parametric data sets

EndValidated

Revi

ewEx

perim

enta

l des

ign

Mod

eling

amp o

ptim

izat

ion

Resu

lts va

lidat

ion

Parametersle 5

Figure 2 Schematic of optimal JME yield using experimental modeling and optimization protocol (customized based on [22])


Table 1 Factors and their uncoded levels

Uncoded variable Symbol Levelsminus2 minus1 0 1 2

Razor shell CaO catalyst loading (wt) 119862 1 2 3 4 5Methanol to oil ratio (molmol) 119872 30 40 50 60 70Reaction time (min) 119879 60 90 120 150 180Heating temperature (∘C) 119867 40 45 50 55 60Stirring speed (rpm) 119877 500 550 600 650 700

250 450 650 850 1050

100

80

60

Wei

ght (

)

02

01

00

minus01

minus02

minus03

minus04

minus05

minus06

Der

ivat

ive w

eigh

t los

s (

)

Temperature (∘C)

Figure 3 Thermal analysis (TGADTA) of Razor shells

(DTA) of uncalcined Razor shell were shown in Figure 3The weight loss indicates quantitative composition of Razorshell catalyst Also the exothermic and endothermic mea-surements presented using DTA curve which shows ther-mal influence on oxidation degradation and physiochemicalchanges From Figure 3 till 650∘C TGA curve continuedconstant and then decomposition initiated over 850∘C Asharp TGA slope between 650∘C and 850∘C is observedwhich conforms CaCO3 thermal decomposition FurtherDTA curve is consistent with TGA and at a temperature of820∘C DTA indicates CaCO3 endothermic conversion to aconstant CaO Therefore the TGADTA analysis confirmscalcination of Razor shells over temperature range of 850∘Cto convert CaCO3 to CaO This result is in agreement withTan et al [14] and Roschat et al [50]

The infrared spectra of Razor shell synthesized CaOand lab grade CaO powder samples are shown in Figure 4The absorption bands over wavelength lt 700 cmminus1 werestrong besides broad medium absorption bands at 990 cmminus11430 cmminus1 and 3640 cmminus1 which attributes presence of Ca-Ostretching According to the reports of Tan et al [14] McDe-vitt and Baun [51] Nasrazadani and Eureste [52] and Zaki etal [53] the strong IR spectral absorption over wavelengths400 cmminus1 and 290 cmminus1 signifies Ca-O which confirms CaOpresence Further weak absorption wavelengths gt 3700 cmminus1specifically 3722 cmminus1 and 3807 cmminus1 were present due tocarbonyl ldquoC=Ordquo and hydroxyl ldquoO-Hrdquo groups asymmetricbending As reported by De Sousa et al [21] Tan et al [14]and Margaretha et al [19] the hygroscopic nature of catalystis highly prone to absorb carbon dioxide and moisture

Razor shell CaO

Lab grade CaO

4000 3500 3000 2500 2000 1500 1000 500 0Wave numbers (1cm)

Tran

smitt

ance

()

Figure 4 IR spectra of calcined lab grade CaO and Razor shell CaO

0500

1000150020002500

0500

1000150020002500

20 25 30 35 40 45 50 55 60 65 70

Inte

nsity ο

ο ο οοο

οο ο ο

Lab grade CaO

Razor shell CaO

Scanning angle (2120579)

lowast

lowast

lowastlowast

lowast

⧫ ⧫⧫

⧫⧫ ⧫

⧫⧫⧫⧫⧫

ο CaO

lowast

⧫ Ca(OH)2CaCO3

Figure 5 XRD spectral graph of analysis of calcined lab grade CaOand Razor shell CaO

from the atmosphere and subsequently forms CaCO3 andCa(OH)2

The crystalline structural information of Razor shellsynthesized CaO and lab grade CaO obtained from XRDanalysis is shown in Figure 5 The Razor shell synthesizedCaO XRD spectral graph shows clear diffraction peaksat scanning angles (2120579) of 2318∘ 2954∘ 3614∘ 3956∘4328∘ 5616∘ 5954∘ and 6334∘ whereas lab grade CaOshows peaks at 2318∘ 2954∘ 3614∘ 3956∘ 4328∘ 472∘4768∘ 4868∘ 5616∘ 5694∘ 5758∘ 5954∘ 6108∘ and


(a) (b)

(c) (d)

Figure 6 SEM monograms of (a b) hydro aerated calcined Razor shell CaO (c d) calcined lab grade CaO

6334∘ The diffraction patterns were verified and consis-tent according to JCPDS file number 00-037-1497 as wellwith published reports by Mirghiasi et al [54] Teo etal [55] Chen et al [56] De Sousa et al [21] and Tanet al [14] The ldquocalcination-hydro aeration-dehydrationrdquoresulted in removal hydroxyl and carbonyl phases andcauses of a pure CaO However after thermal decompositionhigh hygroscopic nature of calcium and minor moistureabsorption at lab temperature cause formation of a fewCa(OH)2 According to Scherrerrsquos equation calculations theaverage crystalline sixe of Razor shell CaO is noted as872 nm

The SEM surface morphology of hydro aerated andcalcined Razor shell CaO was measured at a microscopicmagnification of 20000x and 30000x with 03 120583m shownin Figures 6(a) and 6(b) The SEM monograms of calcinedlab grade CaO surface morphology were viewed at a mag-nification of 5000x shown in Figures 6(c) and 6(d) TheRazor shell CaO SEM monograms encompass a number ofparticles in regular sizes of 145 nmndash371 nm together withagglomerates observed This can be attributed to structuralchanges of isolated isotropic calcium oxide particles afterhydro aeration followed by calcined at high temperatureswhile CaCO3 constituents decompose into CaO and CO2 asa result of decreases in particle sizes These results are fullyin accordance with investigation reports of Tan et al [14] andBuasri et al [10]

The BET and BJH analysis of Razor shell synthesizedhydro aerated and nonaerated calcined CaO and uncalcinedRazor shell together with reference catalyst samples haddetermined 119878BET of 9263m2g 8527m2g 521m2g and366m2g pore diameters of 37311 nm 33342 nm 11355 nmand 13861 nm and also total pore volume of 0613 ccg0423 ccg 00121 ccg and 0126 ccg respectively Com-pared to literature reports Tan et al [14] derived calciumcatalyst from chicken-eggshells (546m2g) and ostrich-eggshells (710m2g) Buasri et al [10] synthesized musselshells (8991m2g) cockle shells (5987m2g) and scallopshells (7496m2g) whileMargaretha et al [19] reported CaOof 17m2g The 119878BET of Razor shell CaO is relatively highmoreover the resulted pore diameter ranges within meso-pores (2 nmndash50 nm) demonstrate high value of the catalystsurface area together with their suitability for adsorptioncatalytic and energy storage applications [57] Hence theCaO of Razor shells synthesized through ldquocalcination-hydroaeration-dehydrationrdquo is an active catalyst owing to highpores and external surface area Further the Razor shellsynthesized CaO particles demonstrated bimodal particlesizes (Figure 7) The particle sizes of hydro aerated calcinedRazor shell CaO are in the range of 082120583mndash555 120583m witha mean particle size of 297 120583m meanwhile the nonaer-ated calcined Razor shell CaO showed particle sizes over08 120583mndash925120583m and mean size of 437 120583m The difference


In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)

X (diameter) (120583m)

Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)

Figure 7 Particle size distribution grid of (a) hydro aerated calcined Razor shell CaO (b) nonaerated calcined Razor shell CaO

in mean and median particle sizes of hydro aerated andnonaerated calcined Razor shell CaO is significantThereforethe ldquocalcination-hydro aeration-dehydrationrdquo caused a mixof micro- and nanocatalyst particles together with few largeagglomeratesThe results are comparable and consistent withthe literature reports of Tan et al [14] and Kesic et al [58]By adding Hammett indicators to Razor shell synthesizedCaO the catalyst samples successfully changed the color ofphenolphthalein (H_ = 82) from being colorless to pinkthymolphthalein (H_ = 100) from being colorless to blueand 24-dinitroaniline (H_ = 150) from yellow to mauverespectively Conversely the catalyst was unsuccessful tochange the color of 4-nitroaniline (H_ = 184) Hence thenewly synthesized CaO catalyst basic strength was labeledas 15 lt H_ lt 184 and therefore the basic strength of newlysynthesized CaO catalyst was a strong basicity for JCOThe basicity of Razor shell CaO agreed with the publishedresults for CaO synthesized from waste materials [15 4344] The Razor shell CaO catalyst was synthesized follow-ing ldquocalcination-hydro aeration-dehydrationrdquo protocolwhichresulted in smaller particle size as well as greater surfacearea According to Thiele [59] Buasri et al [10] and Teo etal [8] catalyst of higher surface area and lesser particle sizeimproves its catalytic activity and reaction kinetics rapidlyby refining the particle diffusion drawbacks Henceforth theRazor shell CaO is labeled as ldquoan active catalystrdquo

32 Jatropha Methyl Ester Production Analysis The JMEwas produced by transesterification of esterified JCO usingmethanol and Razor shell CaO catalyst and in additionthree controlled parameters such as reaction time heatingtemperature and stirring rpm The minimum FFA conditionfrom the acid esterification was opted for Razor shell CaOcatalyzed transesterification of Jatropha triglycerides Thestandard protocol comprising experimental modeling andoptimization and validation operation processes as presentedin Figure 2 was followed in order The selection of optimalexperimental parametric values was determined on the basis

of their relative impact evaluations while optimizing the JMEyield which is discussed in the following sections

33 Regression Model Analysis The experimental results ofsecond step pf transesterification reaction were analyzedusing a two-block half-fraction CCD statistical model as tab-ulated in Table 2 The estimated response surface regressioncoefficients for optimal JME using the uncoded units areas listed in Table 3 A regression modal equation that wasfitting the JME yield as a response parameter to the otherfive significant reaction parameters in terms of their uncodedvalues is as given in

119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867

+ 0931119877 minus 114391198622 minus 141861198722 minus 142241198792

minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879

minus 0846119862119867 minus 0193119862119877 minus 2021119872119879 minus 4479119872119867

+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)

The sign of regression coefficient is an indication of the effectof the corresponding term being synergetic or antagonisticon the response parameter Referring to the mathematicalequation (6) all the five parameters in their linear formshow a positive effect whereas the quadratic terms of theseparameters have a negative effect on the JME yield Howeverthe ten interaction terms have a mix of both positive andnegative effects on the JME yield which will be discussed inthe later part of this section in detail

The regression modal analysis of variance (ANOVA) wasutilized to study the adequacy of the model [60] Table 4summarizes the ANOVA for the model designed The valueof the coefficient of determination1198772 for themodel was notedas 9581 which implies the fitness of the regression modelin attributing good correlation between the percentage ofJME yield and five transesterification parameters studied [61]


Table 2 The CCD design matrix for JME yield prediction (randomized)

Type of points and runs Run Block Coded parameters JME yield119862 119872 119879 119867 119877 Predict Exp

Cubic points 120572 = plusmn1 (16 runs)

1 1 1 minus1 minus1 minus1 minus1 7481 74402 1 1 1 1 1 1 7352 72403 1 1 minus1 1 minus1 1 8258 83404 1 1 minus1 minus1 1 1 8547 85605 1 1 minus1 1 1 minus1 7876 77806 1 1 1 1 minus1 minus1 8080 79607 1 1 1 minus1 1 minus1 8826 89008 1 minus1 1 1 1 minus1 8736 86409 1 1 1 minus1 minus1 1 8390 832010 1 minus1 -1 minus1 1 minus1 7914 782011 1 minus1 1 minus1 1 1 8721 892012 1 minus1 minus1 minus1 minus1 1 8871 890013 1 minus1 1 minus1 minus1 minus1 8778 870014 1 minus1 minus1 1 minus1 minus1 8408 826015 1 minus1 minus1 1 1 1 9009 910016 1 minus1 1 1 minus1 1 9159 9180

Axial points 120572 = plusmn2 (10 runs)

17 2 minus2 0 0 0 0 9019 872018 2 2 0 0 0 0 9071 934019 2 0 0 0 minus2 0 8100 840020 2 0 0 minus2 0 0 9441 930021 2 0 minus2 0 0 0 8366 832022 2 0 0 0 0 2 9167 930023 2 0 2 0 0 0 8555 866024 2 0 0 0 0 minus2 9458 944025 2 0 0 2 0 0 9444 956026 2 0 0 0 2 0 9630 9600

Center points in cube 120572 = 0 (6 runs)

27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

Center points in axial (1 run) 33 2 0 0 0 0 0 9989 9800

and also to confess the successful integrity of the regressionequation among the experimental data appropriately Thedifference between the coefficients of determination (1198772) andthe correlation (1198772adj = 8781) at large discloses the presenceof the nonsignificant parametric terms in the designedregression model The comparative graph of Figure 9 showscoherence between JME predicted and experimental yieldsBesides the119891-test and119875 values were the indications ofmodaland each regression coefficient significance respectively [30]

34 Transesterification Reaction Parameter Effects Analysis onJME Yield Each of the five transesterification parametersrsquosignificance and their effect on JME yield were tested andanalyzed in terms of their parametric interactions throughthe regression model (6) as well as the ANOVA From thedata reported in Table 4 the linear form of the parametricterms of methanol to oil ratio (119872) reaction time (119879) and

heating temperature (119867) was having relatively higher impacton the JME yield owing to the high 119865-values as compared tothe other parameters catalyst loading (119862) and stirring rpm(119877) The interaction between any two selected parameters on JME yield was analyzed by holding the remaining threereaction parameters at their median levels

341 Catalyst Loading (C) Catalyst loading is one of the keyparameters that influence the production of JME in termsof both JME yield percentage and its quality [62ndash64] Theeffect of the Razor shell CaO catalyst loading interactionswith other reaction parameters of the reaction timemethanolto oil ratio heating temperature and stirring speed wasplotted respectively in the contour plots shown in Figures8(a) 8(b) 8(c) and 8(d) Though the catalyst loading wascarried through 1 wtndash5wt JME yield was significantldquogt98rdquo over 2wtndash4wt From the regression equation


Table 3 Estimated response surface regression coefficients for optimal JME yield using uncoded units

Term Coef SE coef 119879 119875Constant 100071 10485 95447 0000Block minus1819 04824 minus3771 0003Linear119862 0262 10603 0247 0810119872 6707 11903 5635 0000119879 4002 10721 3733 0003119867 4515 10907 4140 0002119877 0931 10721 0868 0404

Quadratic1198622 minus11439 19574 minus5844 00001198722 minus14186 19517 minus7269 00001198792 minus14224 19047 minus7468 00001198672 minus11824 19047 minus6208 00001198772 minus6524 19047 minus3425 0006

Interaction119862 times119872 4379 30693 1427 0181119862 times 119879 0493 26488 0186 0856119862 times 119867 minus0846 27161 minus0312 0761119862 times 119877 minus0193 26488 minus0073 0943119872times 119879 minus2021 30062 minus0672 0515119872times119867 minus4479 30693 minus1459 0172119872times 119877 0721 30062 0240 0815119879 times 119867 minus1393 26488 minus0526 0609119879 times 119877 3754 27161 1382 0194119867 times 119877 minus1707 26488 -0645 0532

(6) it is evident that the catalyst loading has a positive impacton the JME yield that is JME yield was proportional tothe utilization of 1 wtndash4wt catalyst It was noted thatthe lower catalyst loading (lt2wt) does not result in aproductive JME yield Furthermore the higher catalyst load-ing (gt4wt) leads to the catalyst secondary reactions withother reactants which result in the reduction of JME yield[65]The calcium based catalysts have demonstrated leachingtendency to the biodiesels during transesterification [12 4647] According to the biodiesel standards EN 142142008allowable concentration of group-I (Na + K) and group-II (Ca + Mg) is max 50mgkg in the biodiesel sampleswhile the residues of excess metal oxides act as impuritiesin the biodiesel fuel produced [66] The catalyst loadinginteractions with methanol to the oil ratio (119862 times 119872) andtransesterification reaction time (119862 times 119879) resulted in positiveinteractions In contrast interactions with reactants heatingtemperature (119862 times 119867) and stirring speed rpm (119862 times 119877) havealleviated the JME yield Among all (119862 times119872) with regressioncoefficient ldquo+4379rdquo demonstrated the highest effect impactin accelerating the transesterification reaction kinetics for thecatalyst loading 2wtndash4wt and about 46ndash65molmolFigure 8(b) leading to ldquogt98rdquo JME yield [67 68]

342 Methanol to Oil Ratio (M) Methanol to oil ratio isa primary reactant parameter in the transesterification ofVO The methanol to oil ratio is determined in correlation

with a type of VO catalyst and other reaction conditionsFigures 8(b) 8(e) 8(f) and 8(g) present the methanol tooil molar ratio with catalyst loading reaction time heatingtemperature and stirring speed interactions respectivelyTheJME yield of ge98 was reported on to 46∘C plusmn 1∘Cndash56∘C plusmn1∘C operating temperatures According to the stoichiometricestimations 30 1molemole methanol to JCO ratio isrequired [69] however in actual esterification experiments acritical methanol to oil ratio which ranges from 30 1 to 210 1molmol was reported to carry out complete reactionthat is transformation of JCO triglycerides into the JMEand glycerin The linear regression coefficient of methanol tooil ratio (119872) in the regression equation (6) ldquo+6707rdquo refersto its greater influence on transformation reaction processas well as on optimal JME yield Although experimentswere performed over a range 30 le 119872 (molmol) le 70lower JME yield results were noted for lt 50molmolof methanol to oil ratio this may be due to the insufficientamount of methanol under the reaction conditions set forthwhile 50ndash60molmol methanol maximum transforma-tion was achieved relatively compared to the molar ratiowhich was 60ndash70molmol which indicates keeping theexcessive amount of methanol hampers in achieving thereaction equilibrium as well as biodiesel cost economics[62] The methanol to oil ratio interaction with the stirringspeed (119872 times 119877) resulted as a positive response This maybe due to increase in the catalytic and transesterification


Table 4 Analysis of variance for optimal JME

Source DF Sum of squares Adj sum of squares Adj mean of squares 119865 119875Blocks 1 9990 9469 94694 1422 00030Regression 20 157549 157549 78775 1183 lt00001

Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040

Square 5 90229 91424 182849 2746 lt000011198622 1 7902 22741 227414 3415 lt000011198722 1 22377 35183 351831 5283 lt000011198792 1 30116 37136 371356 5577 lt000011198672 1 22714 25661 256608 3853 lt000011198772 1 7119 7812 78117 1173 00060

Interaction 10 4043 4043 4043 061 07800119862 times119872 1 670 1355 13552 204 01810119862 times 119879 1 002 023 0231 003 08560119862 times 119867 1 335 065 0647 01 07610119862 times 119877 1 002 004 0035 001 09430119872times 119879 1 301 301 3011 045 05150119872times119867 1 927 1418 14179 213 01720119872times 119877 1 048 038 0383 006 08150119879 times 119867 1 208 184 1841 028 06090119879 times 119877 1 1272 1272 12718 191 01940119867 times 119877 1 277 277 2766 042 05320

Residual error 11 7325 7325 6659Lack-of-fit 7 7322 7322 10460 139468 lt00001Pure error 4 003 003 0008

Total 32 1748641198772 = 9581 1198772pred = 197 and 1198772adj = 8781

kinetics as a whole with the stirring speed and hence thereis a proportional increase in the JME yield togetherwith methanol to oil ratio On the other hand methanolinteractions with parameters heating temperature (119872 times 119867minus4479) and reaction time (119872 times 119879 minus2021) were markedas highly negative on the response surface that is JMEyield This is due to the reason that the reactant heatingtemperatures are close to themethanol boiling point (647∘C)leading to continuous and rapid evaporation ofmethanol andhence lesser availability of the methanol for completing thetransesterification [70]

343 Transesterification Reaction Time (T) The requisiteduration of reaction time for catalyzed transesterification isgoverned by factors such as catalyst type degree of temper-ature and also reactants mixing rpm [70 71] The effectsof transesterification reaction time on JME yield wereinvestigated in conjunction with catalyst loading methanolto oil ratio heating temperature and stirring speed parameterinteractions The analysis of experimental results is showedgraphically in Figures 8(a) 8(e) 8(h) and 8(i) and statisticallyfrom (6) the highest significance for interactions of the

reaction time and stirring speed (119879 times 119877) over interactions(119862times119879) (119879times119867) and (119872times119879) confesses through their regres-sion coefficients ldquo+3753rdquo ldquo+0493rdquo ldquominus1393rdquo and ldquominus2021rdquorespectively At the beginning of the transesterification apassive rate of reaction phase was observed due to thegradual dispersion of methanol into the glycerides in JCO[70 72] As the reaction time increases the amount oftriglycerides conversion into ME besides JME yield wasalso raised Normally across the operational reaction timethe ldquo110 plusmn 5minndash150 plusmn 5minrdquo transesterification iterationsresults revealed a JME yield of ldquoge98rdquo Beyond these reactionduration levels a notable decline in JME yield was reportedThis may be due to the fact that extended reaction timingslead to reversible reactions (1)ndash(3) which result in continualester content fall besides soap and diglyceroxide formation[70 73 74] Both methanol to oil ratio and temperature wereshowing unfavorable interactions with reaction time Hencean appropriate reaction time was maintained

344 Heating Temperature (H) The transesterification reac-tion kinetics was significantly affected by the reactants heat-ing temperature [3] Figures 8(c) 8(f) 8(h) and 8(j) present


180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99

Hold values72ndash7575ndash7878ndash8181ndash8484ndash87

87ndash9090ndash9393ndash9696ndash99

5050600

(a) Reaction time and catalyst concentra-tion (119879 times 119862)

70

60

50

40

30

M

1 2 3 4 5

C

THR

JMElt660 Hold values

12050600

660ndash692692ndash724724ndash756756ndash788788ndash820

820ndash852852ndash884884ndash916916ndash948948ndash980gt980

(b) Methanol to oil ratio and catalyst concen-tration (119872times119862)

60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600



(c) Heating temperature and catalyst concen-tration (119867times 119862)

700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050


920ndash945945ndash970970ndash995gt995

(d) Stirring speed and catalyst concentration(119877 times 119862)

180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600



(e) Reaction time and methanol to oil ratio(119879 times119872)

H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600

(f) Heating temperature and methanol tooil ratio (119867times119872)

700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050



(g) Stirring speed and methanol to oil ratio(119877 times119872)

1801601401201008060

T

H

60

55

50

45

40

CMR


350600



(h) Heating temperature and reaction time(119867times 119879)

1801601401201008060

700

650

600

550

500

T

R

CMH


35050



(i) Stirring speed and reaction time (119877 times 119879)

Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120


885ndash910910ndash935935ndash960960ndash985gt985

(j) Stirring speed and heating temperature (119877 times119867)

Figure 8 Contour plots showing transesterification parametric interactions impact on JME yield

7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()

JME experimental yield ()

Figure 9 Comparative graph of JME predicted and experimentalyields

the interactions of heating temperature over 40∘Cndash60∘C withthe catalyst loading methanol molar ratio reaction time andstirring speed The study of temperature effect is very crucialsince a JME yield of ldquoge98rdquo was reported on to 46∘C plusmn1∘Cndash56∘C plusmn 1∘C Both higher and lower temperature rangesshowed distinct negative impacts on the reaction processTheuse of heterogeneous catalysts suffers from their poor ratesof reaction compared to homogeneous catalysts howeverhigher reaction pressures and temperatures can contributein accelerating the reaction rate [75] The reaction time getsshorter with higher temperatures and accelerates the rate ofreaction but then rises the viscosity of reactants and reducesmethyl esters conversion [3 76] Also the increase in reac-tion temperature eventually results in rapid evaporation ofmethanol which can greatly promotes saponification besidesleading to side reactions and soap formation [3 76] Despite a

proper water cooling condenser attachment if the operatingtemperature approaches close to boiling point of methanol647∘C evaporation of methanol accelerates [70 72] Thiseffect was evident from the experimental results tabulated inTable 2 Likewise the interaction (119872times119867) bears the relativelyhighest negative regression coefficient of ldquominus4479rdquo besides thefact that other interactions include (119862 times 119867) (119879 times 119867) and(119867 times 119877) All these predominantly indicate that an increasein heating temperature does not appreciate the JME yieldrather than reducing the whole reaction activity Thereforethe heating temperature ranges are lower than methanolboiling point which minimizes its exponential vaporizationand allows maintaining sufficient methanol levels during thetransesterification

345 Stirring Speed rpm (R) Stirring speed of reactants isone of the key reaction parameters in the biodiesel pro-duction through heterogeneous catalyzed transesterificationprocess [3 44 77] In Figures 8(d) 8(g) 8(i) and 8(j) thestirring speed interaction effects on JME yield together withthe catalyst loading methanol molar ratio reaction timeand heating temperature were plotted From the graphicalresults JME yield of ldquoge99 plusmn 05rdquo can be seen Besides thestirring speed interactions on the reaction time (119879 times 119877) andmethanol to oil ratio (119872 times 119877) were comparably significantwith regression coefficients ldquo+3759rdquo and ldquo+0721rdquo as notedfrom (6) Even though the other two interactions (119862times119877) and(119867 times 119877) are indicated with negative regression coefficientsFigures 8(d) and 8(j) contour plots demonstrate a JME yieldof ldquo995rdquo and ldquo985rdquo respectively This emphasizes that astirring speed is a productive reaction parameter in achievinga maximum JME yield

35 Optimization of Reaction Parameters and Results Valida-tion Optimal JME yield was obtained by comprehensiveintegration analysis of linear and interaction impacts of all


Table 5 Predicted JME yield data sets validation at optimal conditions with experimental results

Data set

Optimal condition JME yield ()

Catalyst loading(wt)

Methanol to oilratio (molmol)

Reaction time(min)

Heatingtemperature

(∘C)

Stirringspeed (rpm) Predicted Experimental

Set-1 295 5430 15744 5043 62192 9802 9704Set-2 307 5429 15730 5043 62479 9814 9726Set-3 310 5472 15766 5037 62211 9803 9705Set-4 329 5431 15641 5045 62748 9825 9737Set-5 322 5323 13878 5198 56118 9889 9800Set-6 309 5528 10653 5092 63188 9842 9753Set-7 315 5465 15758 5038 62281 9805 9785Set-8 329 5342 13773 5197 56038 9880 9792Set-9 310 5424 12787 5131 61111 9920 9880Set-10 296 5596 12871 5131 61111 9941 9862

Table 6 Fatty acid composition analysis of JCO

Fatty acid JCO ()Palmitic acid (C160) 1435Palmitoleic acid (C161) 152Stearic acid (C180) 702Oleic acid (C181) 4315Linoleic acid (C182) 3392Linolenic acid (C183) 004

five reaction parameters The comparative analysis of bothstatistical and experimental results along with the interactioncontour plots reveals a significant effect of a reaction param-eter at a specific parameter levels However the minimumlevels of any parameter were not intended to obtain optimalJME yield The optimization of transesterification reactionparameters was carried out using a response surface opti-mizer tool and the results were validated for ten sets throughconfirmatory experiments successively Data validation forten sets together with the predicted and experimental resultswere tabulated as listed in Table 5 Among the ten validationtest results 9880 of JME yield was noted at optimal condi-tions 119862 (310 wt)119872 (5424molmol) 119879 (12787min)119867(5131∘C) and 119877 (612 rpm) for the data set-9 A similar resultwith a simple variation of ldquominus018rdquo JME yield was achievedfor data set-10The parametric optimal results are ascertainedwith previously published results [22ndash24 49] Further theRazor shell CaO performance as a catalyst in converting thetriglycerides of JCO to JME is comparable with literaturereports by Tan et al [14]Margaretha et al [19] De Sousa et al[21] Roschat et al [50]McDevitt and Baun [51] Nasrazadaniand Eureste [52] Zaki et al [53] Mirghiasi et al [54] Teo etal [55] and Chen et al [56]

36 Analysis of Razor Shell CaO Reusability Leaching Analy-sis and Transesterificationwith Reference Catalyst TheRazorshell CaO catalyst reusability transesterification experimentsof the pretreated JCO and methanol were carried out with

optimal conditions of 119862 (310 wt) 119872 (5424molmol)119879 (12787min) 119867 (5131∘C) and 119877 (612 rpm) as obtainedand under similar experimental protocols for five successivecatalyst reuse cycles Figure 10(a) shows variations in JMEyield fromfive successive reuse cycles 9762 9575 91528433 and 7640 respectivelyThe SEMmonograms (Fig-ures 10(b)ndash10(f)) depict changes in surface morphology ofreused Razor shell CaO catalyst over five cycles successivelyThe reduction in JME yield may be due to the gradual lossof active sites on the catalyst surface particle agglomera-tions with other reactant molecules andor calcium catalystleaching to the biodiesel [13 14] An averaNge JME yield of936 was noted up to the 4th catalyst reuse cycle Howeverduring the 5th catalyst reuse cycle JME yield was 7640which is remarkably less by 793 from the 4th reuse cycleBesides the leaching of Razor shell CaO catalyst was carriedout successively using AAS for measuring calcium ion (Ca2+)leached to JME The test results indicate Ca2+ dispersionrange of 143 ppm plusmn 011 to 425 ppm plusmn 021 during the1st and 4th reuse cycles which indicate compliance withEN14214 fuel standards However from the 5th reuse cycleCa2+ of 667 ppm plusmn 109 was reported and subsequentlydropped in JME yield besides increased leaching Hence itcan be concluded that the Razor shell CaO is stable for fourreuse cycles Transesterification of JCO using lab grade CaOtogether with catalyst reuse tests was conducted at optimalconditions as obtained Results of JME yield using fromboth Razor shell CaO and lab grade CaO are shown inFigure 10 The JME yield achieved from Razor shell CaO ishigher besides good catalytic performance over its reusabilityMoreover the JME yield obtained frompresent investigationsis comparably higher than other researchers Tan et al [14]reported This variation in JME yield can be attributed to thehigher catalyst surface area particle size and pore volume ofRazor shell CaO compared to catalysts used by Tan et al [14]

37 JME Fuel Properties Analysis The JME fuel propertytest results such as density at 15∘C calorific value flashpoint cetane value specific gravity at 15∘C viscosity at40∘C water content ash content acid value monoglyceride


988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)

Catalyst reuse cycleRazor shell CaO catalystLab grade CaO

(a) (b)

(c) (d) (e)

(f)

Figure 10 (a) JME yield study over Razor shell CaO and lab grade CaO catalysts reuse at optimal transesterification reaction conditions(bndashf) SEM images of Razor shell CaO catalyst presenting catalyst surface structure variations after reuse

Journal of Chemistry 17Table 7 JME fuel properties

Fuel property (units) JME EN 14214 limitDensity at 15∘C (kgm3) 883 860ndash900Calorific value (MJkg) 36284 mdashFlash point (∘C) 167 gt101Cetane value 52 gt47Specific gravity at 15∘C (gml) 0878 086ndash090viscosity at 40∘C (mm2s) 422 35ndash50Water content (Wt) 0044 lt005Ash content (g100 g) lt001 lt001Acid value (Mg KOHg) 028 lt05Monoglyceride (Wt) 0311 lt080Diglyceride (Wt) 0033 lt020Triglyceride (Wt) 0 lt020Free glycerin (Wt) 0 lt002Total ester (Wt) 9911 gt965Total glycerin (Wt) 003 lt025

diglyceride triglyceride free glycerine total ester contentand total glycerine contents are summarized in Table 7 Theresults are compliance with the European biodiesel standardEN14214 thus JME indicates its suitability as a green biodieselsource

4 Conclusions

Synthesis of heterogeneous CaO catalyst using Razor shellsconformed by spectral characterization results of FTIRSEM XRD BETampBJH and PSA with a crystalline size of872 nm 119878BET of 9263m2g pore diameters of 37311 nm andpore volume of 0613 ccg which signifies CaO as an activecatalyst CaO was derived using a green synthesis proto-col ldquocalcination-hydro aeration-dehydrationrdquo The catalystyielded an optimal Jatropha methyl ester (JME) of 9880via two-step transesterification of Jatropha curcas oil (JCO)at 119862 (310 wt) 119872 (5424molmol) 119879 (12787min) 119867(5131∘C) and 119877 (612 rpm) The reaction kinetics and JMEyield optimization were investigated utilizing a five-factor-five-level two-block half factorial central composite design(CCD) based response surface method (RSM) design Theatomic absorption spectroscopic characterization of JMEshowed minimal leaching of calcium to JME until catalyst of4th reuse cycleThe amount of Ca leaching increases for eachtype of reuse and subsequently reduces JME yield The fuelproperties tested according to biodiesel standards EN 14214comply with JMErsquos suitability as a green biodiesel and offerssustainable benefits

Conflicts of Interest

The authors declare that there are no conflicts of interestregarding the publishing of this paper

Acknowledgments

The authors would like to thank Faculty of EngineeringUNIMAS and all the staff members for providing research

facilities and continuous support during this work The firstauthor A N R Reddy would greatly acknowledge andexpress his highest gratitude toMinistry ofHigher EducationMalaysia for awarding prestigious Malaysian InternationalScholarship (MIS) 2015 KPTB600-4112 (60)

References

[1] G B Asheim WPS1302 The World Bank Washington DCUSA 1994 httpwww-wdsworldbankorgservletWDSCon-tentServerWDSPIB19940501000009265_3970716141011RenderedPDFmulti0pagepdf

[2] US-EPA ldquoRFS2 EPA-420-R-10-003 Washington DC USArdquo2010 httpwww3epagovotaqrenewablefuels420r10003pdf

[3] J Qian H Shi and Z Yun ldquoPreparation of biodiesel from Jat-ropha curcas L oil produced by two-phase solvent extractionrdquoBioresource Technology vol 101 no 18 pp 7025ndash7031 2010

[4] L C Meher C P Churamani M Arif Z Ahmed and S NNaik ldquoJatropha curcas as a renewable source for bio-fuelsmdashareviewrdquo Renewable and Sustainable Energy Reviews vol 26 pp397ndash407 2013

[5] I Noshadi N A S Amin and R S Parnas ldquoContinuousproduction of biodiesel fromwaste cooking oil in a reactive dis-tillation column catalyzed by solid heteropolyacid optimizationusing response surface methodology (RSM)rdquo Fuel vol 94 pp156ndash164 2012

[6] E F Aransiola T V Ojumu O O Oyekola T F Madzim-bamuto and D I O Ikhu-Omoregbe ldquoA review of currenttechnology for biodiesel production state of the artrdquo Biomassand Bioenergy vol 61 pp 276ndash297 2014

[7] J M Marchetti V U Miguel and A F Errazu ldquoPossiblemethods for biodiesel productionrdquo Renewable and SustainableEnergy Reviews vol 11 no 6 pp 1300ndash1311 2007

[8] SH Teo YH Taufiq-YapU Rashid andA Islam ldquoHydrother-mal effect on synthesis characterization and catalytic propertiesof calcium methoxide for biodiesel production from crudeJatropha curcasrdquo RSC Advances vol 5 no 6 pp 4266ndash42762015


[9] E W Thiele ldquoRelation between catalytic activity and size ofparticlerdquo Industrial amp Engineering Chemistry vol 31 no 7 pp916ndash920 1939

[10] A Buasri N Chaiyut V Loryuenyong PWorawanitchaphongand S Trongyong ldquoCalcium oxide derived from waste shellsof mussel cockle and scallop as the heterogeneous catalyst forbiodiesel productionrdquo The Scientific World Journal vol 2013Article ID 460923 7 pages 2013

[11] H A Choudhury P P Goswami R S Malani and V SMoholkar ldquoUltrasonic biodiesel synthesis from crude Jatrophacurcas oil with heterogeneous base catalyst mechanistic insightand statistical optimizationrdquo Ultrasonics Sonochemistry vol 21no 3 pp 1050ndash1064 2014

[12] S H Teo U Rashid and Y H Taufiq-Yap ldquoBiodiesel produc-tion from crude Jatropha Curcas oil using calcium based mixedoxide catalystsrdquo Fuel vol 136 pp 244ndash252 2014

[13] Y H Taufiq-Yap H V Lee M Z Hussein and R YunusldquoCalcium-based mixed oxide catalysts for methanolysis ofJatropha curcas oil to biodieselrdquo Biomass and Bioenergy vol 35no 2 pp 827ndash834 2011

[14] Y H Tan M O Abdullah C Nolasco-Hipolito and Y HTaufiq-Yap ldquoWaste ostrich- and chicken-eggshells as heteroge-neous base catalyst for biodiesel production from used cookingoil catalyst characterization and biodiesel yield performancerdquoApplied Energy vol 160 pp 58ndash70 2015

[15] A Kawashima K Matsubara and K Honda ldquoAcceleration ofcatalytic activity of calcium oxide for biodiesel productionrdquoBioresource Technology vol 100 no 2 pp 696ndash700 2009

[16] R Shan C Zhao P Lv H Yuan and J Yao ldquoCatalytic applica-tions of calcium rich waste materials for biodiesel current stateand perspectivesrdquo Energy Conversion andManagement vol 127pp 273ndash283 2016

[17] M Mohamed N A Rashidi S Yusup L K Teong U Rashidand R M Ali ldquoEffects of experimental variables on conversionof cockle shell to calcium oxide using thermal gravimetricanalysisrdquo Journal of Cleaner Production vol 37 pp 394ndash3972012

[18] S Nurdin ldquoActivated Paphia undulate shells waste (APSW) acost-effective catalyst for biodiesel synthesis from Rubber andJatropha curcas seeds oil (RSOME amp JSOME)rdquo InternationalJournal of Chemical Engineering and Applications vol 5 no 6pp 483ndash488 2014

[19] Y Y Margaretha H S Prastyo A Ayucitra and S IsmadjildquoCalciumoxide frompomacea sp shell as a catalyst for biodieselproductionrdquo International Journal of Energy and EnvironmentalEngineering vol 3 no 1 article 33 2012

[20] K N Islam M Z B A Bakar M E Ali et al ldquoA novel methodfor the synthesis of calcium carbonate (aragonite) nanoparticlesfrom cockle shellsrdquoPowder Technology vol 235 pp 70ndash75 2013

[21] F P De Sousa G P Dos Reis C C Cardoso W N Mussel andV M D Pasa ldquoPerformance of CaO from different sources asa catalyst precursor in soybean oil transesterification kineticsand leaching evaluationrdquo Journal of Environmental ChemicalEngineering vol 4 no 2 pp 1970ndash1977 2016

[22] A Okullo A K Temu J W Ntalikwa and P Ogwok ldquoOpti-mization of biodiesel production from Jatropha oilrdquo Interna-tional Journal of Engineering Research inAfrica vol 3 pp 62ndash732010

[23] P Goyal M P Sharma and S Jain ldquoOptimization of ester-ification and transesterification of high FFA Jatropha curcasoil using response surface methodologyrdquo Journal of PetroleumScience and Engineering vol 1 no 3 pp 36ndash43 2012

[24] U Rashid F Anwar B R Moser and S Ashraf ldquoProductionof sunflower oil methyl esters by optimized alkali-catalyzedmethanolysisrdquo Biomass and Bioenergy vol 32 no 12 pp 1202ndash1205 2008

[25] R Anr A A SalehM S Islam S Hamdan andM AMalequeldquoBiodiesel production from crude Jatropha oil using a highlyactive heterogeneous nanocatalyst by optimizing transesterifi-cation reaction parametersrdquo Energy and Fuels vol 30 no 1 pp334ndash343 2016

[26] S Pradhan C S Madankar P Mohanty and S N NaikldquoOptimization of reactive extraction of castor seed to producebiodiesel using response surface methodologyrdquo Fuel vol 97 pp848ndash855 2012

[27] A Kumar Tiwari A Kumar and H Raheman ldquoBiodieselproduction from jatropha oil (Jatropha curcas) with high freefatty acids an optimized processrdquo Biomass and Bioenergy vol31 no 8 pp 569ndash575 2007

[28] G Vicente A Coteron MMartinez and J Aracil ldquoApplicationof the factorial design of experiments and response surfacemethodology to optimize biodiesel productionrdquo IndustrialCrops and Products vol 8 no 1 pp 29ndash35 1998

[29] S Dhingra K K Dubey and G Bhushan ldquoEnhancement inJatropha-based biodiesel yield by process optimisation usingdesign of experiment approachrdquo International Journal of Sus-tainable Energy vol 33 no 4 pp 842ndash853 2014

[30] S Dhingra G Bhushan and K K Dubey ldquoDevelopmentof a combined approach for improvement and optimizationof karanja biodiesel using response surface methodology andgenetic algorithmrdquo Frontiers in Energy vol 7 no 4 pp 495ndash5052013

[31] D Kanakaraju C Jios and S M Long ldquoHeavy metal concen-trations in the Razor Clams (Solen spp) from Muara TebasSarawakrdquo Malaysian Journal of Analytical Sciences vol 12 pp53ndash58 2008

[32] S Akmar and K Ab Rahim ldquoRazor Clam (Solen spp) fisheryin Sarawak Malaysiardquo Kuroshio Science vol 5 no 1 pp 87ndash942011

[33] M F Hossen S Hamdan and M R Rahman ldquoReview onthe risk assessment of heavy metals in Malaysian clamsrdquo TheScientific World Journal vol 2015 Article ID 905497 7 pages2015

[34] K N Islam M Z B A Bakar M M Noordin M Z BinHussein N S B A Rahman and M E Ali ldquoCharacterisationof calcium carbonate and its polymorphs from cockle shells(Anadara granosa)rdquo Powder Technology vol 213 no 1 pp 188ndash191 2011

[35] A N R Reddy A A Saleh S Islam and S Hamdan ldquoOpti-mization of transesterification parameters for optimal biodieselyield fromCrude Jatropha oil using a newly synthesized seashellcatalystrdquo Journal of Engineering Science andTechnology In press

[36] A N R Reddy A Saleh M S Islam and S Hamdan ldquoActiveheterogeneous CaO catalyst synthesis from Anadara granosa(Kerang) seashells for Jatropha biodiesel productionrdquo MATECWeb of Conferences vol 87 Article ID 02008 6 pages 2017

[37] S Ismail A S Ahmed R Anr and S Hamdan ldquoBiodieselproduction from castor oil by using calcium oxide derived frommud clam shellrdquo Journal of Renewable Energy vol 2016 ArticleID 5274917 8 pages 2016

[38] A N R Reddy A A Saleh M D S Islam and S HamdanldquoMethanolysis of Crude Jatropha oil using heterogeneous cata-lyst from the seashells and eggshells as green biodieselrdquo ASEAN


Journal on Science and Technology for Development vol 32 no1 pp 16ndash30 2015

[39] X Deng Z Fang and Y H Liu ldquoUltrasonic transesterificationof Jatropha curcas L oil to biodiesel by a two-step processrdquoEnergy Conversion and Management vol 51 no 12 pp 2802ndash2807 2010

[40] S Niju K M Meera Sheriffa Begum and N AnantharamanldquoEnhancement of biodiesel synthesis over highly active CaOderived from natural white bivalve clam shellrdquo Arabian Journalof Chemistry vol 9 pp 633ndash639 2016

[41] S Niju M S Begum and N Anantharaman ldquoModification ofegg shell and its application in biodiesel productionrdquo Journal ofSaudi Chemical Society vol 18 no 5 pp 702ndash706 2014

[42] B Yoosuk P Udomsap B Puttasawat and P Krasae ldquoImprov-ing transesterification acitvity of CaO with hydration tech-niquerdquo Bioresource Technology vol 101 no 10 pp 3784ndash37862010

[43] A Bazargan M D Kostic O S Stamenkovic V B Veljkovicand G McKay ldquoA calcium oxide-based catalyst derived frompalmkernel shell gasification residues for biodiesel productionrdquoFuel vol 150 pp 519ndash525 2015

[44] P-L Boey G P Maniam and S A Hamid ldquoBiodiesel produc-tion via transesterification of palm olein using waste mud crab(Scylla serrata) shell as a heterogeneous catalystrdquo BioresourceTechnology vol 100 no 24 pp 6362ndash6368 2009

[45] A K Endalew Y Kiros and R Zanzi ldquoHeterogeneous catalysisfor biodiesel production from Jatropha curcas oil (JCO)rdquoEnergy vol 36 no 5 pp 2693ndash2700 2011

[46] H V Lee J C Juan N F Binti Abdullah R NizahMF and YHTaufiq-Yap ldquoHeterogeneous base catalysts for edible palm andnon-edible Jatropha-based biodiesel productionrdquo ChemistryCentral Journal vol 8 no 1 article 30 2014

[47] X Deng Z Fang Y-H Liu and C-L Yu ldquoProduction ofbiodiesel from Jatropha oil catalyzed by nanosized solid basiccatalystrdquo Energy vol 36 no 2 pp 777ndash784 2011

[48] H J Berchmans and S Hirata ldquoBiodiesel production fromcrude Jatropha curcas L seed oil with a high content of free fattyacidsrdquoBioresource Technology vol 99 no 6 pp 1716ndash1721 2008

[49] D Vujicic D Comic A Zarubica R Micic and G BoskovicldquoKinetics of biodiesel synthesis from sunflower oil over CaOheterogeneous catalystrdquo Fuel vol 89 no 8 pp 2054ndash2061 2010

[50] W Roschat T Siritanon T Kaewpuang B Yoosuk and VPromarak ldquoEconomical and green biodiesel production processusing river snail shells-derived heterogeneous catalyst and co-solvent methodrdquo Bioresource Technology vol 209 pp 343ndash3502016

[51] N T McDevitt and W L Baun ldquoInfrared absorption studyof metal oxides in the low frequency region (700-240 cm-1)rdquoSpectrochimica Acta vol 20 no 5 pp 799ndash808 1964

[52] S Nasrazadani and E Eureste ldquoApplication of FTIR for Quan-titative Lime Analysisrdquo Denton Texas 2008 httpswwwntisgov

[53] M I Zaki H Knozinger B Tesche and G A H MekhemerldquoInfluence of phosphonation and phosphation on surface acid-base and morphological properties of CaO as investigated byin situ FTIR spectroscopy and electron microscopyrdquo Journal ofColloid and Interface Science vol 303 no 1 pp 9ndash17 2006

[54] Z Mirghiasi F Bakhtiari E Darezereshki and E Esmaeil-zadeh ldquoPreparation and characterization of CaO nanoparticlesfrom Ca(OH)2 by direct thermal decomposition methodrdquoJournal of Industrial and Engineering Chemistry vol 20 no 1pp 113ndash117 2014

[55] S H Teo A Islam F L Ng and Y H Taufiq-Yap ldquoBiod-iesel synthesis from photoautotrophic cultivated oleoginousmicroalgae using a sand dollar catalystrdquo RSC Advances vol 5no 58 pp 47140ndash47152 2015

[56] G Chen R Shan J Shi and B Yan ldquoUltrasonic-assistedproduction of biodiesel from transesterification of palm oil overostrich eggshell-derived CaO catalystsrdquo Bioresource Technologyvol 171 pp 428ndash432 2014

[57] Y Ren Z Ma and P G Bruce ldquoOrdered mesoporous metaloxides synthesis and applicationsrdquo Chemical Society Reviewsvol 41 no 14 p 4909 2012

[58] Z Kesic I Lukic D Brkic et al ldquoMechanochemical preparationand characterization of CaO∙ZnO used as catalyst for biodieselsynthesisrdquoApplied Catalysis A General vol 427-428 pp 58ndash652012


[60] D C Montgomery Design and Analysis of Experiments JohnWiley amp Sons 8th edition 2012 httpsbooksgooglecommybooksid=XQAcAAAAQBAJ

[61] H Ceylan S Kubilay N Aktas and N Sahiner ldquoAn approachfor prediction of optimum reaction conditions for laccase-catalyzed bio-transformation of 1-naphthol by response surfacemethodology (RSM)rdquo Bioresource Technology vol 99 no 6 pp2025ndash2031 2008

[62] P Verma M P Sharma and G Dwivedi ldquoImpact of alcohol onbiodiesel production and propertiesrdquo Renewable and Sustain-able Energy Reviews vol 56 pp 319ndash333 2016

[63] G Joshi D S Rawat B Y Lamba et al ldquoTransesterificationof Jatropha and Karanja oils by using waste egg shell derivedcalcium based mixed metal oxidesrdquo Energy Conversion andManagement vol 96 pp 258ndash267 2015

[64] A P S Chouhan and A K Sarma ldquoModern heterogeneouscatalysts for biodiesel production a comprehensive reviewrdquoRenewable and Sustainable Energy Reviews vol 15 no 9 pp4378ndash4399 2011

[65] M Sanchez F Bergamin E Pena M Martınez and J AracilldquoA comparative study of the production of esters from Jatrophaoil using different short-chain alcohols optimization and char-acterizationrdquo Fuel vol 143 pp 183ndash188 2015

[66] G Knothe ldquoAnalyzing biodiesel standards and othermethodsrdquoJournal of the American Oil Chemistsrsquo Society vol 83 no 10 pp823ndash833 2006

[67] K Boonmee S Chuntranuluck V Punsuvon and P SilayoildquoOptimization of biodiesel production from Jatropha oil (Jat-ropha curcasL) using response surfacemethodologyrdquo Journal ofSustainable Energy amp Environment vol 299 pp 290ndash299 2010

[68] R SathishKumar K Sureshkumar andRVelraj ldquoOptimizationof biodiesel production from Manilkara zapota (L) seed oilusing Taguchi methodrdquo Fuel vol 140 pp 90ndash96 2015

[69] F Ma and M A Hanna ldquoBiodiesel production a reviewrdquoBioresource Technology vol 70 no 1 pp 1ndash15 1999

[70] D Y C Leung X Wu and M K H Leung ldquoA reviewon biodiesel production using catalyzed transesterificationrdquoApplied Energy vol 87 no 4 pp 1083ndash1095 2010

[71] D Y C Leung and Y Guo ldquoTransesterification of neat andused frying oil optimization for biodiesel productionrdquo FuelProcessing Technology vol 87 no 10 pp 883ndash890 2006

[72] B Freedman E H Pryde and T LMounts ldquoVariables affectingthe yields of fatty esters from transesterified vegetable oilsrdquo


Journal of the American Oil Chemists Society vol 61 no 10 pp1638ndash1643 1984

[73] K Prasertsit P Phoosakul and S Sukmanee ldquoUse of calciumoxide in palm oil methyl ester productionrdquo SongklanakarinJournal of Science and Technology vol 36 no 2 pp 195ndash2002014

[74] M Kouzu T Kasuno M Tajika S Yamanaka and J HidakaldquoActive phase of calcium oxide used as solid base catalystfor transesterification of soybean oil with refluxing methanolrdquoApplied Catalysis A General vol 334 no 1-2 pp 357ndash365 2008

[75] A C Alba-Rubio M L Alonso Castillo M C G AlbuquerqueR Mariscal C L Cavalcante Jr and M L Granados ldquoA newand efficient procedure for removing calcium soaps in biodieselobtained using CaO as a heterogeneous catalystrdquo Fuel vol 95pp 464ndash470 2012

[76] S M Hailegiorgis S Mahadzir and D Subbarao ldquoParametricstudy and optimization of in situ transesterification of Jatrophacurcas L assisted by benzyltrimethylammonium hydroxide asa phase transfer catalyst via response surface methodologyrdquoBiomass and Bioenergy vol 49 pp 63ndash73 2013

[77] P K Roy S Datta S Nandi and F Al Basir ldquoEffect of masstransfer kinetics for maximum production of biodiesel fromJatropha Curcas oil a mathematical approachrdquo Fuel vol 134pp 39ndash44 2014

Submit your manuscripts athttpswwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 201

International Journal ofInternational Journal ofPhotoenergy


Carbohydrate Chemistry

International Journal ofInternational Journal of


Journal of

Chemistry


Advances in

Physical Chemistry

Hindawi Publishing Corporationhttpwwwhindawicom

Analytical Methods in Chemistry

Journal of

Volume 2014

Bioinorganic Chemistry and ApplicationsHindawi Publishing Corporationhttpwwwhindawicom Volume 2014

SpectroscopyInternational Journal of


The Scientific World JournalHindawi Publishing Corporation httpwwwhindawicom Volume 2014

Medicinal ChemistryInternational Journal of


Chromatography Research International


Applied ChemistryJournal of



Theoretical ChemistryJournal of


Journal of

Spectroscopy

Analytical ChemistryInternational Journal of


Journal of


Quantum Chemistry


Organic Chemistry International

ElectrochemistryInternational Journal of



CatalystsJournal of


MG +MeoHCatalystlarr997888997888997888997888rarr Glycerol +ME (3)

Catalytic activity of a solid catalyst is highly influencedby its surface area and particle size distribution [8 9]Moreover rate of a reaction among the reactants significantlyaccelerates with lower particle catalysts since it improvesthe diffusion forces over catalyst particle surfaces and bettermass flow channels [8 10] In addition this phenomenonensures higher reaction rate through availability of largenumber of active reactant molecules that need a minimalactivation energy Calcium based catalysts demonstrate keypromising characteristics that include higher basicity lessersolubility better reusability low costs and easy availabilityA large number of studies have been devoted to investigatebiodiesel applications of pure or mixed calcium catalysts[11ndash15] Buasri et al [10] produced biodiesel from palm oilusing CaO catalyst which synthesized various seashells thatincludemussel cockle and scallop and reported surface areas(119878BET) of 8991m

2g 5987m2g and 7496m2g respectivelyShan et al [16] studied Ca-based heterogeneous catalystperspectives synthesized using rich waste materials suchas bones mollusk shells egg shells and industrial wastesbesides catalytic activity and biodiesel applications of calciumcatalysts prospects and challenges were discussed Mohamedet al [17] derived CaO from cockle shell by calcinationat 850∘C while Nurdin [18] derived CaO catalyst fromPaphia undulata shell wastes through calcination at 680∘C fortransesterification of Jatropha curcas oil (JCO) and Rubber oilto biodiesel Choudhury et al [11] Teo et al [12] and Taufiq-Yap et al [13] investigated the transesterification of JCO usingCaO of 119878BET 7114m2g 92 plusmn 080m2g and 95m2g andobtained a biodiesel of 8936 90 and 85 respectivelywhile Margaretha et al [19] experimented with Pomacea spshells produced CaO with pore volume of 004 ccg and 119878BETof 17m2g for transesterification palm oil to biodiesel Tan etal [14] investigated the transesterification kinetics of wastecooking oil to biodiesel using CaO catalyst synthesized fromostrich and chicken-eggshells besides their 119878BET of 710m2gand 546m2g respectively Islam et al [20] synthesizednano-CaCO3 with particle of 20 plusmn 5 nm diameter fromcockle shells by grinding mechanically in the presence ofdodecyl dimethyl betaine De Sousa et al [21] investigatedtransesterification kinetics of soybean oil using commercialCaO egg shell CaO carb shell CaO 119878BE of 09m2g 43m2gand 40m2g and particle size of 56 nm 184 nm and 74 nmrespectively

The significant transesterification reaction parametersthat influence JME yield include catalyst loading methanolto oil ratio reaction time heating temperature and thestirring rpm [22ndash26] Many researchers explored optimalparametric sufficiency over their minimum and maximumlevelsThe intrinsic impact of a parameter and their potentialinteractions to achieve the optimal FAME yield was investi-gated using the response surface methodology (RSM) as anoptimization and statistical analysis tool [11 22 27] RSMwas widely adopted based on three designs of CCD CCRD[22 27] and Box-Behnken design [11] for optimal FAMEVicente et al [28] testified over two factors temperature

(20∘Cndash75∘C) and catalyst concentration (02ndash18 wt) usingsunflower oil in the presence of various homogeneous andheterogeneous catalysts Goyal et al [23] reported the impactof four reaction parameters including the methanol-oil ratioreaction timeNaOHcatalyst concentration and temperatureover transesterification of JCO A CCD based four-factor-five-level was utilized to analyze the parametric impact on theFAME yield An optimal FAME field of 983 was reportedat 11 1molar ratio 1 wt catalyst 54∘C temperature and110min of reaction time while Dhingra et al investigatedKaranja [29] and Jatropha [30] biodiesels production opti-mization by considering five reaction parameters using theRSM coupled with GA [29] Many studies reported that thechoice of reaction parameters directly contributes in biodieselconversion process and influences FAME yield Also it isnoted that reaction parameters both stirring speed andreaction time were less studied

The literature studies emphasize suitability of calcium cat-alyst for biodiesel production via transesterification Besideshigher surface area large pores and lesser particle size of acatalyst enhance their catalytic efficacy of transesterificationreaction [11ndash15] Ensis arcuatus has been commonly foundto be fishery food source in the sandy coastal locations ofPacific and Antarctic areas and regionally referred to asRazor clams The study reports of Kanakaraju et al [31]Akmar and Rahim [32] and Hossen et al [33] demonstratepotential of Razor clams marine life and abundance in thestate of Sarawak as well as in the west Malaysian provincesThe previous works on synthesis of calcium catalysts arevery limited and have been focused on increasing catalystsurface area and lowering the particle size from naturallyavailable renewable wastes such as aquatic seashells [1820 21 34ndash38] However according to the best of ourbroad literature survey no work has reported on activatedCaO nanocatalyst synthesis using Razor shells Moreovera very scant work was accounted on the study on kinet-ics of transesterification reaction parameters that includecatalyst loading methanol to oil ratio heating tempera-ture stirring speed and reaction time which need to beundertaken

In this study CaO of high surface area and pores as wellas lower particle size was synthesized from a seashell so asto result in an activated heterogeneous catalyst Besides thedirect and interaction impacts of five reaction parameterson the FAME yield were proposed to be investigated overJCO two-step transesterification process Activated CaO wassynthesized using locally available seashell species Razorshells A laboratory scale experimental protocol ldquocalcination-hydro aeration-dehydrationrdquo was developed for Razor shellCaO synthesis besides structural and morphological char-acteristics were analyzed The transesterification reactionkinetics was studied by employing a CCD based on the five-factor-five-level two-block half factorial RSM model JMEproduction optimization protocol using active Razor shellCaO catalyst is shown in ldquoScheme 1rdquo The catalyst stabilityreusability and leaching were investigated The synthesizedJME fuel properties were tested according to the biodieselstandards EN14214


(1)

(2)

(3)(4)

(5)

(6)

(7)

Razor shell



RSM-CCD model



(gt99)

JMEyield 9880

70

60

50

40

301 2 3 4 5

M

C













RCOOH + CH3OHH

2SO

4997904997904997904997904997904rArr RCOOCH3 +H2O (4)






(1)

(2)

(3)

(4)

(5)

(6)

(7)



119884 = 1205730 +119899

sum119894=1

120573119894119896119894 +119899

sum119894=1

1205731198941198941198962119894 +sum

119899

sum119894lt119895=1

120573119894119895119896119894119896119895 + 120576 (5)








Literaturereview




Known

No Yes

No

Yes

Expe

rimen

tal

FitnessNo




Yes





No

Yes


EndValidated

Revi

ewEx

perim

enta

l des

ign

Mod

eling

amp o

ptim

izat

ion

Resu

lts va

lidat

ion

Parametersle 5






250 450 650 850 1050

100

80

60

Wei

ght (

)

02

01

00

minus01

minus02

minus03

minus04

minus05

minus06

Der

ivat

ive w

eigh

t los

s (

)

Temperature (∘C)




Razor shell CaO

Lab grade CaO

4000 3500 3000 2500 2000 1500 1000 500 0Wave numbers (1cm)

Tran

smitt

ance

()


0500

1000150020002500

0500

1000150020002500

20 25 30 35 40 45 50 55 60 65 70

Inte

nsity ο

ο ο οοο

οο ο ο

Lab grade CaO

Razor shell CaO


lowast

lowast

lowastlowast

lowast

⧫ ⧫⧫

⧫⧫ ⧫

⧫⧫⧫⧫⧫

ο CaO

lowast

⧫ Ca(OH)2CaCO3





(a) (b)

(c) (d)






In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(1)

(2)

(3)(4)

(5)

(6)

(7)

Razor shell



RSM-CCD model



(gt99)

JMEyield 9880

70

60

50

40

301 2 3 4 5

M

C













RCOOH + CH3OHH

2SO

4997904997904997904997904997904rArr RCOOCH3 +H2O (4)






(1)

(2)

(3)

(4)

(5)

(6)

(7)



119884 = 1205730 +119899

sum119894=1

120573119894119896119894 +119899

sum119894=1

1205731198941198941198962119894 +sum

119899

sum119894lt119895=1

120573119894119895119896119894119896119895 + 120576 (5)








Literaturereview




Known

No Yes

No

Yes

Expe

rimen

tal

FitnessNo




Yes





No

Yes


EndValidated

Revi

ewEx

perim

enta

l des

ign

Mod

eling

amp o

ptim

izat

ion

Resu

lts va

lidat

ion

Parametersle 5






250 450 650 850 1050

100

80

60

Wei

ght (

)

02

01

00

minus01

minus02

minus03

minus04

minus05

minus06

Der

ivat

ive w

eigh

t los

s (

)

Temperature (∘C)




Razor shell CaO

Lab grade CaO

4000 3500 3000 2500 2000 1500 1000 500 0Wave numbers (1cm)

Tran

smitt

ance

()


0500

1000150020002500

0500

1000150020002500

20 25 30 35 40 45 50 55 60 65 70

Inte

nsity ο

ο ο οοο

οο ο ο

Lab grade CaO

Razor shell CaO


lowast

lowast

lowastlowast

lowast

⧫ ⧫⧫

⧫⧫ ⧫

⧫⧫⧫⧫⧫

ο CaO

lowast

⧫ Ca(OH)2CaCO3





(a) (b)

(c) (d)






In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of






RCOOH + CH3OHH

2SO

4997904997904997904997904997904rArr RCOOCH3 +H2O (4)






(1)

(2)

(3)

(4)

(5)

(6)

(7)



119884 = 1205730 +119899

sum119894=1

120573119894119896119894 +119899

sum119894=1

1205731198941198941198962119894 +sum

119899

sum119894lt119895=1

120573119894119895119896119894119896119895 + 120576 (5)








Literaturereview




Known

No Yes

No

Yes

Expe

rimen

tal

FitnessNo




Yes





No

Yes


EndValidated

Revi

ewEx

perim

enta

l des

ign

Mod

eling

amp o

ptim

izat

ion

Resu

lts va

lidat

ion

Parametersle 5






250 450 650 850 1050

100

80

60

Wei

ght (

)

02

01

00

minus01

minus02

minus03

minus04

minus05

minus06

Der

ivat

ive w

eigh

t los

s (

)

Temperature (∘C)




Razor shell CaO

Lab grade CaO

4000 3500 3000 2500 2000 1500 1000 500 0Wave numbers (1cm)

Tran

smitt

ance

()


0500

1000150020002500

0500

1000150020002500

20 25 30 35 40 45 50 55 60 65 70

Inte

nsity ο

ο ο οοο

οο ο ο

Lab grade CaO

Razor shell CaO


lowast

lowast

lowastlowast

lowast

⧫ ⧫⧫

⧫⧫ ⧫

⧫⧫⧫⧫⧫

ο CaO

lowast

⧫ Ca(OH)2CaCO3





(a) (b)

(c) (d)






In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




(1)

(2)

(3)

(4)

(5)

(6)

(7)



119884 = 1205730 +119899

sum119894=1

120573119894119896119894 +119899

sum119894=1

1205731198941198941198962119894 +sum

119899

sum119894lt119895=1

120573119894119895119896119894119896119895 + 120576 (5)








Literaturereview




Known

No Yes

No

Yes

Expe

rimen

tal

FitnessNo




Yes





No

Yes


EndValidated

Revi

ewEx

perim

enta

l des

ign

Mod

eling

amp o

ptim

izat

ion

Resu

lts va

lidat

ion

Parametersle 5






250 450 650 850 1050

100

80

60

Wei

ght (

)

02

01

00

minus01

minus02

minus03

minus04

minus05

minus06

Der

ivat

ive w

eigh

t los

s (

)

Temperature (∘C)




Razor shell CaO

Lab grade CaO

4000 3500 3000 2500 2000 1500 1000 500 0Wave numbers (1cm)

Tran

smitt

ance

()


0500

1000150020002500

0500

1000150020002500

20 25 30 35 40 45 50 55 60 65 70

Inte

nsity ο

ο ο οοο

οο ο ο

Lab grade CaO

Razor shell CaO


lowast

lowast

lowastlowast

lowast

⧫ ⧫⧫

⧫⧫ ⧫

⧫⧫⧫⧫⧫

ο CaO

lowast

⧫ Ca(OH)2CaCO3





(a) (b)

(c) (d)






In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Literaturereview




Known

No Yes

No

Yes

Expe

rimen

tal

FitnessNo




Yes





No

Yes


EndValidated

Revi

ewEx

perim

enta

l des

ign

Mod

eling

amp o

ptim

izat

ion

Resu

lts va

lidat

ion

Parametersle 5






250 450 650 850 1050

100

80

60

Wei

ght (

)

02

01

00

minus01

minus02

minus03

minus04

minus05

minus06

Der

ivat

ive w

eigh

t los

s (

)

Temperature (∘C)




Razor shell CaO

Lab grade CaO

4000 3500 3000 2500 2000 1500 1000 500 0Wave numbers (1cm)

Tran

smitt

ance

()


0500

1000150020002500

0500

1000150020002500

20 25 30 35 40 45 50 55 60 65 70

Inte

nsity ο

ο ο οοο

οο ο ο

Lab grade CaO

Razor shell CaO


lowast

lowast

lowastlowast

lowast

⧫ ⧫⧫

⧫⧫ ⧫

⧫⧫⧫⧫⧫

ο CaO

lowast

⧫ Ca(OH)2CaCO3





(a) (b)

(c) (d)






In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





250 450 650 850 1050

100

80

60

Wei

ght (

)

02

01

00

minus01

minus02

minus03

minus04

minus05

minus06

Der

ivat

ive w

eigh

t los

s (

)

Temperature (∘C)




Razor shell CaO

Lab grade CaO

4000 3500 3000 2500 2000 1500 1000 500 0Wave numbers (1cm)

Tran

smitt

ance

()


0500

1000150020002500

0500

1000150020002500

20 25 30 35 40 45 50 55 60 65 70

Inte

nsity ο

ο ο οοο

οο ο ο

Lab grade CaO

Razor shell CaO


lowast

lowast

lowastlowast

lowast

⧫ ⧫⧫

⧫⧫ ⧫

⧫⧫⧫⧫⧫

ο CaO

lowast

⧫ Ca(OH)2CaCO3





(a) (b)

(c) (d)






In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


(a) (b)

(c) (d)






In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


In volumeundersize

Q3

(cum

ulat

ive v

alue

s) (

)


Hist

ogra

m[times100]

100

80

60

40

20

0004 01 10 100 1000 5000

(a)

Hist

ogra

m[times200]

In volumeundersize


100

80

60

40

20

0004 01 10 100 1000 5000

Q3

(cum

ulat

ive v

alue

s) (

)

(b)






119884 = 100071 + 0262119862 + 6707119872 + 4002119879 + 4515119867


minus 118241198672 minus 65241198772 + 4379119862119872 + 0493119862119879


+ 0721119872119877 minus 1393119879119867 + 3754119879119877 minus 1707119867119877

(6)











27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of









27 1 0 0 0 0 0 9825 980028 1 0 0 0 0 0 9825 980029 1 0 0 0 0 0 9526 976030 1 0 0 0 0 0 9526 976031 1 0 0 0 0 0 9825 980032 1 0 0 0 0 0 9825 9780

















Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of












Linear 5 63277 39359 78717 1182 lt00001119862 1 1115 041 0405 006 08100119872 1 32866 21145 211452 3175 lt00001119879 1 10168 928 92800 1394 00030119867 1 18728 11413 114130 1714 00020119877 1 400 502 5021 075 04040










180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


180

160

140

120

100

80

60

T

1 2 3 4 5

C

MHR

JMElt72

gt99



5050600


70

60

50

40

30

M

1 2 3 4 5

C

THR


12050600




60

55

50

45

40

H

1 2 3 4 5

C

MTR


50120600




700

650

600

550

500

R

1 2 3 4 5

C

MTH


5012050




180

160

140

120

100

80

6030 40 50 60 70

T

M

CHR

JMElt60 Hold values

350600




H

30 40 50 60 70

M

60

55

50

45

40

CTR

JMElt62

gt98



3120600


700

650

600

550

500

R

30 40 50 60 70

M

CTH


312050




1801601401201008060

T

H

60

55

50

45

40

CMR


350600




1801601401201008060

700

650

600

550

500

T

R

CMH


35050




Figure 8 Continued


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


6055504540

700

650

600

550

500

H

R

CMT


350120





7000

7500

8000

8500

9000

9500

10000

7000 7500 8000 8500 9000 9500 10000

JME

pred

icte

d yi

eld

()









Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Data set




Reaction time(min)

Heatingtemperature

(∘C)










988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


988

976

2

957

5

915

2

843

3

764

902

4

867

3

806

743

6

691

3

645

60

65

70

75

80

85

90

95

100

Fresh CaO 1 2 3 4 5

JME

yiel

d (

)


(a) (b)

(c) (d) (e)

(f)





4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




4 Conclusions




Acknowledgments



References




























































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of




















































































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of

Active Razor Shell CaO Catalyst Synthesis for Jatropha...

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Transcript of Active Razor Shell CaO Catalyst Synthesis for Jatropha...