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Anh Trieu Ly1

Catalytic Combustionof 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 Engineering

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

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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.

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

Table 1: chemical analysis of biodiesel (BG100) from the Renewable Energy Group

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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 Cheapo Stable and resistant to oxidation at high

temperatures and rich oxygen conditions.o Conduct lattice oxygeno 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)

0 1 2 3 4 5 6 70.00%

20.00%40.00%60.00%80.00%

100.00%

CO yield CO2 yield Conversion

time (h)

Conv

ersio

n, y

eild

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LaMnO3 supported in YSZ

• It was supported by YSZ (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] Firgue 1: Unit cell of

Lathanum manganese oxide[2].

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CO2

H2O

Catalytic Combustion Hypothesis

CxHyOz

O2

O2CxHyOz La-Mn O2 e

H2O CO2

LaMnO3YSZ

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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

Drying90oC

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 YSZNoCA

YSZ YSZCA

Less Active SitesMore Active Sites

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XRD analysis of fresh LM-YSZ

15wt% LaMnO3-YSZ- By comparing with

the pure LM, we identify exactly crystal structure of LM and YSZ by X-ray diffraction method(XRD).

10 20 30 40 50 60 70 800

500

1000

1500

2000

2500

3000

3500

4000

4500

5000XRD analysis of fresh LM-YSZ

2-Theta Degree

Inte

nsity

(cps

)

LM

YSZ

LM

LM-YSZ

YSZFirgue 2: size of

LaMnO3 supported in YSZ

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Experiment Setup

GC, Temperature controller, HV supply

Reactor Set up

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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.

0 1 2 3 4 5 6 7 80.00%

5.00%

10.00%

15.00%

20.00%

25.00%

30.00%

CO yield CO2 yield Conversion

time (h)

Conv

ersi

on, y

eild

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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

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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 10 20 30 40 50 60 70 800

500

1000

1500

2000

2500

3000

3500

before and after 24h experiment of LM-YSZ

LM-YSZ(spent24h)

original

2-Theta

Inte

nsity

(cps

)

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.

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Performance of catalyst with canola bio-diesel

• Methyl Oleate is an good model for canola biodiesel because the performance is same.

0 5 10 15 20 250.00%

10.00%20.00%30.00%40.00%50.00%60.00%70.00%80.00%90.00%

100.00%

Combustion of canola biodiesel in 15wt% LM-YSZ

CO yield CO2 yield Conversion

time (h)

Conv

ersio

n, y

eild

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)

LM (u

nsupp

orted

)

LM-YS

Z (im

pregna

tion)

LM-YS

Z (ph

ysical

mixin

g) YSZ

0.00%20.00%40.00%60.00%80.00%

100.00%

CO yield CO2 yield Conversion

Conv

ersio

n, y

eild - 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)

Fuel Flexibility

0 5 10 15 20 250.00%

20.00%40.00%60.00%80.00%

100.00%

CO yield CO2 yield Conversion

time(h)

Conv

ersio

n, y

eild

0 0.5 1 1.5 2 2.5 30.00%

10.00%20.00%30.00%40.00%50.00%60.00%70.00%80.00%90.00%

100.00%

CO yield CO2 yield Conversion

time(h)

Conv

ersio

n, y

eild

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)

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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.

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Future Work

•They will test the 15wt% LM-YSZ in the real catalytic

combustion engine at US Army Laboratory.

•The result of this work will be summarized in a

manuscript for future publication.

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Acknowledgements

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DeVlieg Fellowship

O.H. Reaugh Foundation

FMIC Center

Dr. Su Ha’s research group

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Questions ?

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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, Chao Wang, 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