WP2.2 Advanced Catalyst Development

INGAS 18-months Meeting, Paris, France, 20-21 May 2010INGAS 18-months Meeting, Paris, France, 20-21 May 2010

INGAS INtegrated GAS PowertrainINGAS INtegrated GAS Powertrain

Institute of Catalysis and Surface Chemistry

Polish Academy of Sciences

18 months research activities

WP2.2 Advanced Catalyst Development



Objective: Design of an active and stable catalyst for CH4 combustion

based on transition metal mixed oxides

Scope of work:• synthesis

• physico-chemical characterization

• catalytic testing

Innovative aspect:• novel precursors - hydrotalcites, pillared clays

• new compositions/modified synthesis methods for known structures (spinels, perovskites, hexaaluminates)

• synthesis in the presence of support suitable for washcoat preparation

WP2.2 Advanced Catalyst DevelopmentMixed Oxide Catalysts (ICSC PAS)



Summary of catalyst synthesis and characterization work(over 80 catalyst formulations):

Spinels and perovskites derived from hydrotalcite-like precursors (metal elements: Cu, Mn, Co, Cr, Ce, Zr, Pd, La, Al, different

stoichiometries)

Spinels and perovskites prepared by sol-gel procedure from citrate precursors

(metal elements: Cu, Mn, Co, Al, Fe, La, Pd)

Hexaaluminates (metal elements: Mn, Mg,Al, La)

Pillared clays (metal elements: Zr, Al, Pd, clay: montmorillonite)

Characterization methods: XRD, chemical analysis (ICP-OES), SEM, XPS, FT-IR, TG/DTG/DSC, TPR, N2 adsorption at 77 K

WP2.2 Advanced Catalyst DevelopmentMixed oxide catalyst (ICSC PAS)




2 12 22 32 42 52 62 722 theta CuKα

Inte

nsi

ty [

a.u

.] .

CuOCuMn2O4/Cu1.5Mn1.5O4Mn3O4

MnAl (2:1)Ht

CuMnAl (2:1:1)Ht

CuAl (2:1)Ht

CuMnAl (4:4:1)Ht

CuMnAl (1:2:1)Ht

CuMnAl (1:1:1)Ht

CuMnAl (2.5:5:1)Ht

5 15 25 35 45 55 65 75

2 theta CuKa

Inte

nsi

ty [

a.u

.]

MnLaAl(1:1:11)Ha-fresh

MnMgLaAl(0.5:0.5:1:11)Ha-fresh

MnLaAl(1:1:11)Ha-500

MnMgLaAl(0.5:0.5:1:11)Ha-500

MnLaAl(1:1:11)Ha-1100

MnLaAl(1:1:11)Ha-800

MnMgLaAl(0.5:0.5:1:11)Ha-1100

MnMgLaAl(0.5:0.5:1:11)Ha-800

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

0 10 20 30 40 50 60 70 80

2 theta Ka

Inte

ns

ity

[a

.u.]

CuMnAlZrCe(3.5:4:1:0.4:0.1)Ht

CuMnAlZrCe(4:3.5:1:0.4:0.1)Ht

CuMnAlZrCe(3.7:3.7:1:0.5:0.1)Ht

CuMnAlZrCePd(3.7:3.7:1:0.4:0.1:0.1)Ht

CuMnAlZr(3.5:4:1:0.5)Ht

CuMnAlCe(3.9:4:1:0.1)Ht

CuMnAl(4:4:1)Ht

Cu1,5Mn1,5O4/CuMn2O4

3 13 23 33 43 53 63

2 theta CuKa

inte

nsi

ty [

a.u

.]

Al-PILC

Pd2-Al-PILC

Pd5-Al-PILC

Zr-PILC

Pd2-Zr-PILC

Pd2-Al,Zr-PILC

Al,Zr-PILC

montmorillonite

PdO

adventitious impurities

2,00 12,00 22,00 32,00 42,00 52,00 62,00 72,00

2 theta CuKa

Inte

nsi

ty [

a.u

.]

MnAl(1:2)cit

MnAl(2:1)cit

CuMn(1:2)cit

Cu1.5Mn1.5O4/CuMn2O4

Mn2O3

CoLa(1:1)cit

MnLa(1:1)cit

LaCoO3

La2O3

Spinels/HtSpinels/Ht

Spinels, Perovskites/Cit

PILC

Hexaaluminates24 m2/g

19 m2/g

257 m2/g

197 m2/g

185 m2/g

229 m2/g

239 m2/g

182 m2/g

229 m2/g

265 m2/g

280 m2/g

200 m2/g

215 m2/g

114 m2/g

98 m2/g

101 m2/g

118 m2/g

94 m2/g

85 m2/g

66 m2/g

18 m2/g

76 m2/g

324 m2/g

33 m2/g

17 m2/g

30 m2/g

66 m2/g

86 m2/g

104 m2/g

98 m2/g

55 m2/g

237 m2/g

-100,0

900,0

1900,0

2900,0

3900,0

4900,0

5900,0

6900,0

7900,0

8900,0

9900,0

5 15 25 35 45 55 65 75

2 Theta CuKa

Inte

nsi

ty [

a.u

.]

LaFePd(1:0.95:0.05)Cit 800oC

LaFePd(1:0.95:0.05)Cit 550oC

LaFe(1:1)Cit 800oC

LaFe(1:1)Cit 550oC

LaFePd(1:0.95:0.05)Ht/pH8 700oC

LaFePd(1:0.95:0.05)Ht/pH10 700oC

Perovskites/Cit, Ht3 m2/g

16 m2/g

2 m2/g

26 m2/g

2 m2/g

17 m2/g

Different structures

Different compositions

Different specific surfaces

Ht – hydrotalcite-derivedCit – citrate-derived perovskitePILC – pilllared clays




Different morphologies

76 m2/gMnAl(2:1)Cit

237 m2/gMnAl(2:1)Ht

18 m2/gCuMn(1:2)Cit

151 m2/gCuMn(2:1)Cit/Puralox

33 m2/gLaCo(1:1)Cit

19 m2/gMnLaAl(1:1:11)Ha

182 m2/gPd2-Zr-PILC

LaFe(1:1)Cit2 m2/g



Catalytic testing – summary

hydrotalcite-derived mixed oxide catalysts belong to most active catalysts hexaaluminates form the least active group selected citrate-derived mixed oxides and pillared clays also display appreciable activity all tested mixed oxide catalysts are much less active than the reference noble metal ECOCAT sample.

0

20

40

60

80

100

120

100 150 200 250 300 350 400 450 500 550 600

Temperature [oC]

CH

4 c

on

vers

ion

[%

]ECOCAT reference (Pd/Rh catalyst)

Hydrotalcite-derived mixed oxides

Citrate-derived spinels

Citrate-derived perovskites

Hexaaluminates

Pillared clays

SV=10000 h-1

As received catalysts

WP2.2 Advanced Catalyst DevelopmentMixed Oxide Catalysts – Catalytic Screening

over 120 catalytic tests, carried out at SV=10000 and 50000 h-1 on as received and thermally aged catalysts




Supporting on a Puralox carrier (γ-Al2O3 + 5% ZrO2 and 2% CeO2)

Beneficial influence of the support

0

10

20

30

40

50

60

70

80

90

100

100 150 200 250 300 350 400 450 500 550

Temperature [oC]

CH

4 C

on

ve

rsio

n [

%]

CuMn(1:2)Cit

CuMn(1:2)Cit/Puralox



50 000 h-1 as received

0,0

20,0

40,0

60,0

80,0

100,0

0 100 200 300 400 500 600 700

Temperature [oC]

CH

4 c

on

vers

ion

[%

]

CuMn(1:2)Cit/PuraloxCuMn(1:2)Cit/Puralox-Pd-2 (NO3)CuMn(1:2)Cit/Puralox-Pd-5 (NO3)CuMn(1:2)Cit/Puralox-Pd-5 (ACAC)LaFe(1:1)CitLaFe(1:1)Cit_ox_red_oxLaFePd(1:0.95:0.05)CitLaFePd(1:0.95:0.05)Cit_ox_red_oxLaFe(1:1)HtLaFePd(1:0.95:0.05)HtMnLaAl(1:1:11)HaMnLaAl(25:1:11)HtPd-0.4-MnLaAl(25:1:11)HtCuMnAl(2.5:5:1)HtPd-0.4-CuMnAl(2.5:5:1)HtPd-1-CuMnAl(2.5:5:1)HtPd-2-CuMnAl(2.5:5:1)HtPd-2-Zr-PILCEcocat


50 000 h-1 aged 5h 600deg

0,0

20,0

40,0

60,0

80,0

100,0

0 100 200 300 400 500 600 700

Temperature [oC]

CH

4 c

on

vers

ion

[%

]

CuMn(1:2)Cit/PuraloxCuMn(1:2)Cit/Puralox-Pd-2 (NO3)CuMn(1:2)Cit/Puralox-Pd-5 (NO3)CuMn(1:2)Cit/Puralox-Pd-5 (ACAC)LaFe(1:1)CitLaFe(1:1)Cit_ox_red_oxLaFePd(1:0.95:0.05)CitLaFePd(1:0.95:0.05)Cit_ox_red_oxLaFe(1:1)HtLaFePd(1:0.95:0.05)HtMnLaAl(1:1:11)HaMnLaAl(25:1:11)Ht/PuraloxPd-0.4-MnLaAl(25:1:11)Ht/PuraloxCuMnAl(2.5:5:1)Ht/PuraloxPd-0.4-CuMnAl(2.5:5:1)Ht/PuraloxPd-1-CuMnAl(2.5:5:1)Ht/PuraloxPd-2-CuMnAl(2.5:5:1)Ht/PuraloxPd-2-Zr-PILCEcocat

50 000 h-1 aged 10h 800 deg

0

20

40

60

80

100

0 100 200 300 400 500 600 700

Temperature [oC]

CH

4 c

on

vers

ion

[%

]

CuMn(1:2)Cit/PuraloxCuMn(1:2)Cit/Puralox-Pd-2 (NO3)CuMn(1:2)Cit/Puralox-Pd-5 (NO3)CuMn(1:2)Cit/Puralox-Pd-5 (ACAC)MnLaAl(1:1:11)HaLaFe(1:1)CitLaFe(1:1)Cit_ox_red_oxLaFePd(1:0.95:0.05)CitLaFePd(1:0.95:0.05)Cit_ox_red_oxLaFe(1:1)HtLaFePd(1:0.95:0.05)HtMnLaAl(25:1:11)Ht/PuraloxPd-0.4-MnLaAl(25:1:11)Ht/PuraloxCuMnAl(2.5:5:1)Ht/PuraloxPd-0.4-CuMnAl(2.5:5:1)Ht/PuraloxPd-1-CuMnAl(2.5:5:1)Ht/PuraloxPd-2-CuMnAl(2.5:5:1)Ht/PuraloxPd-2-Zr-PILCEcocat

Thermal ageing tests – summary

λ=1, SV=50000 h-1

5h 600oC, 10 h 800oC,




50 000 h-1 as received - most active

0,0

20,0

40,0

60,0

80,0

100,0

100 200 300 400 500 600 700Temperature [oC]

CH

4 c

on

vers

ion

[%

]


CuMn(1:2)Cit/Puralox-Pd-5 (ACAC)

LaFe(1:1)Cit

Pd-1-CuMnAl(2.5:5:1)Ht

Pd-2-CuMnAl(2.5:5:1)Ht

Pd-2-Zr-PILC

Ecocat

50 000 h-1 aged 10h 800 deg - most active

0

20

40

60

80

100

100 200 300 400 500 600 700Temperature [oC]

CH

4 c

on

ve

rsio

n [

%]


CuMn(1:2)Cit/Puralox-Pd-5 (NO3)


Pd-1-CuMnAl(2.5:5:1)Ht/Puralox


Ecocat

50 000 h-1 aged 5h 600deg - most active

0,0

20,0

40,0

60,0

80,0

100,0

100 200 300 400 500 600 700

Temperature [oC]

CH

4 c

on

vers

ion

[%

]



LaFe(1:1)Ht



Pd-2-Zr-PILC

Ecocat

Thermal ageing tests – most active catalysts

Cu-Mn-based mixed oxides form most active group




Thermal ageing tests λ=1, 5h 600oC, 10 h 800oC, SV=50000 h-1

0

20

40

60

80

100

0 100 200 300 400 500 600 700

Temperature [oC]

CH

4 C

on

vers

ion

[%

]

Ecocat as received

Ecocat after 600 deg

Ecocat after 800 deg

0,0

20,0

40,0

60,0

80,0

100,0

0 100 200 300 400 500 600 700

Temperature [oC]

CH

4 C

on

vers

ion

[%

]

CuMn(1:2)Cit/Puralox after 600 deg

CuMn(1:2)Cit/Puralox as received

CuMn(1:2)Cit/Puralox after 800 deg

Cu-Mn-based mixed oxide catalysts supported on Puralox (γ-Al2O3 + 5%ZrO2 + 2%CeO2)

show good thermal stability



Conclusions

Best catalysts are based on CuMn mixed oxide systems and show

activity exceeding that described in literature for mixed oxide

systems. However, severe thermal treatment foreseen by InGas

boundary conditions causes significant drop in catalytic

performance of unsupported active phase.

Use of appropriate support improves thermal stability of mixed

oxide active phase and renders the material ready for washcoat

preparation. Addition of small amount of Pd at the stage of

precursor synthesis is beneficial for the activity.

WP2.2 Advanced Catalyst DevelopmentMixed Oxide Catalysts – Conclusions and Outlook



Outlook

Optimization of selected formulations aimed at enhancement

of activity, prevention of sintering and maximization of the specific

surface area via:

use of promoters (including noble metals) and carriers

synthesis modification (e.g. reverse microemulsions, ultrafine

grinding) trageted especially at increase of dispersion of thermally

stable low surface area oxidic phases (perovskites,

hexaaluminates)




Oil phase

Surfactant

Water (reaction medium)

Reverse microemulsion

limits particle size of precipitate

Ht – reverse microemulsion

Ht – conventional synthesis


Documents

WP2.2 Advanced Catalyst Development