CATALYST DEVELOPMENT

AND STABILIZATION
FOR SELECTIVE SO3 TO SO2
CONVERSION
Fahim Bin Abdur Rahman
Supervised by
Dr. John R. Monnier
Dr. John R. Regalbuto
Introduction

 SO2 is not only used as a refrigerant, preservative or reagent in the laboratory but also
can be used as a reducing agent for various chemical reactions.

 Sulfur-based thermochemical water splitting processes are some of the examples of

such reactions where SO2 is being used as a reducing agent to split the water into H2.
𝑆𝑂2 𝑔 + 2𝐻2 𝑂 𝑔 → 𝐻2 𝑔 + 𝐻2 𝑆𝑂4 𝑎𝑞

 SO2 is produced by catalytic decomposition of H2SO4 by following reactions:

𝐻2 𝑆𝑂4 𝑎𝑞 → 𝑆𝑂3 𝑔 + 𝐻2 𝑂 𝑔
1
𝑆𝑂3 𝑔 → +𝑆𝑂2 𝑔 + 𝑂2 𝑔
2

 Although SO3 is formed rapidly by thermal decomposition of sulfuric acid at 7000C, the
conversion of SO3 to SO2 is equilibrium limited and kinetic controlled reaction.

 Therefor, a catalyst is being needed to increase the rate of production of SO2 from
SO3.
2
Introduction

 Catalytic decomposition of SO3 to SO2

occurs at temperature  7500C.
Thermal decomposition
 However, at his temperature
𝐻2 𝑆𝑂4 𝑎𝑞 → 𝐻2 𝑂 𝑔 + 𝑆𝑂3 𝑔
 Most of the metal oxides have lower
Catalytic decomposition
activity due to the sulfate formation.
𝟏
 Other catalysts failed due to formation of 𝑺𝑶𝟑 𝒈 → 𝑶𝟐 𝒈 + 𝑺𝑶𝟐 (𝒈)
𝟐
volatile acid salts and catalyst poisoning.
S-based water splitting reaction
 The development of an active and stable
catalyst for the selective conversion of SO3 𝑆𝑂2 𝑔 + 2𝐻2 𝑂 𝑔 → 𝐻2 𝑔 + 𝐻2 𝑆𝑂4 𝑎𝑞
to SO2 is one of the main challenges to
produce H2 from H2O.

3
Objectives

Catalyst
Catalyst evaluation
characterization
Catalyst
synthesis
Material
selection

4
 Materials Selection
Literature showed that Titania supported Pt-group metals (Pt, Pd, Rh, Ir, Ru) effectively
catalyze the decomposition reaction

Activity of metal-oxide supported Pt

Activity of various PGMs1 catalyst at 8000C2
1S. N. Rashkeev, D. M. Ginosar, L. M. Petkovic, and H. H. Farrell, Catal. Today, vol. 139, no. 4, pp. 291–298, 2009.
2Daniel M. Ginosar; Lucia M.Petkovic; Anne W.Glenn; Kyle C. Burch, Int. J. Hydrogen Energy, no. 32, pp. 482–488, 2007. 5
 Support stabilization
 Lower temperature treated support has lost significant surface area when it exposed to
higher temperature, resulting in catalyst instability

Intensity (a.u.)
1000°C, 8h

900°C, 8h

800°C, 8h

700°C, 4h

Fresh

20 30 40 50 60

2ϴ (°)
surface area measurement of Titania P- Ex-situ acquired XRD patterns of Titania P-25 support
25 support after calcination treatments. after calcination treatment.
6
Dry Impregnation

Drying
Overnight drying in air+drying in
maffle furnace at 800C for 6h.

Reduction
At 3000C for 2h in hydrogen flow.

Calcination
 Support: TiO2 (Titania P25)- calcined at
At 8000C for 8h in static air.
8000C for 8h in static air.
 Precursors: Pt(NH3)4(OH)2, H2IrCl6, Characterization
Ru(NH3)4Cl3. Xray-Diffraction (XRD) and Pulse
Chemisorption

7
X-ray diffraction (XRD) of 1%Pt/TiO2

8
XRD of TiO2 supported monometallic catalysts
1%Ru/TiO₂, Fresh 1%Ru/TiO₂, Calcined
1%Ir/TiO₂, Fresh 1%Ir/TiO₂, Calcined
1%Pt/TiO₂, Fresh 1%Pt/TiO₂, Calcined
TiO₂, Calcined @800⁰C, 8h TiO₂, Calcined @800⁰C, 8h
Intensity

Intensity
Pt(111)
Pt(111) Pt(200)
Pt(200)

35 40 45 50 35 40 45 50
2q 2q
• No peaks corresponding to the metallic Ir or Ru were detected after high temperature
treatment.
• Ir and Ru is more stable on TiO2 than Pt after 8000C calcination treatment.

9
Electroless deposition (ED)
Hypothesis: Lower SFE metal will be deposited on high SEF core metal using ED
Meta SFE
l (ergs/cm2)
Cu 1934
Pd 2043 Batch ED
Ni 2364
Pt 2691
Co 2709
Rh 2828 Parameters
Mo 2877 Temperature 500C
Fe 2939 Pt:DMAB:EN 1:5:4
Nb 2983 Pt loading 1%
Ir 3231 pH of ED bath ~10
Ru 3409 pH adjusted by NaOH/HCl
10
W 3468
XRD of 1%Pt on 1%Ir/TiO2 and 1%Ru/TiO2

1%Pt on 1%Ru/TiO₂, Fresh 1%Pt on 1%Ru/TiO₂, Calcined

1%Pt on 1%Ir/TiO₂, Fresh 1%Pt on 1%Ir/TiO₂, Calcined
TiO₂, Calcined @800⁰C, 8h TiO₂, Calcined @800⁰C, 8h

Pt (111) Pt (200)
RuO2
Intensity

Intensity
30 35 40 45 50 30 35 40 45 50
2q 2q

 Pt sinters for both bimetallic catalysts after calcination at 8000C for 8 hr in static air.
 Ru oxidized very quickly, forming RuO2, which is a mobile species that can adversely affects to
catalyst stability.
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XRD of 1%Pt on 5%Ir/TiO2 and 5%Ru/TiO2

1%Pt on 5%Ru/TiO₂, Calcined

1%Pt on 5%Ru/TiO₂, 1%Pt on 5%Ir/TiO₂, Calcined
Fresh TiO₂, Calcined @800⁰C, 8h
Pt (111) Pt (200)
RuO2
Ru (100) Ru (002)
Intensity

Intensity
Ir (111)
Ir (200) IrO2

35 40 45 50 30 35 40 45 50
2q 2q

 More intense RuO2 formed with increasing metal loading, which has low SFE that can contribute
to less stability of the catalyst system.

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Summary for particle size (nm)

Fresh Calcined
Catalyst
Ru/Ir Pt Pt RuO2/IrO2
1%Pt on 1%Ir/TiO2 - - 34.0 -
1%Pt on 5%Ir/TiO2 5.1 - 23.4 10.0
1%Pt on 1%Ru/TiO2 - - 34.0 15.0
1%Pt on 5%Ru/TiO2 6.5 - 26.3 20.4

 Higher Ru loading catalyst oxidized readily, forming a more mobile RuO2 that can
decrease the stability of the catalyst.
 Sintering of Pt catalysts was improved when deposited on Ir. However, still significant
growth of Pt size after calcination suggesting to increase the active sites of base metal. Ir.

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Metallic surface area

Chemisorption of Ir/TiO2
 Metallic surface area increases
Metallic Surface (m²/g-catalyst)

3.54 3.61 with increasing wt-loading of Ir

metal in base catalysts.
2.72
 Increasing surface area of base
catalysts may reduce the sintering
of Pt0 after higher temperature
treatment
0.7

1% Ir/TiO₂ 5% Ir/TiO₂ 7.5% Ir/TiO₂ 10% Ir/TiO₂

14
XRD of 1%Pt on different wt% of calcined Ir/TiO2

1%Pt (ED) on
10%Ir/TiO₂, Calcined

1%Pt (ED) on
Pt(20.8 nm); IrO2 (8.1 nm) 7.5%Ir/TiO₂, Calcined

1%Pt (ED) on
5%Ir/TiO₂, Calcined
Intensity

Pt(21.6 nm); IrO2 (8.5 nm) 1%Pt (ED) on

1%Ir/TiO₂, Calcined

TiO₂, Calcined @800⁰C,

Pt(23.4 nm); IrO2 (10.0 nm) 8h

Pt

Pt(34 nm); No IrO2

IrO2

Ir

30 35 40 45 50
2q
15
Evaluation of TiO2 supported catalysts

16
Boron Nitride (BN)

Surface area as function of T Samples are calcined @8000C for 8h

75
BET surface area (m2/g)

TiO₂ BN Vpore Dave

60
Sample
(cm3/g) (nm)
45 BN-fresh 0.21 13.7
30 BN-6000C 0.18 13.8
BN-8000C 0.17 13.1
15
BN-9000C 0.13 7.4
0 BN-9500C 0.11 4.6
Fresh 700⁰C 800⁰C
Temperature BN-10000C 0.11 3.5
The formation of smaller pores are
BN is more stable support than TiO2 with possibly due to the oxidation of support
small loss of surface area at 8000C creating defects on the surface.
17
XRD of 1%Pt on different wt% of calcined Ir/BN

1%Pt (ED) on
7.5%Ir/BN, Calcined

1%Pt (ED) on
5%Ir/BN, Calcined
Intensity

1%Pt (ED) on
1%Ir/BN, Calcined

BN, Calcined
@800⁰C, 8h

Pt

IrO2

32 34 36 38 40 42 44 46 48
2q

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Pt sintering on supported Pt-Ir catalysts

BN TiO2
Calcined samples
Pt (nm) IrO2 (nm) Pt (nm) IrO2 (nm)

1%Pt 13.2 - 34.0 -

1%Pt ED on 5%Ir 13.4 16.8 23.4 10.0
1%Pt ED on 7.5%Ir 13.3 13.3 21.6 8.5

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Evaluation of BN supported catalysts

30
SO2 Yield (%)

20

10

0
0 20 40 60 80
Time (hr)
1% Pt/5% Ir/BN 1% Pt/7.5% Ir/BN

Test conditions included temperature of 800 °C, pressure

of 1 bar and H2SO4 concentration of 91.4 wt %.
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Conclusion
 High temperature pretreatment of support minimizes the support collapse during
reaction at extreme conditions.

 Pt is more stable with supported Ir-catalysts compare to supported Ru-catalysts

through the difference of SFE between Pt and Ru is higher compare to Pt and Ir.

 85% of the surface area has been lost for TiO2 while BN has lost only 15% when
exposed at 8000C.

 After calcination at 8000C, Pt sinters less for BN supported Pt-Ir catalysts compare to
TiO2 supported Pt-Ir catalysts.

 1%Pt on 7.5%Ir/BN shows far better stability compare to any catalysts prepared on
TiO2 support.

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Future Work
 The co-ED method will be studied in order to minimize the oxide formation of core
metal at extreme temperature.

 Since iridium is expensive, the same study will be done with a low-cost metal that will
minimize the cost of the catalysts.

There is no real ending in catalysis, it’s just a new

opening to a new beginning.

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