research article green biodiesel synthesis using waste...

Research ArticleGreen Biodiesel Synthesis Using Waste Shells as SustainableCatalysts with Camelina sativa Oil

Yelda Hangun-Balkir

Manhattan College Department of Biochemistry and Chemistry 4513 Manhattan College Parkway Riverdale NY 10471 USA

Correspondence should be addressed to Yelda Hangun-Balkir yeldahangunbalkirmanhattanedu

Received 6 September 2016 Revised 8 November 2016 Accepted 10 November 2016

Academic Editor Eri Yoshida

Copyright copy 2016 Yelda Hangun-BalkirThis is an open access article distributed under theCreativeCommonsAttribution Licensewhich permits unrestricted use distribution and reproduction in any medium provided the original work is properly cited

Waste utilization is an essential component of sustainable development and waste shells are rarely used to generate practicalproducts and processes Most waste shells are CaCO

3rich which are converted to CaO once calcined and can be employed as

inexpensive and green catalysts for the synthesis of biodiesel Herein we utilized lobster and eggshells as green catalysts for thetransesterification of Camelina sativa oil as feedstock into biodiesel Camelina sativa oil is an appealing crop option as feedstockfor biodiesel production because it has high tolerance of cold weather drought and low-quality soils and contains approximately40 oil content The catalysts from waste shells were characterized by X-ray powder diffraction Fourier Transform Infrared Spec-troscopy and Scanning Electron Microscope The product biodiesel was studied by 1H NMR and FTIR spectroscopy The effectsof methanol to oil ratio reaction time reaction temperature and catalyst concentration were investigated Optimum biodieselyields were attained at a 12 1 (alcohol oil) molar ratio with 1 wt heterogeneous catalysts in 3 hours at 65∘C The experimentalresults exhibited a first-order kinetics and rate constants and activation energy were calculated for the transesterification reactionat different temperatures The fuel properties of the biodiesel produced from Camelina sativa oil and waste shells were comparedwith those of the petroleum-based diesel by using American Society for Testing and Materials (ASTM) standards

1 Introduction

Development of alternative fuels has been widely studiedbecause of the depletion of fossil fuels and increased con-cerns for environment One of the most promising areas ofrenewable fuel development is the production of biodieselBiodiesel which is a renewable nontoxic and biodegradablefuel can be used in diesel engines without engine modi-fications Biodiesel burns cleaner than conventional dieselfuel substantially reduces carbon monoxide hydrocarbonsparticulate matter and eliminates sulfur dioxide emissions[1] It contributes no net carbon dioxide to the atmosphereand it reduces greenhouse gas emissions by 41 comparedwith diesel [2] In addition biodiesel has high cetane numberhigh flash point and excellent lubricity and miscibility withpetroleum diesel at all ratios [3]

Biodiesel fatty acid methyl ester (FAME) is traditionallymade by transesterification reaction fromvarious types of oilsand either ethanol ormethanol in presence of a homogeneouscatalyst [4] Transesterification is a reversible process which

requires a strong acid or a strong base The main productof the transesterification reaction is biodiesel and glycerol isformed as a by-product The transesterification reaction isshown in Figure 1 [5]

Most of the current biodiesel production comes fromsoybean as edible oil feedstock in the United States as aresult production of biodiesel competes for food Worldwidedemand for food is estimated to double within the fiftyyears and need for fuel is anticipated to increase even morerapidly [6] There is a great need for biodiesel that does notcause significant environmental harm and does not competewith food supply Biodiesel that can be produced frominedible crops on agriculturally marginal lands with minimalfertilizer pesticide and fossil energy inputs has potential toprovide energy over the longer term [7] Camelina sativaoil offers a valuable substitute for the edible oils becauseCamelina sativa plant grows quickly in infertile groundsCamelina sativa oil is high in erucic acid and glucosinolateswhich limits the usage as food [8] It contains approximately35ndash45 oil content and it has lower fertilizer water and

Hindawi Publishing CorporationJournal of ChemistryVolume 2016 Article ID 6715232 10 pageshttpdxdoiorg10115520166715232

2 Journal of Chemistry

Biodiesel

O

OR998400CO-CH2

OR998400CO-CH

R998400CO-CH2

+ 3 CH3OHCatalyst

3 R998400COOCH3 +

HO-CH2

HO-CH

HO-CH2

Figure 1 Transesterification reaction of triglycerides to biodiesel

pesticide requirements than other traditional oilseed cropssuch as soybean canola or corn [9] It can be grown on soilsreclaimed from mine spoils and abandoned farmlands Thecrop can stand of extreme climate conditions and poor soilquality and it might be grown in the cycle of crop rotationThe oil has significantly low production cost compared toother crops compared to soybean or corn oils [10]

Traditionally transesterification is achieved in the pres-ence of a homogeneous catalyst such as KOHorNaOHThesewidely used catalysts KOH and NaOH are easily soluble inmethanol forming potassiummethoxide or sodiummethox-ide respectively Although homogeneous catalyzed biodieselreactions are comparatively faster and showhigh conversionsthey present numerous drawbacks [11] The homogeneouscatalysts cannot be recovered and reused and they mustbe neutralized and separated from the biodiesel whichcauses a generation of excess waste water The oil feedstockshould have low free fatty acids otherwise the reactionforms soap The soap formation consumes the catalyst anddecreases the efficiency of the reaction In addition the soapprevents glycerol separation from biodiesel Production costof utilization of homogeneous catalysts is relatively high asthe process involves number of washing and purificationsteps in order to meet quality standards On the other handheterogeneous catalysts are more environmentally benignalternatives to homogeneous counterparts and they havemany advantages [12] The use of heterogeneous catalystsdoes not cause the soap formation and there is no need forneutralization Reactions with heterogeneous catalysts havesimpler biodiesel separation and purification steps Hetero-geneous catalysts do not produce waste water and they couldbe easily separated from liquid products by filtration and canbe designed to give higher activity selectivity and longerlifetimes [13] The catalysts are reusable which reduces theenvironmental impact and process cost Use of heterogeneouscatalysts instead of homogeneous catalysts could potentiallylead to cheaper production costs and opportunities to operatein a fixed bed continuous process [14] Overall they act asenergy efficient nontoxic and greener option

The production of biodiesel needs an efficient and low-cost heterogeneous catalyst tomake the process economicallyviable and environmentally friendly Alkaline earth metaloxides were widely studied as basic heterogeneous catalystsfor biodiesel synthesis [15] Calcium oxide was employedspecifically as a transesterification catalyst because of itsavailability low cost and excellent catalytic performanceunder ambient conditions The reactivity of CaO can befurther improved upon calcination At the beginning ofthe process CaO is converted to Ca(OCH

3)2 which is

an initiating reagent for transesterification reaction bymixing with methanol [16] CaO has high basicity andlow environmental impact due to its low solubility inmethanol [17] In addition CaO is easy to handle abundantnontoxic and economically feasible catalyst compared to itshomogeneous counterpart KOH Both waste eggshell andlobster shells are composed of approximately 95 of calciumcarbonate and the remaining components are magnesiumcarbonate calcium phosphate and organic matter [18 19]Since the shells mainly consist of CaCO

3 they decompose to

CaO via calcination Waste shells including avian eggshellsand seashells are excellent raw materials for the preparationof the heterogeneous catalysts For sustainable developmentwastes should be recycled and reused towards the productionof other goods Over the years it has become very costlyto dispose the waste shells in landfills and the landfillsare reaching their capacity Waste shells remain largelyunutilized as they are discarded wrongly The waste shells aremade up of calcium carbonate that can be used to produceheterogeneous catalysts for biodiesel synthesis Figure 2shows a flow diagram for transesterification process fromCamelina oil and waste shells as heterogeneous catalysts

Utilization of waste shells as catalysts will protect theenvironment by reducing the waste and create cost-effectivebiodiesel synthesis In this paper we utilized waste eggshellslobster shells and CaO as exemplary heterogeneous cata-lysts for the transesterification of Camelina sativa oil intobiodiesel The parameters such as methanol to oil ratio reac-tion time reaction temperature and catalyst concentrationwere studied and a kinetic study was performed by using thedata obtained from the optimization experiments The studydemonstrates several fundamental green principles includingthe use of renewable feedstocks catalysis and design fordegradation

2 Materials and Methods

Cold-pressed and unrefinedCamelina sativa oil was obtainedfromOleWorldOils Company Calciumoxidewas purchasedfrom Alfa Aesar Waste eggshells and lobster shells were col-lected from collegersquos cafeteria and neighborhood restaurantsAnhydrous methanol was purchased from Fischer Scientific

21 Catalyst Preparation Calcium oxide was used as it wasreceived The eggshells and lobster shells were rinsed withtap water to remove organic materials and impurities anddried at 110∘C for 2 hoursThe dried waste shells were grindedand calcined at 900∘C in air atmosphere with a heating rateof 10∘C per minute for 3 hours All catalysts were kept ina desiccator to avoid the interaction with air The raw andcalcined samples of the shells were analyzed by X-ray powderdiffraction (XRD) Fourier Transform Infrared Spectroscopy(FTIR) and Scanning ElectronMicroscope (SEM)The XRDcharacterization was studied on Bruker X-Ray D-2 Phaserdiffractometer over a 2120579 range from 5∘ to 60∘ with a step sizeof 001∘ and FTIR spectroscopy was performed on ThermoNexus 470 FTIR spectrometer The spectra were obtainedin the 500ndash4000 cmminus1 region and 32 scans were recorded

Journal of Chemistry 3

Camelina sativaoil

Transesterificationreaction

Calcined wasteshells amp methanol

Waste lobster ampeggshells

Crude biodieselamp glycerol

Filtration amp drying

Pure biodiesel

Recovered waste shells

Figure 2 The flowchart for the biodiesel reaction from Camelina sativa oil and waste shells

Table 1 Properties of Camelina sativa oil

Specific gravity Viscosity Caloric value Acid value Cetane number Pour point (∘C)092 146 445 320 3580 minus23

Surface structure and the morphology of the heterogeneouscatalysts were studied by Zeiss LEO Gemini 1550 ScanningElectron Microscope (SEM)

22 Characteristics of Camelina sativa Oil Fatty acid com-position of Camelina sativa oil which was provided by themanufacturer indicates 324 184 160 and 151 as120572-Linolenic Acid (18 3) Linoleic Acid (18 2) Oleic Acid(18 1) and cis-Eicosenoic Acid (20 1) respectively The acidvalue ofCamelina sativa oil was reported as 158 of free fattyacid [20] As stated by the literature the yield of biodieselsignificantly decreases when the free fatty acid level exceeds3 (ww) since the soap formation inhibits the separationbetween the biodiesel and glycerol and decreases the yieldof the final product [21] Table 1 shows the properties ofCamelina sativa oil

23 Transesterification Reaction The transesterification reac-tion was performed using 500mL round bottom flask with amagnetic stirrer thermometer and reflux condenser 100mLof Camelina sativa oil was heated to 100∘C for one hour toremove impurities before starting the transesterification reac-tion The oil was allowed to cool down to 65∘C The reactionwas carried out with a 12 1 molar ratio of methanol oil ratioand 1 (ww) of the chosen waste shell catalyst Pulverizedcalcined waste shell was stirred withmethanol at 65∘C for onehour to activate waste shell catalyst The mixture was addedto the oil and vigorously stirred at 65∘C for 3 hours to ensurecomplete conversion of the oil into biodiesel The waste shellcatalyst was recovered through filtration and the reactionmixture transferred to separatory funnel was allowed to settlefor 1 hour The lower layer which contains glycerol was

removed from the methyl esters Due to the low solubilityof glycerol in the esters the separation takes place rapidlyThe crude biodiesel remained in the top layer Yellow colorbiodiesel was dried using anhydrous sodium sulfateThe yieldof biodiesel was calculated by using the following equation

Yield =Weight of Biodiesel

Weigth of Camelina Oiltimes 100 (1)

The conversion of oil to biodiesel was analyzed by 1HNMR and FTIR spectroscopies An Eft-60 NMR spectrom-eter (Anasazi Instruments Indianapolis IN) and a ThermoNicolet NEXUS 470 FTIR spectrometer (Thermo ScientificWaltham MA) were used for the analyses The FTIR spectraof the samples were obtained in the 500ndash4000 cmminus1 regionafter 32 scans were recorded for each sample The qualityof biodiesel product was analyzed according to AmericanSociety for Testing and Materials (ASTM) specificationsdesignated in D-6751

3 Results and Discussion

The percent conversions of Camelina oil with CaO wasteeggshell and lobster shell catalysts to biodiesel are 991972 and 900 for the given reaction conditions respec-tively

31 Catalyst Characterization

311 X-Ray Diffraction Analysis The XRD patterns of rawand calcined lobster shell are given in Figure 3 The calcina-tion at 900∘C causes the removal of CO

2from CaCO

3in the


600

500

400

300

200

100

0

Inte

nsity

Calcined lobster shell

Raw lobster shell

10 20 30 40 50 60

2120579 (degree)

Figure 3 XRD pattern of raw and calcined lobster shell

600

500

400

300

200

100

0

Inte

nsity

CaO

Lobster shellEggshell

30 40 50

2120579 (degree)

Figure 4 XRD pattern of calcined CaO eggshell and lobster shell

natural waste lobster shell and results in CaO [22] Narrowand high intense peaks of the calcined catalyst define thewell-crystallized structure of the CaO Figure 4 shows the XRDpatterns for calcined eggshell lobster shell and commercialCaO The waste shell catalysts showed clear and sharp peakswhichmatch the crystalline phase of CaOThe peaks for bothcalcined eggshell and lobster shell at 900∘C show 2120579 values of3240 3750 and 5410 which are the characteristic peaks forCaO [23]

312 FTIR Analysis FTIR spectroscopy with Smart DiffuseReflectance whichwas used for characterization of the uncal-cined (raw) and calcined lobster shells is shown in Figure 5KBr was used as infrared transparent matrix for characteriza-tionThe broad absorption band at around 3420 cmminus1 is mostlikely due to O-H vibrations in water molecules The absorp-tion bands of uncalcined lobster shell at 1425 cmminus1 878 cmminus1and 710 cmminus1 were attributed to asymmetric stretch out-of-plane bend and in-plane bend respectively of CO3

2minus ionsThe broad absorption band around 3420 cmminus1 disappearsupon calcination at 900∘C Calcination causes the lobstershell to lose carbonate since CaCO

3decomposes into CaO

While the intensity of CaCO3peaks decreases a new sharp

stretching band appears at 3630 cmminus1 which is correspondingto O-H stretching vibration The peaks around 1450 cmminus1

0102030405060708090

100

tr

ansm

ittan

ce

100015002000250030003500Wavenumbers (cmminus1)

Calcinedlobstershell

Uncalcinedlobstershell

Figure 5 Infrared spectrum of uncalcined and calcined lobstershell

re

flect

ance


CaO

Lobster shell

Eggshell

80

70

60

50

40

30

20

10

0

minus10

minus20

minus30

Figure 6 Infrared spectrum of calcined CaO eggshell and lobstershell

correspond to the bending vibration of O-Ca-O groupA detailed study about temperature effects on shells waspublished by Engin et al and our results agree with theliterature findings [24] Figure 6 shows the FTIR spectra ofcalcinedCaO lobster and eggshell Bothwaste shells have thesame absorption bands as the bands of CaO

313 SEM Analysis The surface morphology of uncalcinedand calcined lobster shell catalysts is shown in Figure 7The uncalcined shells display a typical layered architecture[25] Both uncalcined and calcined shells contain varioussized and shaped particles The morphology of CaO wastelobster and waste eggshell calcined at 900∘C is shown inFigure 8 Calcined lobster shell shows regular morphologyof sphere particles with the size range from 120 to 50120583mof width Upon calcination the microstructures of the shellsare changed from layered architecture to porous structureTheparticle shape becamemore regularwith smaller particlesas a result of release of gaseous molecules Calcination ofthe catalyst derived from the waste shells causes an increasein surface area leading to better catalytic activity [26] Thesmall particles were combined together to yield agglomerates


(a) Uncalcined lobster shell (b) Calcined lobster shell

Figure 7 SEM images of uncalcined and calcined lobster shell

(a) Calcined CaO (b) Calcined lobster shell

(c) Calcined eggshell

Figure 8 SEM images of calcined CaO lobster and eggshell

because of CaO formation from calcium carbonate decom-position during the calcination process

32 Analysis of Biodiesel

321 NMRAnalysis Theconversion ofCamelina sativa oil tobiodiesel catalyzed by waste shells was analyzed by using 1HNMR spectroscopy The spectra for starting Camelina sativaoil and biodiesel are shown in Figure 9 Starting oil has a435 ppm signal which was lost during the transesterificationreactionThebiodiesel spectra showed the characteristic peakof methoxy protons that was prominently indicated by astrong singlet at 368 ppm and 120572-CH

2protons as a triplet

at 230 ppm These two peaks confirm the presence of fattyacidmethyl ester formation from starting oilThe other peakswere observed at 08 ppm due to terminal methyl protons astrong peak at 13 ppm is related to the methylene protons ofcarbon chain and multiplet at 21 ppm is due to 120573-carbonylmethylene protons respectivelyThe peak at 54 ppm is solelydue to olefinic protons on the carbon chain

322 FTIR Analysis FTIR spectroscopy was used to analyzebiodiesel and the spectrum is shown in Figure 10 The mostintense peak at 1745 cmminus1 is the characteristic of the estercarbonyl stretch ester -C=O The absorption bands at 12481198 and 1176 cmminus1 can be used to identify the methyl ester


8 6 4 2 0

Biodiesel

Camelina oil

(PPM)

Figure 9 1HNMRspectra ofCamelinaoil and synthesized biodieselcatalyzed by waste lobster shells

110

100

90

80

70

60

50

40

30

20

10

0

tr

ansm

ittan

ce

4000 3500 3000 2500 2000 1500 1000

Wavenumber (cmminus1)

Figure 10 FTIR spectra of biodiesel catalyzed by waste lobstershells

C-O-C stretching vibrations in the biodiesel The absorptionbands at 2850 and 2925 indicate the axial deformation ofCH2bond While the stretching vibrations of CH appear at

3050 cmminus1 a weak absorption band at 3445 cmminus1 indicatesOH stretching vibrationThe bands at 1465 and 1448 cmminus1 arethe indication of CH

2and CH

3bending vibrations

33 Effect of Parameters on Biodiesel Synthesis

331 Effect of Methanol to Camelina sativa Oil Molar Ratio onBiodiesel Yield Methanol to oil molar ratio was varied from6 1 to 18 1 while catalyst concentration and temperaturewere kept constant at 1 (ww) and 65∘C respectivelyFigure 11(a) shows the effect of methanol to oil molar ratio onbiodiesel yield for CaO eggshell and lobster shell catalyzedtransesterification reaction While the transesterification ofCamelina oil requires three moles of methanol for each mole

of oil excess methanol is required to shift the equilibriumtowards the direction of biodiesel formation The highamount of methanol promotes the formation of methoxyspecies which leads to higher yields The biodiesel yieldsharply increased while the molar ratio was increased from6 1 to 12 1 and slightly decreased exceeding 12 1 methanol tooil ratio According to literature excess methanol inhibits theseparation of glycerol since there is an increase in solubility[27] Higher amount of glycerol drives the equilibrium backto the left and lowering the yield of biodiesel The maximumyield was achieved at 12 1 molar ratio

332 Effect of Reaction Time on Biodiesel Yield The biodieselyield was significantly affected by reaction time which wasvaried from 1 hour to 6 hours for experiments with threeheterogeneous catalysts During the trials the methanol tooil molar ratio catalyst concentration and temperature werekept at 12 1 and 1 (ww) and 65∘C respectively As shown inFigure 11(b) as reaction time was increased from 1 to 3 hoursthe yield increased for all catalysts Longer reaction timemay enhance the probability of contact between methanoland Camelina oil with catalystsrsquo basic sites which improvethe biodiesel yield The yield slightly decreased after 3 hourswhich may be attributed to hydrolysis of methyl esters

333 Effect of Reaction Temperature on Biodiesel Yield Theeffect of the reaction temperature on the product yield isshown in Figure 11(c) Throughout the experiments themethanol to oil molar ratio and catalyst concentration werekept at 12 1 and 1 (ww) respectively Reaction temperaturewas a significant factor in biodiesel synthesis as the yieldincreased significantly for all three catalysts between 25∘Cand 65∘C Addition of heterogeneous catalysts to reactioncreates a triple phase system oil-methanol-catalyst and theinterface of the triple phase probably accommodates thetransesterification process [28] Increasing reaction temper-ature reduces the viscosity of Camelina oil and enhancesthe product yield because of the inhibition of mass transferresistance For all catalysts biodiesel yields were low at lowtemperatures Optimum yields (99 97 and 90 for CaOeggshell and lobster shell resp) were achieved when thereactionsrsquo temperature was held at 65∘C Further increase intemperature caused a decrease in biodiesel yield for all threecatalysts whichmay be attributed to evaporation ofmethanol

334 Effect of Catalyst Concentration on Biodiesel Yield Theyield of biodiesel was greatly dependent on the catalystconcentration Reactions were carried out with differentconcentrations of catalysts ranging from 025 to 2 weightand the results are illustrated in Figure 11(d) The reactionswere carried out at 65∘C for 3 hours with a methanolto oil ratio of 12 1 There was a significant increase inyield for all catalysts from 025 to 10 and optimumconversion was obtained for 10 wt catalyst concentrationPretreating catalysts with methanol a small amount of CaOwas converted into Ca(OCH

3)2 which acted as the initiating

reagent for transesterification The catalysts provide activebasic sites that transform the methanol into methoxide


50

60

70

80

90

100

3 6 9 12 15 18

Yiel

d (

)

CaOEggshellLobster shell

Methanol oil

(a)

50

60

70

80

90

100

0 1 2 3 4 5 6

Yiel

d (

)

Reaction time (hours)CaOEggshellLobster shell

(b)

50

60

70

80

90

100

10 30 50 70 90

Yiel

d (

)


Reaction temperature (∘C)

(c)

50

60

70

80

90

100

0 1 2 3

Yield

()

Catalyst concentration (wt)CaOEggshellLobster shell

(d)Figure 11 Effects of the (a) methanol to oil molar ratio (b) reaction time (c) reaction temperature and (d) catalyst concentration on thebiodiesel yield

which attacks the carbonyl carbon structure of oil As theconcentration of catalyst increases the available active sitesalso increase leading to the improvement of biodiesel yield[29] Beyond 1 the yieldwas not greatly affected by catalystsrsquoconcentration because the reaction mixture became moreviscous and all active sites are loaded

34 Kinetic Studies Kinetic studies of the transesterificationreaction of Camelina sativa oil were performed by lobster

waste shell heterogeneous catalyst at three different tempera-tures 50∘C 65∘C and 70∘C while the methanol to oil molarratio and catalyst concentration were kept at 12 1 and 1(ww) As expected decrease in temperature from 70∘C to50∘C causes decrease in reaction rates Rate expression of thereaction is shown as follows [30]

minusRate = minus119889 [CS Oil]119889119905

= 119896 [CS Oil] (2)


Table 2 Fuel properties of Camelina petroleum diesel and the ASTM biodiesel standards

Properties Petroleum diesel Camelina biodiesel Biodiesel standards(ASTM D6751) ASTM testing method Unit

Kinematic viscosity (40∘C) 26 31 19ndash60 D4451 mm2sSpecific gravity 085 088 087ndash090 D287Calorific value 42 46 D240 MJkgPour point minus20 minus10 minus5 to 10 D97 ∘CCetane number 46 49 47ndash65 D613 min

000

100

200

300

0 60 120 180 240 300Time (min)

50∘C

65∘C

70∘C

k70∘C = 0021minminus1



minusln

(1minusX

FAM

E)

Figure 12 Plot of ln(1minus119883FAME) versus time of the transesterificationreaction catalyzed by waste lobster shells

[CS Oil] represents the concentration of Camelina sativa oilExcess methanol was used in the reaction in order to shiftthe equilibrium towards the product side Since methanoldoes not affect the overall order the transesterificationreaction was assumed to follow first-order kinetics [31] Theintegration of (2) results as

ln [CS Oil]0 minus ln [CS Oil]119905 = 119896119905 (3)

The initial concentration of Camelina oil and the concen-tration of Camelina oil at time 119905 are shown as [CS Oil]

0

and ln[CS Oil]119905 respectively The fraction conversion of

Camelina biodiesel119883FAME can be cooperated into (3) as

119889119883FAME119889119905= 119896 (1 minus 119883FAME) (4)

and the integration of the equation becomes

minus ln (1 minus 119883FAME) = 119896119905 (5)

Figure 12 shows the graph between ln(1 minus 119883FAME) and timeat the three temperatures to obtain rate constant values Theplots are linear plots at three temperatures which indicate thatthe transesterification reaction obeys first-order kinetics

Arrhenius equation was utilized to calculate the activa-tion energy and preexponential factor for the transesterifica-tion reaction ofCamelina oil catalyzed by waste lobster shells

29 295 3 305 31

Slope = minus752

Intercept = 1815

ln k

minus35

minus4

minus45

minus5

minus55

1T times 103 Kminus1

Figure 13 Arrhenius plot of ln 119896 and 1119879 of the transesterificationreaction catalyzed by waste lobster shells

The activation energy and preexponential factor were deter-mined as 625 kJmolminus1 and 762 times 107minminus1 respectively byArrhenius plot shown in Figure 13

35 Fuel Properties of Camelina Biodiesel Biodiesel wascharacterized for its fuel properties by ASTM D287 445240 613 and 97 methods Table 2 shows the propertiesof the synthesized biodiesel and petroleum biodiesel Thecomparison showed that most of the fuel properties of theCamelina biodiesel are quite comparable to those of ASTMpetroleum diesel standards [32] The kinematic viscosityof Camelina based biodiesel was similar to regular dieselfuel viscosity so no modifications of engine are requiredThe cetane number was found higher than regular dieselstandards Cetane number is ameasure of a fuelrsquos autoignitionquality characteristics Since biodiesel is largely composed ofaliphatic hydrocarbons it usually has a higher cetane numberthan petroleum diesel [33] Higher cetane number indicatesmore complete combustion of the fuel better fuel efficiencyand quick ignition delay time of fuel The pour point ofCamelina biodiesel shows a good compatibility for placeswith cold climate

4 Conclusion

Every year enormous amount of waste shells are disposedof in landfills Waste shells such as eggshells or seashellsare rarely used to produce practical products and utilization


of the waste shells will help sustainable development Wasteshells can be utilized as economical and environmentallybenign solid catalysts for the biodiesel synthesis CaO lobsterand eggshell catalysts were effectively employed for biodieselsynthesis fromCamelina sativa oil andmethanol at 60∘CThefuel properties of the biodiesel favorably match petroleum-based diesel counterparts Biodiesel synthesis that employswaste shells andCamelina sativa oil will reducewaste disposalproblem and cut the price of biodiesel making biodiesela viable fuel alternative compared to petroleum-derivedbiodiesel

Competing Interests

The author declares that there is no competing interestsregarding the publication of this paper

Acknowledgments

The author acknowledges Manhattan College and School ofScience for supporting the project and would like to thankDr Alexander Santulli for SEM analysis

References

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

[2] J Manuel ldquoBattle of the biofuelsrdquo Environmental Health Per-spectives vol 115 no 2 pp A92ndashA95 2007

[3] G Knothe ldquolsquoDesignerrsquo biodiesel optimizing fatty ester compo-sition to improve fuel propertiesrdquo Energy amp Fuels vol 22 no 2pp 1358ndash1364 2008

[4] E C Bucholtz ldquoBiodiesel synthesis and evaluation an organicchemistry experimentrdquo Journal of Chemical Education vol 84no 2 pp 296ndash298 2007

[5] A Perea T Kelly and Y Hangun-Balkir ldquoUtilization of wasteseashells and Camelina sativa oil for biodiesel synthesisrdquo GreenChemistry Letters and Reviews vol 9 no 1 pp 27ndash32 2016

[6] N V Fedoroff and J E Cohen ldquoPlants and population is theretimerdquo Proceedings of the National Academy of Sciences of theUnited States of America vol 96 no 11 pp 5903ndash5907 1999

[7] P D Patil V G Gude and S Deng ldquoBiodiesel productionfrom jatropha curcas waste cooking and camelina sativa oilsrdquoIndustrial amp Engineering Chemistry Research vol 48 no 24 pp10850ndash10856 2009

[8] E A Waraich Z Ahmed R Ahmad et al ldquoCamelina sativa aclimate proof crop has high nutritive value and multiple-usesa reviewrdquo Australian Journal of Crop Science vol 7 no 10 pp1551ndash1559 2013

[9] B R Moser ldquoCamelina (Camelina sativa L) oil as a biofuelsfeedstock golden opportunity or false hoperdquo Lipid Technologyvol 22 no 12 pp 270ndash273 2010

[10] S Pinzi I L Garcia F J Lopez-Gimenez M D L DeCastroG Dorado and M P Dorado ldquoThe ideal vegetable oil-basedbiodiesel composition a review of social economical andtechnical implicationsrdquo Energy and Fuels vol 23 no 5 pp2325ndash2341 2009

[11] M Di Serio M Cozzolino M Giordano R Tesser P Patronoand E Santacesaria ldquoFrom homogeneous to heterogeneous

catalysts in biodiesel productionrdquo Industrial and EngineeringChemistry Research vol 46 no 20 pp 6379ndash6384 2007

[12] M Di Serio R Tesser L Pengmei and E SantacesarialdquoHeterogeneous catalysts for biodiesel productionrdquo Energy ampFuels vol 22 no 1 pp 207ndash217 2008

[13] K Tanabe and W F Holderich ldquoIndustrial application of solidacid-base catalystsrdquo Applied Catalysis A General vol 181 no 2pp 399ndash434 1999

[14] C Lingfeng X Guomin X Bo and T Guangyuan ldquoTransester-ification of cottonseed oil to biodiesel by using heterogeneoussolid basic catalystsrdquo Energy and Fuels vol 21 no 6 pp 3740ndash3743 2007

[15] H Mootabadi B Salamatinia S Bhatia and A Z AbdullahldquoUltrasonic-assisted biodiesel production process from palmoil using alkaline earth metal oxides as the heterogeneouscatalystsrdquo Fuel vol 89 no 8 pp 1818ndash1825 2010

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

[17] A A Refaat ldquoBiodiesel production using solid metal oxidecatalystsrdquo International Journal of Environmental Science andTechnology vol 8 no 1 pp 203ndash221 2011

[18] F Boszligelmann P Romano H Fabritius D Raabe and MEpple ldquoThe composition of the exoskeleton of two crustaceathe american lobster Homarus americanus and the edible crabCancer pagurusrdquoThermochimica Acta vol 463 no 1-2 pp 65ndash68 2007

[19] WT Tsai JM Yang CW Lai YHCheng C C Lin andCWYeh ldquoCharacterization and adsorption properties of eggshellsand eggshell membranerdquo Bioresource Technology vol 97 no 3pp 488ndash493 2006

[20] P D Patil V G Gude and S Deng ldquoTransesterification ofCamelina sativa oil using supercritical and subcritical methanolwith cosolventsrdquoEnergyampFuels vol 24 no 2 pp 746ndash751 2010

[21] J Van Gerpen ldquoBiodiesel processing and productionrdquo FuelProcessing Technology vol 86 no 10 pp 1097ndash1107 2005

[22] L M Correia R M A Saboya N de Sousa Campelo etal ldquoCharacterization of calcium oxide catalysts from naturalsources and their application in the transesterification of sun-flower oilrdquo Bioresource Technology vol 151 pp 207ndash213 2014

[23] 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

[24] B Engin H Demirtas and M Eken ldquoTemperature effectson egg shells investigated by XRD IR and ESR techniquesrdquoRadiation Physics and Chemistry vol 75 no 2 pp 268ndash2772006

[25] J Geist K Auerswald and A Boom ldquoStable carbon isotopes infreshwater mussel shells environmental record or marker formetabolic activityrdquo Geochimica et Cosmochimica Acta vol 69no 14 pp 3545ndash3554 2005

[26] A Buasri P Worawanitchaphong S Trongyong and VLoryuenyong ldquoUtilization of scallop waste shell for biodieselproduction from palm oilmdashoptimization using Taguchimethodrdquo APCBEE Procedia vol 8 pp 216ndash221 2014

[27] A Murugesan C Umarani T R Chinnusamy M Krishnan RSubramanian andNNeduzchezhain ldquoProduction and analysisof biodiesel from non-edible oils a reviewrdquo Renewable andSustainable Energy Reviews vol 13 no 4 pp 825ndash834 2009


[28] T-L Kwong and K-F Yung ldquoHeterogeneous alkaline earthmetalndashtransition metal bimetallic catalysts for synthesis ofbiodiesel from low grade unrefined feedstockrdquo RSC Advancesvol 5 no 102 pp 83748ndash83756 2015

[29] M Kouzu and J-S Hidaka ldquoTransesterification of vegetable oilinto biodiesel catalyzed by CaO a reviewrdquo Fuel vol 93 pp 1ndash122012

[30] 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

[31] A K Singh and S D Fernando ldquoReaction kinetics of soybeanoil transesterification using heterogeneous metal oxide cata-lystsrdquo Chemical Engineering and Technology vol 30 no 12 pp1716ndash1720 2007

[32] httpwwwafdcenergygovfuelsbiodiesel basicshtml[33] K J Harrington ldquoChemical and physical properties of vegetable

oil esters and their effect on diesel fuel performancerdquo Biomassvol 9 no 1 pp 1ndash17 1986

Submit your manuscripts athttpwwwhindawicom

Hindawi Publishing Corporationhttpwwwhindawicom Volume 2014

Inorganic ChemistryInternational Journal of

Hindawi Publishing Corporation httpwwwhindawicom Volume 2014

International Journal ofPhotoenergy


Carbohydrate Chemistry

International 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


Biodiesel

O

OR998400CO-CH2

OR998400CO-CH

R998400CO-CH2

+ 3 CH3OHCatalyst

3 R998400COOCH3 +

HO-CH2

HO-CH

HO-CH2

Figure 1 Transesterification reaction of triglycerides to biodiesel

pesticide requirements than other traditional oilseed cropssuch as soybean canola or corn [9] It can be grown on soilsreclaimed from mine spoils and abandoned farmlands Thecrop can stand of extreme climate conditions and poor soilquality and it might be grown in the cycle of crop rotationThe oil has significantly low production cost compared toother crops compared to soybean or corn oils [10]

Traditionally transesterification is achieved in the pres-ence of a homogeneous catalyst such as KOHorNaOHThesewidely used catalysts KOH and NaOH are easily soluble inmethanol forming potassiummethoxide or sodiummethox-ide respectively Although homogeneous catalyzed biodieselreactions are comparatively faster and showhigh conversionsthey present numerous drawbacks [11] The homogeneouscatalysts cannot be recovered and reused and they mustbe neutralized and separated from the biodiesel whichcauses a generation of excess waste water The oil feedstockshould have low free fatty acids otherwise the reactionforms soap The soap formation consumes the catalyst anddecreases the efficiency of the reaction In addition the soapprevents glycerol separation from biodiesel Production costof utilization of homogeneous catalysts is relatively high asthe process involves number of washing and purificationsteps in order to meet quality standards On the other handheterogeneous catalysts are more environmentally benignalternatives to homogeneous counterparts and they havemany advantages [12] The use of heterogeneous catalystsdoes not cause the soap formation and there is no need forneutralization Reactions with heterogeneous catalysts havesimpler biodiesel separation and purification steps Hetero-geneous catalysts do not produce waste water and they couldbe easily separated from liquid products by filtration and canbe designed to give higher activity selectivity and longerlifetimes [13] The catalysts are reusable which reduces theenvironmental impact and process cost Use of heterogeneouscatalysts instead of homogeneous catalysts could potentiallylead to cheaper production costs and opportunities to operatein a fixed bed continuous process [14] Overall they act asenergy efficient nontoxic and greener option

The production of biodiesel needs an efficient and low-cost heterogeneous catalyst tomake the process economicallyviable and environmentally friendly Alkaline earth metaloxides were widely studied as basic heterogeneous catalystsfor biodiesel synthesis [15] Calcium oxide was employedspecifically as a transesterification catalyst because of itsavailability low cost and excellent catalytic performanceunder ambient conditions The reactivity of CaO can befurther improved upon calcination At the beginning ofthe process CaO is converted to Ca(OCH

3)2 which is

an initiating reagent for transesterification reaction bymixing with methanol [16] CaO has high basicity andlow environmental impact due to its low solubility inmethanol [17] In addition CaO is easy to handle abundantnontoxic and economically feasible catalyst compared to itshomogeneous counterpart KOH Both waste eggshell andlobster shells are composed of approximately 95 of calciumcarbonate and the remaining components are magnesiumcarbonate calcium phosphate and organic matter [18 19]Since the shells mainly consist of CaCO

3 they decompose to

CaO via calcination Waste shells including avian eggshellsand seashells are excellent raw materials for the preparationof the heterogeneous catalysts For sustainable developmentwastes should be recycled and reused towards the productionof other goods Over the years it has become very costlyto dispose the waste shells in landfills and the landfillsare reaching their capacity Waste shells remain largelyunutilized as they are discarded wrongly The waste shells aremade up of calcium carbonate that can be used to produceheterogeneous catalysts for biodiesel synthesis Figure 2shows a flow diagram for transesterification process fromCamelina oil and waste shells as heterogeneous catalysts

Utilization of waste shells as catalysts will protect theenvironment by reducing the waste and create cost-effectivebiodiesel synthesis In this paper we utilized waste eggshellslobster shells and CaO as exemplary heterogeneous cata-lysts for the transesterification of Camelina sativa oil intobiodiesel The parameters such as methanol to oil ratio reac-tion time reaction temperature and catalyst concentrationwere studied and a kinetic study was performed by using thedata obtained from the optimization experiments The studydemonstrates several fundamental green principles includingthe use of renewable feedstocks catalysis and design fordegradation

2 Materials and Methods

Cold-pressed and unrefinedCamelina sativa oil was obtainedfromOleWorldOils Company Calciumoxidewas purchasedfrom Alfa Aesar Waste eggshells and lobster shells were col-lected from collegersquos cafeteria and neighborhood restaurantsAnhydrous methanol was purchased from Fischer Scientific

21 Catalyst Preparation Calcium oxide was used as it wasreceived The eggshells and lobster shells were rinsed withtap water to remove organic materials and impurities anddried at 110∘C for 2 hoursThe dried waste shells were grindedand calcined at 900∘C in air atmosphere with a heating rateof 10∘C per minute for 3 hours All catalysts were kept ina desiccator to avoid the interaction with air The raw andcalcined samples of the shells were analyzed by X-ray powderdiffraction (XRD) Fourier Transform Infrared Spectroscopy(FTIR) and Scanning ElectronMicroscope (SEM)The XRDcharacterization was studied on Bruker X-Ray D-2 Phaserdiffractometer over a 2120579 range from 5∘ to 60∘ with a step sizeof 001∘ and FTIR spectroscopy was performed on ThermoNexus 470 FTIR spectrometer The spectra were obtainedin the 500ndash4000 cmminus1 region and 32 scans were recorded


Camelina sativaoil






Pure biodiesel
















2from CaCO

3in the


600

500

400

300

200

100

0

Inte

nsity


Raw lobster shell

10 20 30 40 50 60

2120579 (degree)


600

500

400

300

200

100

0

Inte

nsity

CaO


30 40 50

2120579 (degree)








0102030405060708090

100

tr

ansm

ittan

ce





re

flect

ance


CaO

Lobster shell

Eggshell

80

70

60

50

40

30

20

10

0

minus10

minus20

minus30

















8 6 4 2 0

Biodiesel

Camelina oil

(PPM)


110

100

90

80

70

60

50

40

30

20

10

0

tr

ansm

ittan

ce

4000 3500 3000 2500 2000 1500 1000





2and CH

3bending vibrations










50

60

70

80

90

100

3 6 9 12 15 18

Yiel

d (

)


Methanol oil

(a)

50

60

70

80

90

100

0 1 2 3 4 5 6

Yiel

d (

)


(b)

50

60

70

80

90

100

10 30 50 70 90

Yiel

d (

)



(c)

50

60

70

80

90

100

0 1 2 3

Yield

()







= 119896 [CS Oil] (2)





000

100

200

300

0 60 120 180 240 300Time (min)

50∘C

65∘C

70∘C




minusln

(1minusX

FAM

E)





0



119889119883FAME119889119905= 119896 (1 minus 119883FAME) (4)





29 295 3 305 31

Slope = minus752

Intercept = 1815

ln k

minus35

minus4

minus45

minus5

minus55





4 Conclusion




Competing Interests


Acknowledgments


References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


Camelina sativaoil






Pure biodiesel
















2from CaCO

3in the


600

500

400

300

200

100

0

Inte

nsity


Raw lobster shell

10 20 30 40 50 60

2120579 (degree)


600

500

400

300

200

100

0

Inte

nsity

CaO


30 40 50

2120579 (degree)








0102030405060708090

100

tr

ansm

ittan

ce





re

flect

ance


CaO

Lobster shell

Eggshell

80

70

60

50

40

30

20

10

0

minus10

minus20

minus30

















8 6 4 2 0

Biodiesel

Camelina oil

(PPM)


110

100

90

80

70

60

50

40

30

20

10

0

tr

ansm

ittan

ce

4000 3500 3000 2500 2000 1500 1000





2and CH

3bending vibrations










50

60

70

80

90

100

3 6 9 12 15 18

Yiel

d (

)


Methanol oil

(a)

50

60

70

80

90

100

0 1 2 3 4 5 6

Yiel

d (

)


(b)

50

60

70

80

90

100

10 30 50 70 90

Yiel

d (

)



(c)

50

60

70

80

90

100

0 1 2 3

Yield

()







= 119896 [CS Oil] (2)





000

100

200

300

0 60 120 180 240 300Time (min)

50∘C

65∘C

70∘C




minusln

(1minusX

FAM

E)





0



119889119883FAME119889119905= 119896 (1 minus 119883FAME) (4)





29 295 3 305 31

Slope = minus752

Intercept = 1815

ln k

minus35

minus4

minus45

minus5

minus55





4 Conclusion




Competing Interests


Acknowledgments


References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


600

500

400

300

200

100

0

Inte

nsity


Raw lobster shell

10 20 30 40 50 60

2120579 (degree)


600

500

400

300

200

100

0

Inte

nsity

CaO


30 40 50

2120579 (degree)








0102030405060708090

100

tr

ansm

ittan

ce





re

flect

ance


CaO

Lobster shell

Eggshell

80

70

60

50

40

30

20

10

0

minus10

minus20

minus30

















8 6 4 2 0

Biodiesel

Camelina oil

(PPM)


110

100

90

80

70

60

50

40

30

20

10

0

tr

ansm

ittan

ce

4000 3500 3000 2500 2000 1500 1000





2and CH

3bending vibrations










50

60

70

80

90

100

3 6 9 12 15 18

Yiel

d (

)


Methanol oil

(a)

50

60

70

80

90

100

0 1 2 3 4 5 6

Yiel

d (

)


(b)

50

60

70

80

90

100

10 30 50 70 90

Yiel

d (

)



(c)

50

60

70

80

90

100

0 1 2 3

Yield

()







= 119896 [CS Oil] (2)





000

100

200

300

0 60 120 180 240 300Time (min)

50∘C

65∘C

70∘C




minusln

(1minusX

FAM

E)





0



119889119883FAME119889119905= 119896 (1 minus 119883FAME) (4)





29 295 3 305 31

Slope = minus752

Intercept = 1815

ln k

minus35

minus4

minus45

minus5

minus55





4 Conclusion




Competing Interests


Acknowledgments


References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of














8 6 4 2 0

Biodiesel

Camelina oil

(PPM)


110

100

90

80

70

60

50

40

30

20

10

0

tr

ansm

ittan

ce

4000 3500 3000 2500 2000 1500 1000





2and CH

3bending vibrations










50

60

70

80

90

100

3 6 9 12 15 18

Yiel

d (

)


Methanol oil

(a)

50

60

70

80

90

100

0 1 2 3 4 5 6

Yiel

d (

)


(b)

50

60

70

80

90

100

10 30 50 70 90

Yiel

d (

)



(c)

50

60

70

80

90

100

0 1 2 3

Yield

()







= 119896 [CS Oil] (2)





000

100

200

300

0 60 120 180 240 300Time (min)

50∘C

65∘C

70∘C




minusln

(1minusX

FAM

E)





0



119889119883FAME119889119905= 119896 (1 minus 119883FAME) (4)





29 295 3 305 31

Slope = minus752

Intercept = 1815

ln k

minus35

minus4

minus45

minus5

minus55





4 Conclusion




Competing Interests


Acknowledgments


References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of


50

60

70

80

90

100

3 6 9 12 15 18

Yiel

d (

)


Methanol oil

(a)

50

60

70

80

90

100

0 1 2 3 4 5 6

Yiel

d (

)


(b)

50

60

70

80

90

100

10 30 50 70 90

Yiel

d (

)



(c)

50

60

70

80

90

100

0 1 2 3

Yield

()







= 119896 [CS Oil] (2)





000

100

200

300

0 60 120 180 240 300Time (min)

50∘C

65∘C

70∘C




minusln

(1minusX

FAM

E)





0



119889119883FAME119889119905= 119896 (1 minus 119883FAME) (4)





29 295 3 305 31

Slope = minus752

Intercept = 1815

ln k

minus35

minus4

minus45

minus5

minus55





4 Conclusion




Competing Interests


Acknowledgments


References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of





000

100

200

300

0 60 120 180 240 300Time (min)

50∘C

65∘C

70∘C




minusln

(1minusX

FAM

E)





0



119889119883FAME119889119905= 119896 (1 minus 119883FAME) (4)





29 295 3 305 31

Slope = minus752

Intercept = 1815

ln k

minus35

minus4

minus45

minus5

minus55





4 Conclusion




Competing Interests


Acknowledgments


References













































Journal of

Chemistry


Advances in

Physical Chemistry



Journal of

Volume 2014














Journal of

Spectroscopy



Journal of


Quantum Chemistry






CatalystsJournal of



Competing Interests


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

research article green biodiesel synthesis using waste...

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