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Mixed Oxides of Ca-Zn as Heterogeneous Catalyst in Biodiesel Production from

Refined Palm Oil

J.J. PARRA-SANTIAGO J.F. SIERRA-CANTOR

C.A. GUERRERO-FAJARDO

CHEMISTRY DEPARTMENTNATIONAL UNIVERSITY OF COLOMBIA

2014

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OUTLINE

• INTRODUCTION

• CATALYST PRODUCTION AND CHARACTERIZATION

• CATALYST ACTIVITY

• CONCLUSIONS

• REFERENCES

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INTRODUCTION

BD FROM OIL SEEDS AND FATS

• Mixture of fatty acid alkyl esters.

• Produced from fats and oils by the transesterification process.

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A. N. Talebian-Kiakalaieh and H. Mazaheri, "A review on novel processes of biodiesel production from waste cooking oil," Applied Energy, vol. 104, pp. 683-710, 2013. P. Benjumea, J. Agudelo and A. Agudelo, "Basic properties of palm oil biodiesel-diesel blends," Fuel, pp. 2069-2075, 2008

TRANSESTERIFICATION REACTION

Source: B. Mooser, "Biodiesel Production, Properties, and Feedstocks," In Vitro Cellular & Developmental Biology - Plant, vol. 45, no. 3, 2009.

PARAMETERS

Raw materials Quality

Catalyst used

Operational Conditions: Temperature, Stirring, Pressure, Reaction time.

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CATALYST PRODUCTION AND

CHARACTERIZATION

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PREPARATION METHODOLOGY

Calcium-Zinc Carbonates Co-Precipitation from nitratesAtomic Relation Zn/Ca: 3-4.5

Growth at 60 °C by 24 h, Washing, Drying and Milling

Calcination at 800 °CT = 5 °C/min

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CHARACTERIZATION

• Composition Analysis: X-Ray Flourescence (XRF)

• X-Ray Powder Diffraction (XRPD)

• Infrared Analysis (IR)

• Scanning Electronic Microscopy (SEM)

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Composition Analysis: X-Ray Flourescence (XRF)

Compound Catalyst

Zn/Ca: 4.5Catalyst

Zn/Ca: 3.0

ZnO 87.004 % 81.517 %

CaO 12.912 % 18.483 %

K2O 0.084 % --

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X-Ray Powder Diffraction (XRPD)

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X-Ray Powder Diffraction (XRPD)

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INFRARED ANALYSIS (IR)

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Scanning Electronic Microscopy

ZnO/ CaO: 3.0 ZnO/ CaO: 4.5

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CATALYST ACTIVITY

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BIODIESEL PRODUCTION METHODOLOGY

Add Oil, methanol &

catalyst

Reflux by 2 h with

constant stirring

Filtered to reaction mixture

Decanting

ORGANIC PHASE

Methanol Removing

Biodiesel Purification

BIODIESEL GC analysis

according to ASTM D6584

SOLIDRICH GLYCERIN-

METHANOL PHASE

METHANOL

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RESULTS

Zn/Ca Molar

Ratio in Catalyst

MeOH/Oil Molar

Ratio

%wt. of catalyst

Composition (%wt.)

EM MG DG TG

4.5 10 5.0 84.01 6.07 7.28 2.644.5 10 10.0 78.72 1.71 8.09 11.494.5 15 7.5 34.07 8.95 19.32 37.664.5 20 7.5 79.48 9.49 4.65 6.394.5 20 10.0 42.97 7.76 20.78 28.494.5 30 10.0 26.31 12.60 19.53 41.563.0 15 10.0 41.36 5.73 7.54 45.373.0 10 7.5 18.10 8.51 19.83 53.563.0 15 5.0 40.21 6.02 8.76 45.013.0 20 5.0 62.68 4.31 9.58 23.433.0 30 5.0 82.91 1.76 2.81 12.523.0 30 7.5 86.99 1.02 1.59 10.40

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RESULTS

Yield = 86.99 % catalyst = 7.5 % wt.

Atomic Ratio Zn/Ca = 3.0

Molar Ratio MeOH- Oil 30:1

Reaction time = 2 h Temperature = 56.9 °C

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CONCLUSIONS

CONCLUSIONS

• CaO/ZnO doesn´t generate new compounds, only the Calcium oxides particles growth over Zinc Oxides Particles

• The carbonates and hydroxides should be avoided to optimize the catalyst activity.

• The transesterification reaction is controlled by diffusion.

• CaO surface is the main parameter to catalyst activity. This surface doesn´t increase proportionally with the CaO concentration.

• The maximum BD production, 86.99 % was obtained with 7.5 % wt. catalyst and atomic ratio Zn/Ca 3.0, molar ratio MeOH- Oil 30:1, reaction time: 2 h. T: 56.9 °C.

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REFERENCES

• A. N. Talebian-Kiakalaieh and H. Mazaheri, "A review on novel processes of biodiesel production from waste cooking oil," Applied Energy, vol. 104, pp. 683-710, 2013.

• P. Benjumea, J. Agudelo and A. Agudelo, "Basic properties of palm oil biodiesel-diesel blends," Fuel, pp. 2069-2075, 2008.

• B. Mooser, "Biodiesel Production, Properties, and Feedstocks," In Vitro Cellular & Developmental Biology - Plant, vol. 45, no. 3, 2009.

• E. F. Aransiola, T. V. Ojumu, O. Oyekola and T. Madzimbamuto, "A Review of Current Technology for Biodiesel Production: State of the Art," Biomass and Bioenergy, pp. 276-297, 2014.

• K. Ramachandran, T. Suganya, N.-G. N. and S. Renganathan, "Recent Developments for Biodiesel Production by Ultrasonic Assist Transesterification Using Different Heterogeneous Catalyst: A Review," Renewable and Sustainable Reviews, vol. 22, pp. 410-418, 2013.

• Y. Yan, X. Li, G. Wang, X. Gui, G. Li, F. Su, X. Wang and T. Liu, "Biotechnological preparation of biodiesel and its high-valued derivatives: A review," Applied Energy, vol. 113, p. 1614–1631, 2014.

• L. J. Konwar, J. Boro and D. Deka, "Review on latest developments in biodiesel production using carbon-based catalyst," Renewable and Sustainable Energy Reviews, vol. 29, pp. 546-564, 2014.

• M. Borges and L. Díaz, "Recent developments on heterogeneous catalysts for biodiesel production by oil esterification and transesterification reactions: A review," Renewable and Sustainable Energy Reviews, vol. 16, pp. 2839-2849, 2012.