- The document describes a study investigating the catalytic combustion of biodiesel over perovskite catalysts. Specifically, it examines combusting canola biodiesel and its surrogate methyl oleate over a 15wt% LaMnO3-YSZ catalyst. - Testing showed the catalyst achieved near 95% carbon conversion and CO2 yield, releasing maximum heat. Characterization found the catalyst structure was stable after testing. - The mechanism involves O2 from YSZ oxidizing combustion intermediates and LaMnO3 fully oxidizing residual CO to CO2. The catalyst also effectively combusted gasoline, demonstrating fuel flexibility. - Future work will involve engine testing and publishing results. The catalyst shows potential as a

1. Anh Trieu Ly1
Catalytic Combustion
of Bio-diesel over Perovskite Catalyst
Instructor: Research Prof. Oscar Marin-Flores2
Principle Investigator: Prof. Grant Norton2 ,Prof. Su Ha1
April 2016
1 School of Chemical Engineering and Bioengineering 2 School of Mechanical and Materials Engineering1

2. Outline
• Catalytic Combustion.
• Biodiesel.
• Catalyst material.
• Hypothesis.
• Catalyst synthesis and characterization.
• Experiment setup.
• Performance and analysis of catalyst.
• Conclusion.
• Acknowledgement.
2

3. Purpose of Catalytic Combustion
• The temperature at the center
of the flame is around 2000°C.
• Nitrogen and oxygen react at
this temperature to produce
nitrogen oxides (NOx).
• In traditional combustion,
fuels are burnt to
generate heat.
3

4. Benefit of Canola Biodiesel
- Biodiesel is a renewable fuel made from canola oil.
- Canola biodiesel was made from canola tree which is not edible. (Corn biodiesel)4

5. canola
Canola Biodiesel
Biodiesel
Methyl Oleate
Main Components Global Formula % in Weight
Hexadecanoic acid methyl ester C17H34O2 2.914
9,12 - Octadecadienoic acid (Z,Z) - methyl ester C19H34O2 11.909
9 - Octadecenoic acid - methyl ester C19H36O2 59.327
Octadecanoic acid methyl ester C19H38O2 2.657
11 - Eicosenoic acid methyl ester C21H40O2 0.731
Eicosanoic acid methyl ester C21H42O2 0.399
Docosanoic acid methyl ester C23H46O2 0.178
Table 1: chemical analysis of biodiesel (BG100) from the
Renewable Energy Group
5

6. Previous Study
o Previous work has been done with a dodecane and biodiesel over Ru-YSZ
catalysts.[1][3]
o We must find a material that is:
o Cheap
o Stable and resistant to oxidation at high
temperatures and rich oxygen conditions.
o Conduct lattice oxygen
o Produce maximum carbon conversion for
maximum heat energy production
Graph 1: Performance of
biodiesel in 0.5 wt%Ru-
YSZ catalyst. O2/C= 1.6,
T = 450oC, WHSV = 272 h-1
C19H36O2 + 28 O2 → 19 CO2 + 18 H2O ΔHc = -11887 kJ/mol (Source: NIST)
Qreleased = (Flowrate of fuel) * (Carbon Conversion) * (Heat of Combustion) 6
0.00%
20.00%
40.00%
60.00%
80.00%
100.00%
0 2 4 6 8
Conversion,yeild
time (h)
CO yield CO2 yield Conversion

7. LaMnO3 supported in YSZ
• It was supported byYSZ (Yttrium
Stabilized Zirconium oxide) which is an
good oxygen ion conductor.[2]
• Perovskite LaMnO3(LM)(a) is a mixture of
lanthanum in its highest oxidation state
and manganese, so it is not oxidized in rich
oxygen condition.
• It has been applied successfully in toluene
combustion.[2]
7
Firgue 1: Unit cell of Lathanum
manganese oxide[2].

8. CO2
H2O
Catalytic Combustion Hypothesis
CxHyOz
O2
O2CxHyOz La-Mn O2 e
H2O CO2
LaMnO3
YSZ
8

9. LaMnO3 synthesis
Equation 1: How to calculate
mass of La(NO3)3 and Mn(NO3)2
and Citric acid[2]
Mn(NO3)3.4H2O, La(NO3)3 .6H2O + Water Citric Acid
Wet
Impregnation
Drying
90oC
Calcination 750oC, 2 h, 5oC/min
YSZ
Eliminate CA(200oC, 1oC/min)
Procedure
18 La(NO3)3.6H2O + 18Mn(NO3)2.6H2O + 25 C6H8O7 . H2O
18LaMnO3 + 45 N2 + 150 CO2 + 341 H2O∆ 𝐻
Calcination
YSZ YSZ
No
CA
YSZ YSZ
CA
Less
Active
Sites
More
Active
Sites
9

10. XRD analysis of fresh LM-YSZ
15wt% LaMnO3-YSZ
- By comparing with the
pure LM, we identify
exactly crystal structure
of LM andYSZ by X-ray
diffraction
method(XRD).
0
1000
2000
3000
4000
5000
6000
10 20 30 40 50 60 70 80
Intensity(cps)
2-Theta Degree
XRD analysis of fresh LM-YSZ
LM
YSZ
LM
LM-YSZ
YSZ
10
Firgue 2: size of LaMnO3
supported inYSZ

11. Experiment Setup
GC,Temperature controller, HV supply
Reactor Set up 11

12. Performance of catalyst in
bio-diesel surrogate(Methyl Oleate)
Chart 1: Performance of blank experiment,
0.2 ml Methyl Oleate, O2/C = 1.6, 45ooC
-Without catalyst,
the carbon
conversion and
CO2 yield is under
30% which lead to
really low heat
production.
12
0.00%
5.00%
10.00%
15.00%
20.00%
25.00%
30.00%
0 1 2 3 4 5 6 7 8
Conversion,yeild
time (h)
CO yield CO2 yield Conversion

13. Performance of catalyst in
bio-diesel surrogate(Methyl Oleate)
Chart 2: Performance 15wt% LaMnO3-YSZ,
0.2 ml Methyl Oleate, O2/C = 1.6, 45ooC,WHSV = 272h-1
-In the presence of our
catalyst, the carbon
conversion and CO2
yield is around 95%
which leads to maximum
heat production.
CO2 and Carbon
conversion
13

14. XRD Analysis
15wt% LaMnO3-YSZ( before and after combustion)
- The catalyst is
stable after 24 h
experiments
because all the
peak of the fresh
catalyst and the
spent catalyst is
matched.
0
500
1000
1500
2000
2500
3000
3500
0 10 20 30 40 50 60 70 80
Intensity(cps)
2-Theta
before and after 24h experiment of LM-YSZ
LM-YSZ(spent24h)
original
14

15. TEM, SEM image of the
fresh and spent sample
a) b)
c) d)
Firgue 3: a)TEM image LM-YSZ(fresh), b)TEM image LM-YSZ(spent) ,
c) SEM image LM-YSZ(fresh), d) SEM image LM-YSZ(spent)
• The particle size does not
change much which implies no
sintering occurs.
• Morphology of catalyst is not
changing, and there are no sign
of agglomeration.

16. Performance of catalyst
with canola bio-diesel
• Methyl Oleate is an good model for canola biodiesel because the performance is same.
Conversion,yeild
time (h)
Combustion of canola biodiesel in 15wt% LM-YSZ
CO yield CO2 yield Conversion
16

17. Mechanism of combustion in LM-YSZ
Firgue 4: a)Performance of
LM( unsupported), LM-YSZ(impregnation),
LM-YSZ(physical mixture),YSZ
(0.2 ml/h Methyl Oleate, O2/C = 1.6,
T= 45ooC)
0.00%
10.00%
20.00%
30.00%
40.00%
50.00%
60.00%
70.00%
80.00%
90.00%
100.00%
LM
(unsupported)
LM-YSZ
(impregnation)
LM-YSZ
(physical
mixing)
YSZ
Conversion,yeild
CO yield CO2 yield Conversion
- Combustion of Methyl Oleate in YSZ:
C19H36O2 + O2 → CO + CO2 + H2O ( in
YSZ )
- CO is converted completely to CO2 in
the present of LaMnO3.
2CO + O2 → 2 CO2 (in LM)

18. Fuel Flexibility
0.00%
20.00%
40.00%
60.00%
80.00%
100.00%
0 5 10 15 20 25
Conversion,yeild
time(h)
CO yield CO2 yield Conversion
0.00%
10.00%
20.00%
30.00%
40.00%
50.00%
60.00%
70.00%
80.00%
90.00%
100.00%
0 0.5 1 1.5 2 2.5 3
Conversion,yeild
time(h)
CO yield CO2 yield Conversion
Firgue 5: Performance of 15wt%LM-YSZ (O2/C = 1.6,T= 45ooC,WHSV = 272 h-1)
a) Canola biodiesel, b) Premium Gasoline
a) b)

19. Conclusion
- LM-YSZ catalyst has high selectivity of CO2 (almost 95% conversion,
WHSV = 272 h-1) and it is stable during 24h testing period.
- Methyl Oleate is a good model for canola biodiesel based on
chemical analysis and performance of catalytic experiment.
- Catalytic combustion of biodiesel is an important Green Energy
Technology because it releases maximum heat production without
generating harmful emissions (e.g. NOx) and because it closes the
carbon cycle.
19

20. Future Work
• They will test the 15wt% LM-YSZ in the real catalytic combustion
engine at USArmy Laboratory.
• The result of this work will be summarized in a manuscript for
future publication.
20

21. Acknowledgements
18
DeVlieg
Fellowship
O.H. Reaugh
Foundation
FMIC Center
Dr. Su Ha’s research group
21

22. Questions ?
22

23. Reference
1. Jeffrey G. St. Clair, Douglas A. Behrens, Ivan C. Lee, Catalytic combustion of 1-
butanol coupled with heat harvesting for compact power, Combustion and
Flame, Volume 158, Issue 10, October 2011, Pages 1890-1897, ISSN 0010-2180.
2. Anne Giroir-Fendler, Maira Alves-Fortunato, Melissandre Richard, ChaoWang,
Jose Antonio Díaz, Sonia Gil, Chuanhui Zhang, Fabien Can, Nicolas Bion,
Yanglong Guo, Synthesis of oxide supported LaMnO3 perovskites to enhance
yields in toluene combustion, Applied Catalysis B: Environmental, Volume 180,
January 2016, Pages 29-37, ISSN 0926-3373.
3. Teresa A.Wierzbicki, Ivan C. Lee, Ashwani K. Gupta, Rh assisted catalytic
oxidation of jet fuel surrogates in a meso-scale combustor, Applied Energy,
Volume 145, 1 May 2015, Pages 1-7, ISSN 0306-2619
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