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 DEPARTMENT
NATIONAL UNIVERSITY OF COLOMBIA
2014

OUTLINE
INTRODUCTION
CATALYST PRODUCTION AND
CHARACTERIZATION
CATALYST ACTIVITY
CONCLUSIONS
REFERENCES
2

INTRODUCTION

BD FROM OIL SEEDS AND FATS

Mixture of fatty acid alkyl esters.

Produced from fats and oils by the

transesterification process.
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

PARAMETERS

Raw materials Quality

Catalyst used

Operational Conditions:
Pressure, Reaction time.

Temperature,

Stirring,

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

CATALYST
PRODUCTION AND
CHARACTERIZATION

PREPARATION METHODOLOGY
Calcium-Zinc Carbonates Co-Precipitation from
nitrates
Atomic Relation Zn/Ca: 3-4.5

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

Calcination at 800 C
T = 5 C/min
8

CHARACTERIZATION
Composition Analysis: X-Ray
Flourescence (XRF)
X-Ray Powder Diffraction (XRPD)
Infrared Analysis (IR)
Scanning Electronic Microscopy (SEM)
9

Composition Analysis:
X-Ray Flourescence (XRF)

Compound

Catalyst
Zn/Ca: 4.5

Catalyst
Zn/Ca: 3.0

ZnO

87.004 %

81.517 %

CaO

12.912 %

18.483 %

K2O

0.084 %

-10

X-Ray Powder Diffraction (XRPD)

11

X-Ray Powder Diffraction (XRPD)

12

INFRARED ANALYSIS (IR)

13

Scanning Electronic Microscopy

ZnO/ CaO: 3.0

ZnO/ CaO: 4.5

14

CATALYST ACTIVITY

15

BIODIESEL PRODUCTION
METHODOLOGY
SOLID

Add Oil,
methanol &
catalyst

BIODIESEL

GC
analysis according
to ASTM D6584

Reflux by 2 h
with constant
stirring

Biodiesel
Purification

Filtered to
reaction
mixture

Methanol
Removing

RICH GLYCERINMETHANOL
PHASE

Decanting

ORGANIC
PHASE

METHANOL

16

RESULTS
Composition (%wt.)

Zn/Ca
Molar
Ratio in
Catalyst

MeOH/Oil
Molar
Ratio

%wt. of
catalyst

EM

MG

DG

4.5
4.5
4.5
4.5
4.5
4.5
3.0
3.0
3.0
3.0
3.0

10
10
15
20
20
30
15
10
15
20
30

5.0
10.0
7.5
7.5
10.0
10.0
10.0
7.5
5.0
5.0
5.0

84.01
78.72
34.07
79.48
42.97
26.31
41.36
18.10
40.21
62.68
82.91

6.07
1.71
8.95
9.49
7.76
12.60
5.73
8.51
6.02
4.31
1.76

7.28
8.09
19.32
4.65
20.78
19.53
7.54
19.83
8.76
9.58
2.81

TG
2.64
11.49
37.66
6.39
28.49
41.56
45.37
53.56
45.01
23.43
12.52 17

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
18

CONCLUSIONS

19

CONCLUSIONS
CaO/ZnO doesnt 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 doesnt 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.

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. 546564, 2014.
M. Borges and L. Daz, "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.

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