Water-Gas Shift Reaction

Dimitris I. Kondarides
Laboratory of Heterogeneous Catalysis Department of Chemical Engineering University of Patras GR 26504 Patras, GREECE

RESTOENE Workshop 8-10 June 2011 Residencia la Cristalera, Miraflores de la Sierra, Madrid, Spain

Outline
1. Introduction 2. Industrial WGS catalysts and reactors
Thermodynamics Industrial catalysts and reactors HTS catalysts LTS catalysts Reaction mechanism and kinetics

3. WGS catalysts for fuel cell applications

Effect of the nature of the support Effect of the nature of the metallic phase Effect of addition of alkali promoters Effect of metal loading and crystallite size Effect of primary crystallite size of the support

4. Conclusions

Introduction
Water-Gas is a synthesis gas containing H2 and CO, originally made by passing steam over red-hot coke or coal. Heat supply for this endothermic reaction was usually provided by alternating the steam with an air stream.

C + H2O CO + H2
H = 131.2 kJ/mol

C + O2 CO2
H = 393.5 kJ/mol

2C + O2 2CO
H = 221 kJ/mol
Water gas apparatus
http://chestofbooks.com/crafts/scientific-american/sup4/Apparatus-For-TheProduction-Of-Water-Gas.html

Introduction
Today, water gas (synthesis gas) can be manufactured by the reaction of a carbonaceous material (e.g., coal, coke, natural gas, naphtha, etc.) with steam, oxygen, or CO2.

H2 /CO ratio

H (kJ/mol)
131.2

C + H2O CO + H2 CH4 + H2O CO + 3H2

CH4 + 1 O2 CO + 2H2 2

3
2 1

206.3

35.6

CH4 + CO2 2 CO + 2 H2

247.4

With the exception of partial oxidation, reactions are generally endothermic. The molar ratio of H2 to CO varies depending on the source of carbon/oxygen. Steam reforming reactions are mostly used when the ultimate objective is generation of pure hydrogen.

The water-gas shift (WGS) reaction

The WGS reaction is used to produce H2, to reduce CO content in a H2-rich stream or to adjust the CO/H2 ratio of water gas. The reaction has been first reported in 1888 and was then used widely as a source of hydrogen for the Haber process for the manufacture of ammonia.

CO + H2O CO2 + H2
= 41.1 kJ/mol

The reaction was catalyzed by oxides of iron and chromium (BASF) at 400-500 C.

Ammonia plant

. Steam reforming B. HT-WGS C. LT-WGS D. CO2 adsorption

E. Methanation F. Ammonia synthesis G. NH3 separation

Industrial applications
The water gas is used extensively in the industry for the manufacture of Ammonia Methanol Hydrocarbons (Fischer-Tropsch process) Metals (reduction of the oxide ore)

Hydrogen Hydrotreating Hydrocracking of petroleum fractions Hydrogenations in the petroleum refining and petrochemical industry

H2 production process

. Steam reforming B. HT-WGS C. LT-WGS D. CO2 adsorption

E. Methanation F. Ammonia synthesis G. NH3 separation

Thermodynamics of the WGS reaction

The WGS reaction is a reversible, moderately exothermic and equilibrium limited. High CO conversions can only be achieved at low temperatures, however with favorable kinetics at higher temperatures. The equilibrium constant decreases by a factor of 80 with increase of temperature from 200 to 400 oC.

CO + H2O CO2 + H2
= 41.1 kJ/mol

10 8 6

ln Kp

KP

PH2 PCO2 PH2OPCO

4 2 0 100 200 300 400 500 600

Thermodynamically, the efficiency of the WGS reaction is maximized at low temperature, high water and low hydrogen concentration.

Temperature ( C)
Variation of the equilibrium constant of the WGS reaction with temperature

ln( K eq ) =

5693.5 49170 + 1.077 ln T + 5.44 104 T 1.125 107 T 2 13.148 2 T T

Thermodynamics of the WGS reaction

The industrial realization of WGS takes place in a series of adiabatic converters where the water gas is converted in two stages.

CO + H2O CO2 + H2
= 41.1 kJ/mol

3%CO + 10%H2O

100

% CO at exit (dry basis)

4 3 2 1 0 200 300 400

o

Conversion of CO (%)

90 80 70 60 50 40 30 20 10 0 0 100 200 300 400

o

+ 6%CO2 + 20%H2
3% CO-10% H2O 3% CO-10% H2O-6% CO2 3% CO-10% H2O-20% H2 3% CO-10% H2O-20% H2-6% CO2

+ 6%CO2 + 20%H2

500

500

Temperature ( C)
CO levels typically achieved at the exit of the HTS and LTS reactors

Temparature ( C)

Variation of the equilibrium CO conversion with feed composition and temperature

Thermodynamics of the WGS reaction

The industrial realization of WGS takes place in a series of adiabatic converters where the water gas is converted in two stages. A high temperature shift (HTS) reactor is used for rapid CO conversion and a LTS reactor is used to shift equilibrium toward H2 production.
5

CO + H2O CO2 + H2
= 41.1 kJ/mol

% CO at exit (dry basis)

4 3 2
LT shift

HT shift

Inter-bed cooling Water gas

1 0 200 300 400

o

500
HT CO shift LT CO shift

Temperature ( C)
CO levels typically achieved at the exit of the HTS and LTS reactors

WGS reactors

Industrial catalysts and operating conditions

HTS reactor The catalyst used in HTS reactors is usually promoted Fe/Cr oxide. Typically, the inlet temperature is 300-360 oC and the total pressure between 10 and 60 bar. Under normal operating conditions, the temperature rises progressively through the catalyst bed and can increase up to 500 oC. The CO content can be reduced to 4% or lower. When used in conjunction with LTS, the exit gas of the HTS unit must be cooled. This is usually done by quenching with water, thus providing additional steam to the process.
HT CO shift LT CO shift

CO + H2O CO2 + H2
= 41.1 kJ/mol

Fe/Cr oxide P: 10-60 bar T: 350 oC CO: ~ 45% 450 oC 4%

Water gas

WGS reactors

Industrial reactors and catalysts

LTS reactor The catalyst used in LTS reactors is usually promoted Cu/Zn/Al. The inlet temperature is 190-230 oC and the total pressure does not usually exceed 40 bar. Inlet CO concentration varies between 1 and 5% depending on the performance of the HTS installed upstream. Exit temperatures can reach 280 oC and the CO content is typically reduced to < 0.5%. Commercial LTS catalysts are kinetically limited at <190 oC even at moderate space velocities. Because of the relatively low melting point of Cu (1084 oC), the catalyst is sensitive to deactivation caused by sintering and the maximum operating temperature should not exceed 280 oC.

CO + H2O CO2 + H2
= 41.1 kJ/mol

Fe/Cr oxide P: 10-60 bar T: 350 oC CO: ~ 45% 450 oC 4%

Cu/Zn/Al oxide P: < 40 bar T: 200 oC CO: 1- 4% 280 oC <0.5%

Water gas

HT CO shift

LT CO shift

WGS reactors

Industrial HTS catalysts

Industrial HTS converters exclusively apply Fe-based catalysts because of their excellent thermal stability, poison resistance and good selectivity. The stable ion phase under conditions is Fe3O4 (magnetite). This is combined minimizes catalyst promotion. reaction
Specific surface area 30-100 m2/g, depending of Cr2O3 content and calcination temperature

with chromia, which sintering by textural

The commercially available catalysts are applied in the form of pellets, containing 8-12% Cr2O3, and small amounts of CuO (~2%) as an activity and selectivity enhancer.

Industrial HTS catalysts

CH4 C2+ hydrocarbons

Effects of promotion of Fe-Cr oxide catalyst on CH4 formation and C2+ hydrocarbon production
Ratnasamy and Wagner, Chem. Rev. 51 (2009) 325-440

The commercially available catalysts are applied in the form of pellets, containing 8-12% Cr2O3, and small amounts of CuO (~2%) as an activity and selectivity enhancer. The catalyst is usually unsupported and available commercially in tablet or ring form. Major drawbacks (a) Toxicity of the water-soluble Cr6+ ions (b) Low volumetric catalytic activity (GHSV= 10000-15000 h-1), especially at low temperatures where CO conversion is favored thermodynamically.

Industrial HTS catalysts Activation

Commercial Fe/Cr/Cu catalysts must be activated before operation using a specific process to control reduction of the oxides to the catalytically active sites. Improper deactivation has a detrimental effect on the activity and life of the catalyst. The catalyst is typically prepared via a precipitation process in the form of Fe2O3 (hematite). The active Fe3O4 catalyst (magnetite) is formed upon reduction with gas mixtures containing H2, N2, CO, CO2 and H2O.

3Fe2O3 + H2 2Fe3O4 + H2O 3Fe2O3 + CO 2Fe3O4 + CO2

= 16.3 kJ/mol = + 24.8 kJ/mol

Special care should be taken to avoid further reduction of the active phase (Fe3O4) toward lower oxides, carbides or metallic Fe. Metallic Fe catalyzes the unwanted methanation and Fischer-Tropsch reactions

CO + 3H2 CH4 + H2O

= 206.2 kJ/mol

Industrial HTS catalysts Activation

These side reactions are unwanted because they lead in: (a) Consumption of H2 (b) Development of hot spots in the reactor (c) Lowering of the mechanical strength of the catalyst pellets and, therefore, increase of the pressure drop in the reactor. In industrial practice, a reduction factor (R) is used, which allows prediction of the degree of catalyst reduction as a function of feed composition.

R=

[CO] + [H2 ] [CO2 ] + [H2O]

When R < 1.2, there are usually no problems related to reduction of magnetite. The opposite is true for R > 1.6. The activated Fe3O4 catalyst is pyrophoric. Upon exposure to air, the catalyst must be re-reduced and stabilized by surface oxidation using an inert gas with low concentration of oxygen. Fe2O3-Cr2O3 catalysts have a lifetime of 3-5 years depending, mainly, on the temperature of operation.

Industrial LTS catalysts

The commercial LTS catalyst is composed of copper, zinc oxide, and alumina. Cu/Zn/Al commercial catalysts are applied in the form of tablets, extrusions, or spheres and are usually produced by co-precipitation of metal nitrates. Utilization of this sulfur-sensitive catalyst became possible only after the development of highly efficient hydrodesulfurization technologies using Co(Ni)-MoO3-Al2O3 catalysts (< 1.0 ppm sulfur). The active phase is copper, which remains active at temperatures as low as 190-200 oC. Exit temperatures can reach 380 oC and the CO content is typically reduced to < 0.5%. ZnO and Al2O3 protect copper against sintering during activation. ZnO provides some protection of Cu from sulfur poisoning by reaction with adsorbed sulfur compounds.
HT CO shift LT CO shift Water gas

CuO-ZnO-Al2O3

WGS reactors

Industrial LTS catalysts

The principal deactivation mechanism for LTS catalysts is poisoning by sulfur and chlorides contained in the process gas. The deactivation process begins as soon as the catalyst is placed on stream and CO leakage is usually detected within 6-12 months. Many plants have installed guard beds of LTS catalysts immediately ahead the main LTS unit (about the size of the main unit). The aim is to promote WGS and to sacrificially screen poisons from the main bed.
Mechanism of sulfur retention

2Cu + H2S Cu2 S + H2

= 59.4 kJ/mol
Mechanism of chloride protection

Trapping of S and Cl poisons over LTS catalysts.

SYNETIX (Katalco 83-3)

Industrial LTS catalysts Activation

Care must be taken to avoid steam condensation and to minimize the re-oxidation of the catalyst upon shutdown. Careful startup, inert purging to prevent condensation and sequestration during shutdown of industrial reactors can increase the life of the catalyst from months to years. Before reduction, the composition of the catalyst is typically: 32-33 wt.% CuO 34-53 wt.% ZnO, and 15-33 wt.% Al2O3 The reduction of CuO is highly exothermic and is carried out at temperatures not exceeding 220-230 oC to avoid sintering. For the same reason, reaction temperature should not exceed 300 oC. When formulated properly and operated under standard LTS conditions, Cu-ZnO-Al2O3 catalyst lasts a few years.
Cu/Zn/Al oxide P: < 40 bar T: 200 oC CO: 1- 4% Water gas 280 oC <0.5%

HT CO shift

LT CO shift

WGS reactors

WGS mechanisms and kinetics

The kinetics and reaction mechanism of the WGS reaction have been investigated extensively and various mechanisms have been proposed. (A) Redox mechanism The reactants induce a cyclic change of the oxidation state of the catalytic material. Water decomposes toward H2 and O on the reduced catalyst surface This is followed by reduction of the catalyst by CO, which leads to evolution of CO2. (B) Associative mechanism Chemisorbed CO and H2O interact on the catalyst surface to form and intermediate, which then CO + 2 decomposes to yield reaction products.

Cu/Cu+ 2 + Red CO + Ox

Fe2+/Fe3+ H2 + Ox CO2 + Red

CO2 + 2

Acidic oxide HCOOH

CO +H2O CO2 +H2

Metal/metal oxide

Fields of research in WGS catalysis

Development of more active catalysts that can operate at gas hourly space velocities above 40000 h-1 (e.g., promotion with noble metals). Development of catalysts that can operate at lower steam to gas ratios (lower operating costs). Replacement of Cr by non-toxic elements. Development of sulfur tolerant WGS catalysts

Why is there still interest in the WGS reaction ?

Fuel Cell applications

H2 for fuel cell applications

Fuel, air, steam

steam

steam

Steam reforming of fuel e.g. CH4, CH3OH, C2H5H, gasoline, ect.

8-10% CO

High Temperature WGS

3-5% CO

Low Temperature WGS

0.3-1% CO 0.3-

CO+H2O

CO2+H2

CO+H2O

CO2+H2

T= 350 - 400OC

T= 190 - 240OC
air

Electricity
PEM

<50 ppm CO Fuel Cell H2

Heat

Preferential oxidation of CO

CO + 1/22

CO2

T=120-150OC

H2 for fuel cell applications

Commercially available WGS catalysts (Cu-ZnO, Fe-Cr) can not be used in fuel cell application, due to problems related to: Volume, weight and cost (30-50% of the fuel processor) Transient response to changes in feed composition and temperature Pyrophoricity Deactivation in the presence of excess steam A lengthy precondition step is necessary for catalyst activation

Advantages of noble metal catalysts High activity at a wider temperature range No need for activation prior to use No degradation on exposure to air or temperature cycles Availability of wash-coating technologies, which may result in - reduced size and weight - improved ruggedness

WGS catalysts for fuel cell applications

The WGS reaction may take place over noble metals (e.g., Au, Pt-group metals) dispersed on metal oxide supports.

Identification of the key parameters which determine catalytic activity of supported noble metal catalysts

Effect of the nature of the support Effect of the nature of the dispersed metallic phase Effect of addition of alkali promoters Effect of metal loading and crystallite size Effect of primary crystallite size of the support

To develop active, selective and stable LT-WGS catalysts suitable for Fuel Cell applications

Catalysts
All catalysts were prepared with the wet impregnation method, followed by reduction with H2 at 300oC.

x% Me/MOx

Me= Pt, Ru, Rh, Pd x= 0 - 5 wt.%

Commercial oxide powders used as supports Metal precursors (NH3)2Pt(NO2)2 Ru(NO)(NO3)3 (NH3)2Pd(NO2)2 Rh(NO3)3 Reducible oxides CeO2 (3.3 m2/g) TiO2 (50 m2/g) MnO (0.4 m2/g) YSZ (12 m2/g) La2O3 (7.0 m2/g) Irreducible oxides Al2O3 (83 m2/g) MgO (22 m2/g) SiO2(144 m2/g)

Effect of the nature of the support Pt catalysts

0.5%Pt/MOx
100

Conversion of CO (%)

80

60

40

TiO2 La2O3 CeO2 YSZ MnO Al2O3 MgO SiO2

The catalytic performance of Pt is improved significantly when supported on reducible rather than on irreducible metal oxides.

20

Experimental conditions
Temperature range: 150 550oC Mass of catalyst: 100 mg Particle size: 0.18 < dp < 0.25 mm Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O (balance He)

0 200 300 400

o

500

Temperature ( C)
WGS activity of Pt catalysts supported on commercial oxide supports.

Effect of the nature of the support Pt catalysts

0.5%Pt/MOx
MnO

A strong effect of the support on catalytic activity of Pt is observed.

1
SiO2 MgO

TOF (s )

The TOF of Pt supported on TiO2, CeO2 and La2O3 is 1-2 orders of magnitude higher than that of Pt supported on irreducible oxides. For example, at 250oC, TOF of Pt/TiO2 is:
La2O3

-1

0.1

0.01 1.2 1.4 1.6

Al2O3

TiO2 CeO2

~ 90 times higher than that of Pt/SiO2 ~ 22 times higher than that of Pt/Al2O3.

YSZ

1.8

2.0
-1

2.2

2.4

1000/T (K )
Turnover frequencies (TOF) of Pt catalyst dispersed on the indicated metal oxides

Effect of the nature of the support Pt catalysts

Apparent activation energy (Ea) and dispersion of platinum
Metal Oxide

0.5%Pt/MOx
MnO

Ea
(kcal/mol)

Dispersion %

1
SiO2 MgO

TOF (s )

-1

MnO La2O3 CeO2

La2O3

27.4 24.6 21.4 17.2 24.9 27.9 15.2 13.3

18 24 49 54 62 66 86 100

0.1

0.01 1.2 1.4 1.6

Al2O3

TiO2 CeO2

MgO Al2O3 YSZ TiO2 SiO2

YSZ

1.8

2.0
-1

2.2

2.4

1000/T (K )
Turnover frequencies (TOF) of Pt catalyst dispersed on the indicated metal oxides

Effect of the nature of the support Ru catalysts

The WGS activity of NM catalysts depends strongly on the nature of the support.

0.5%Ru/MOx
100

1
TiO2 CeO2 YSZ Al2O3

Conversion of CO (%)

80

-1

60

TOF (s )

0.1

40

Al2O3 0.01 CeO2

TiO2

20

YSZ

0 200 300 400

o

500

1.6

1.7

1.8

1.9
-1

2.0

2.1

Temperature ( C)
Catalytic performance of Ru supported on selected commercial oxides.

1000/T (K )
Arrhenius plot of TOFs of Ru dispersed on the indicated oxides

Effect of the nature of the dispersed metal

0.5%M/TiO2
100

0.5%M/TiO2

Conversion of CO (%)

80 60

Rh

TOF (s )

Ru Pd
0.1

Pt
40 20

Pd Ru

-1

Pt
0.01

Rh
1.4 1.6 1.8 2.0
-1

0 200 300 400

o

500

2.2

2.4

Temperature ( C)
Effect of reaction temperature on the conversion of CO over Pt, Rh, Ru and Ru catalysts supported on TiO2.

1000/T (K )

Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on TiO2

Effect of the nature of the dispersed metal

The apparent activation energy of the reaction is practically the same for all metals examined: 15.7 17.1 kcal/mol

0.5%M/TiO2

Ea does not depend on the nature

of the metal but, mainly, on the nature of the support. This implies that the dominating contribution to Ea originates from a reaction step associated with the support (e.g. water adsorption/ activation, surface reaction, etc.) TOF follows the order: Pt > Rh > Ru > Pd with Pt being about 20 times more active than Pd.
TOF (s )
-1

Ru Pd
0.1

Pt
0.01 1.4 1.6 1.8 2.0
-1

Rh
2.2 2.4

1000/T (K )

Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on TiO2

Effect of the nature of the dispersed metal

The dependence of TOF on the nature of the dispersed metal is relatively weak.

0.5%M/CeO2
Ea= 24 kcal/mol
1

0.5%M/TiO2

Pd

TOF ( s )

TOF (s )

-1

-1

Rh Pt

Ru Pd
0.1

0.1

Pt
0.01 1.4 1.6 1.8

Ru
2.0
-1

0.01
2.2 2.4

Rh
1.4 1.6 1.8 2.0
-1

2.2

2.4

1000/T (K )
Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on CeO2

1000/T (K )

Arrhenius plot of TOFs obtained over Pt, Rh, Ru and Pd dispersed on TiO2

Effect of metal loading / crystallite size - Pt/TiO2

x%Pt/TiO2
100

Conversion of CO (%)

rCO (mol.s .gcat )

-1

80 60 40 20 0 200 300 400

o

1E-5

Pt loading (wt.%) 0.0 0.1 0.5 2.0 5.0

-1

5.0 1E-6 0.1 1E-7 2.0 0.5

500

1.6

1.8

2.0
-1

2.2

2.4

Temperature ( C)

1000/T (K )

Conversion of CO at a given temperature increases significantly with increasing Pt loading in the range of 0.1 5.0%. The activation energy of the reaction does not practically change.

Effect of metal loading / crystallite size - Pt/TiO2

x%Pt/TiO2
1.2<dPt<3.1 (nm)
1
Pt loading (wt. %) 0.1 0.5 2.0 5.0 2.0 (600 C, 2h) 5.0 (600 C, 2h) 5.0 (650 C, 4h)
o o o o

<16.2 (nm)

Reaction rate does not depend on Pt loading and crystallite size but only on the amount of exposed surface metal atoms. The rates of transfer of catalytically active species to or from the support are fast, compared to the overall reaction rate.

TOF (s )

-1

0.1

0.01 1.4

5.0 (700 C, 4h)

1.6

1.8

2.0
-1

2.2

2.4

1000/T (K )

TOFs of CO conversion obtained over Pt/TiO2 catalysts of variable metal loading and crystallite size

Effect of metal loading / crystallite size

Ru/TiO2
1.0 < dRu < 4.5 (nm)

Pt/CeO2

2.0 < dPt < 9.1 (nm)

TOF (s )

TOF (s )

0.1

Ru loading (wt. %) 0.1 0.5 1.0 2.0 5.0

1
-1

Pt loading (wt. %) 0.1 0.5 1.0 5.0

-1

0.1

0.01 1.4 1.6 1.8 2.0 2.2

-1

0.01
2.4

1.4

1.6

1.8

2.0

2.2
-1

2.4

1000/T (K )

1000/T (K )

TOF does not depend on the structural and morphological characteristics of the dispersed metal, including loading, dispersion and mean crystallite size.

Effect of the morphology of the support -TiO2

(101)

Characteristics of the i2 powders used as supports

(200) (105) (211)

UV
(204) (215)
(301)

PC
100 9 159

P25 AT
75 23 41 100 30 8

Intensity

(004) (103) (112)

(213)

(116) (220)

Composition (% anatase) Crystallite size (nm) Surface area (m2/g)

100 9 238

AT
(110)

(101) (111)

(211) * (220) (310)

P25 UV PC

20

30

40

50

60

70

80

Diffraction angle (2)

X-ray diffractograms of commercial TiO2 powders used as supports

UV: Hombikat UV100, Sachtleben Chemie PC: PC-500, Millenium Chemicals P25: P-25, Degussa AT: AT-1, Millenium Chemicals

Effect of the morphology of the support -TiO2

0.5%Pt/TiO2
100

Conversion of CO (%)

80

60

40

20

TiO2 support UV PC P25 AT

200 300 400
o

The catalytic performance of Pt is improved when supported on TiO2 with small primary crystallite size (high surface area).

0 500

Temperature ( C)
Effect of the type of the TiO2 support on the catalytic performance of dispersed Pt.

Effect of the morphology of the support -TiO2

0.5%Pt/TiO2
10

16 nm

25 TOF (s )
1
-1

18
UV

16

35

14

0.1 AT 0.01 1.6 1.8 2.0

-1

PC

12

P25

0
2.2 2.4

10 15 20 25 30 35

1000/T (K )

Primary crystallite size of TiO2 (nm)

Reaction rate per surface Pt atom increases by more than two orders of magnitude (a factor of 120 at 250C) by decreasing the primary crystallite size of the TiO2 carrier from 35 to 16 nm. This is accompanied by a decrease of the apparent activation energy of the reaction from 16.9 to 11.9 kcal/mol.

Activation Energy, (kcal/mol)

18

TOF at 250 C (s )

-1

Effect of the morphology of the support -TiO2

The catalytic performance of Pt is significantly improved when supported on TiO2 with smaller primary particle size.

Why ?
Redox mechanism The strong dependence of TOF on the type of TiO2 support employed may be related to the effect of TiO2 crystallite size on its reducibility. It has been reported that reducibility of small oxide clusters depends on its size (at least for CeO2 and La2O3)
R.J. Gorte and coworkers
J. Phys. Chem. 100 (1996) 18128 J. Phys. Chem. 100 (1996) 785 Appl. Catal. B 17 (1998) 101

Associative mechanism Structural characteristics of TiO2 may influence the type, number, density and reactivity of surface hydroxyl groups, which play a key role in the formation of formate-type intermediates. Hydroxyl concentration on TiO2 surface decreases with increasing crystallite size.

Reducibility of TiO2 H2 TPR

0.5%Pt/TiO2
500 ppm PC

PtOx TiO2

Pt TiO2-x
Ti3+ + OH-

H2 consumption

Ti4+ + H(a) + O2dTiO2

UV

P25 AT

Surface reduction of TiO2 is enhanced with decrease of particle size of TiO2

100 200 300 400 500 600

Temperature ( C)
H2-TPR over preoxidized Pt/TiO2 catalysts

Reducibility of TiO2 Raman spectroscopy

0.5%Pt/TiO2
Realtive Intensity, (a.u.) Raman intensity a.u. Pt/TiO2 catalysts O2, 30oC O2, 30 C
SiO2 AT

Oxidizing atmosphere
Peak (cm-1) 485 398 516 640 Assignment

AT

(e)

(*)

(*)

P25 P25 PC PC

SiO2 (reactor)

(d) (c)

UV

UV
SiO2

}
}

TiO2 (anatase)

(b) (a)

SiO2
800 600 400
-1

1000

200

447 612

Raman shift, cm Raman shift (cm-1)

TiO2 (rutile)

In situ Raman spectra obtained over preoxidized Pt/TiO2 catalysts under O2 flow at 30oC

Reducibility of TiO2 Raman spectroscopy

Pt/TiO2(UV)
Pt/TiO2(UV) catalyst 4.3%H2/N 4.3% H2/N2 2 Relative Intensity, a.u. Raman intensity (a.u.)
450 C
(f) (e) (d)
355 315 270

H2 reduction
Peak (cm-1) 355 315 270 Assignment

450C o 350oC 250C o

o

350 C 250 C

(c) (b) (a)

Ti2O3

150 C 150 C
30 C SiO2 SiO

30oC

TiO2

30oC
2

150-250oC
800 600 400
-1

Ti2O3

1000

200

Raman Shift, cm Raman shift (cm-1)

350-450oC
In situ Raman spectra obtained upon exposure of the Pt/TiO2 catalysts to H2/N2 mixture at 30-450 oC.

TiO, Ti2O (Raman silent)

Reducibility of TiO2 Raman spectroscopy

Pt/TiO2 catalysts 4.3%H2/N2 H2, 150 C Relative Intensity, a.u. Raman intensity (a.u.)
(A)
(*) (*)

P25 PC

P25
(c)

460

360 320 270

UV

dTiO2

PC (b)

(a) UV

T= 150oC
800 600 400
-1

1000

200

Raman shift (cm Raman shift, cm -1)

In situ Raman spectra obtained upon exposure of the indicated Pt/TiO2 catalysts to H2/N2 mixture at 150 oC.

Reducibility of TiO2 Raman spectroscopy

T= 250oC
1000 800 600
(*)

400
(*)

200
P25 PC

Relative Intensity, a.u. Raman intensity (a.u.)

Pt/TiO2 catalysts 4.3%H2/N2 H2, 250 C

P25
(c)
440

(B)

UV
355 315270

The reducibility of TiO2 increases with decrease of particle size.

PC
(b)

dTiO2

UV
(a)

P25 PC UV 1000 800 600 400 200

Raman shift (cm-1)

In situ Raman spectra obtained upon exposure of the indicated Pt/TiO2 catalysts to H2/N2 mixture at 150 oC.

Reducibility of TiO2 CO TPR

0.5%Pt/TiO2
H2-TPR, Raman, CO-TPR
500 ppm PC

CO2 or H2 production

The reducibility of Pt/TiO2 catalysts increases with decrease of particle size of the support.

UV

PtOx + xCO TiO2 + xCO

Pt + xCO2 TiO2-x + xCO2 CO2(g) + H2(g) +O2-(S)

P25 AT

CO(M) + 2OH -(S)

100 200 300 400 500 600

Temperature ( C)
CO-TPR over preoxidized Pt/TiO2 catalysts

Reducibility and MOx crystallite size

The WGS activity of noble metals is improved when dispersed on reducible oxides (MOx) with small crystallite size.

100

0.5%Pt /10%MOx/Al2O3
Co Ni Ti Cr Mn Cu

Conversion of CO (%)

80 60 40 20 0 200 250

How can we use this result ?

MOx can be dispersed on high surface area supports, such as Al2O3 and TiO2
Experimental conditions

Fe Pt/Al2O3

300

350

400
o

450

500

Temperature ( C)
Conversion of CO as a function of reaction temperature obtained over 0.5%Pt/MOx/Al2O3

Mass of catalyst: 100 mg Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O

Reducibility and MOx crystallite size

100

0.5%Pt /10%MOx/TiO2
Nd Ho Y

Conversion of CO (%)

80 60 40 20 Ce Gd Pt/TiO2

Experimental conditions
0 150 200 250 300 350
o

400

450

Temperature ( C)
Conversion of CO as a function of reaction temperature obtained over 0.5%Pt/MOx/TiO2

Mass of catalyst: 100 mg Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O

Reducibility and MOx crystallite size

Dispersion of Pt on combined mixed oxide catalysts results in materials with enhanced WGS activity.

60

Conversion of CO (%)

40

CeOx/TiO2 NdOx/TiO2 TiO2 Al2O3 CeOx/Al2O3

20

Experimental conditions
0 200 250 300 350 400
o

450

500

Temperature ( C)
Conversion of CO as a function of reaction temperature obtained over Pt catalysts supported on mixed oxides

Mass of catalyst: 100 mg Total flow rate: 200 cm3/min Feed composition: 3%CO + 10% H2O 6% CO2 + 20% H2

Methods to improve activity of noble metals

The relatively weak (factor of 20 - 30) dependence of TOF on the nature of the dispersed metal reflects the narrow range of strengths of CO interaction with the metals investigated.

Can we alter the metal-CO bond strength?

Addition of promoters (e.g. alkalis) Use bimetallic catalysts Metal-support interactions (doping) Electrochemical promotion (NEMCA) .

Volcano-type correlation between TOF of metals and their respective CO heats of adsorption.
Grenoble, Estadt, Ollis, J. Catal. 67 (1981) 90.

Effect of addition of alkalis

0.5%Pt/(TiO2-alkali)
Conversion of CO (%)
100
-1 -1

alkali : Pt = 1:1
1E-4

80 60 40 20 0
alkali (wt. %) 0.0 alkali 0.34 Cs 0.10 K 0.018 Li 0.06 Na
o

rCO(mol.gcat s )

1E-5
alkali (wt. %) 0.0 % alkali 0.34% Cs 0.10% K 1E-6 0.018% Li 0.06% Na

1.8

2.0

2.2
-1

Temperature ( C)

1000/T(K )

Effects of addition of alkalis on the WGS activity of Pt/TiO2 catalyst

Effect of addition of alkalis

0.5%Pt/TiO2 - x% Cs
100

1E-4 Ea=16 kcal/mol

Conversion of CO (%)

rCO(mol.gcat s )

80 60 40 20 0 200 300 400 Cs content (wt.%) 0.0 0.17 0.34 0.68

-1 -1

1E-5 x% Cs 0.0 0.17 0.34 0.68

-1

1E-6

Temperature ( C)
Effect of addition of Cs on the catalytic performance of 0.5%/TiO2 catalysts

500

1.7 1.8 1.9 2.0 2.1 2.2 2.3

1000/T (K )
Arrhenius plot of reaction rates over Cspromoted 0.5%Pt/TiO2 catalysts

Effect of addition of alkalis

In both cases, the maximum is observed for alkali:Pt ratios of 1:1

x% Cs
1.6 1.2 0.8 220 C 0.4 0.0 0.0 0.2 0.4 0.6
0.4 0.0 0.00
o o

x% Na
1.6 250 C
o

TOF (s )

-1

-1

250 C

TOF (s )

1.2 0.8 220 C

o

0.05

0.10

0.15

0.20

Cs content (wt.%)

Na content (wt.%)

Effect of alkali-promotion on TOFs of Pt/TiO2 catalysts

Effect of addition of alkalis H2 TPD

Alkali, X:Pt=1
Hydrogen adsorbed on the metal Hydrogen adsorbed on the support Hydrogen adsorbed at the metal-support interface
K

Promoter Cs

Na

Li

Desorption temperature reflects the chemisorption strength of surface sites The adsorption strength of sites located at the metal-support interface is affected strongly by the presence of alkali promotes

none
100 200 300
o

400

Temperature ( C)

H2-TPD patterns obtained over alkali-promoted Pt/TiO2

Effect of addition of alkalis H2 TPD

Alkali, X:Pt=1 x% Na
Na content (wt.%) 0.20
Promoter Cs
100 ppm

x% Cs
Cs content (wt.%) 0.68

0.12
K

100 ppm

0.34
Na

0.06

Li

0.017

0.17

none
100 200 300
o

0.00 100 200 300 400

o

0.00 100 200 300 400

o

400

500

500

Temperature ( C)

Temperature ( C)

Temperature ( C)

H2-TPD patterns obtained over alkali-promoted Pt/TiO2

Effect of addition of alkalis H2 TPD

Desorption temperature (Tmax) reflects the chemisorption strength of surface sites

Ru/Na-TiO2
wt.% Na 0.2

280

Tmax ( C)

260 240 220 200 0 1 2

Promoter none Li Na K Cs

0.06 0.0
100 200 300 400
o

500

Temperature ( C)

Pd/Cs-TiO2
wt.% Cs 0.68

3
0.34 0.0

Alkali:Pt atomic ratio

Effects of alkali promotion on the desorption temperature (Tmax) of hydrogen adsorbed at the metal-support interface
100 200 300
o

400

500

Temperature ( C)

Effect of addition of alkalis H2-TPD

The effect is qualitatively similar to that observed for M/Al2O3 catalysts Alkali promotion of TiO2 affects the chemisorption strength of sites located at the metalsupport interface
M/Al2O3 T= 300oC Log (turnover rate)

TOF250 C (s )
o

-1

1.5

1.0

Promoter none Li Na K Cs

0.5

200

220

240
o

260

280
-Hads (CO), kJ/mol

Tmax( C)
Dependence of TOF at 250 oC on the desorption temperature of hydrogen adsorbed at the metal-support interface

Effect of addition of alkalis CO TPR

500 ppm

0.68% Cs

CO2, H2 production

Alkali promotion of TiO2 affects the chemisorption strength of sites located at the metalsupport interface Alkali promotion also affects the reducibility of TiO2 Qualitatively similar results were obtained upon doping of TiO2 with alkaline earth metals.

0.20% Na

0.12% Na
CO2 H2

Unpromoted 100 200 300 400 500 600

Temperature ( C)

CO TPR patterns obtained over alkalipromoted Pt/TiO2 catalysts

Performance of optimized catalyst

0.5%Pt/(1%CaO-TiO2)
HTS conditions: 9.7% 38.7% 44.8% 6.8%
100 80 60 40 20 0 200 250 300 350
o

CO H2O H2 CO2

LTS conditions: 1.6% 29.9% 52.2% 16.3%

100 80 60 40 20 0

CO H2O H2 CO2

Conversion of CO (%)

Conversion of CO (%)

GHSV (h ) 4000 7400 10000

-1

GHSV (h ) 4000 7400 10000

400 450

-1

200

250

300
o

350

Temperature ( C)

Temperature ( C)

Effect of space velocity on the catalytic performance of 0.5%Pt/1%CaO-TiO2 catalyst under realistic feed compositions

Performance of optimized catalyst

0.5%Pt/(1%CaO-TiO2)
100 80 60 40 20 0 0 10 20 30 40 50 60

Conversion of CO (%)

T=300 C

Pt/TiO2 Pt/TiO2(1% CaO)

Time-on-stream (h)
Long-term stability tests of Pt/TiO2 and Pt/TiO2(1%CaO) catalysts. Feed composition: 3%CO, 10% H2O, 20%H2, 6%CO2; T= 300 oC; SV= 29000 h-1.

Mechanistic studies CO TPR/DRIFTS

0.5%Pt/TiO2 (PC)
450 C
2060 3667
o

(CO) region (OH) region

400 C 350 C
1945
o

1525

Formates/carbonates (support)
1384

3711 3667

1690

1566

Absorbance (a.u.)

300 C 250 C O 200 C 150 C

2068
o o

2120 2175

2062

1625 1690

CO(Pt) + OH(TiO2)
1560

[HCOO](Pt/TiO2)

100 C
1837

1572 1622 1525

(formate mechanism)

75 C
2081 2112 3665 3727 3603
o

1579

2185

1435

25 C

4000

3500 2250

2000

1750
-1

1500

Wavenumber (cm )

FTIR spectra obtained upon heating the preoxidized Pt/TiO2(PC) catalyst under 1%CO flow from 25 to 450 oC.

Mechanistic studies CO TPR/DRIFTS

0.5%Pt/TiO2 (PC)
2060

O C

350 C

1945 Absorbance (a.u.)

300 C
o

Pt-

Pt0 TiO2

iOx

Ti3+

e-

250 C

200 C

Creation of new adsorption sites [Ti3+-Pt] at the metalsupport interface

150 C
o

1830
100 C
o

Retated to the SMSI effect ??

2000
-1

2250

1750

Wavenumber (cm )

Mechanistic studies Active sites

Pt/TiO2
2056 450 400 350

Pt/TiO2-Na(0.2%)
450 400

Pt/TiO2-Cs(0.68%)
450 400 350 2043 300

2056
350

Absorbance (a.u.)

Absorbance (a.u.)

300

300

Absorbance (a.u.)

250 1975 1745 200 1940 150

250

250

1965 1755
200

200 1935 150

150

100 1830 25

2030 1815

100

2025 1820

100

25

25

2200

2000

1800

1600
-1

2200

2000

1800

1600
-1

2200

2000

1800

1600
-1

wavenumber (cm )

wavenumber (cm )

wavenumber (cm )

FTIR spectra obtained following adsorption of CO (1%) at 25oC and subsequent heating at 450C under He flow

Mechanistic studies Active sites

Pt/TiO2-CaO(1%)
450 400 350

Pt/TiO2-WO3(4%)
450 400 350
2050

Pt/SiO2
400 350

Absorbance (a.u.)

Absorbance (a.u.)

300 1925 1700 250 200

X
2077

300 250 200

Absorbance (a.u.)

300

X
2085

250

200

150

150

150 2063 1740 100 1800 25

100 1837

100

1628

25

25

2200

2000

1800

1600
-1

2200

2000

1800

1600
-1

2200

2000

1800

1600
-1

wavenumber (cm )

wavenumber (cm )

wavenumber (cm )

FTIR spectra obtained following adsorption of CO (1%) at 25oC and subsequent heating at 450C under He flow

Mechanistic studies Active sites

Pt/CeO2
400 350 300
2045

Pt/YSZ
2045

400 350 300

Adsorption sites at the metal-support interface are directly related with catalytic activity The LF band in the (CO) region is the fingerprint of active WGS catalysts

250

Absorbance (a.u.)

Absorbance (a.u.)

250

200

150

200

2087

1975

1995

100

150

1570 1630 1822

2091

100
1628

25
1827

25

2200

2000

1800
-1

1600

2200

2000

1800

1600
-1

wavenumber (cm )

wavenumber (cm )

FTIR spectra obtained following adsorption of CO (1%) at 25oC and subsequent heating at 450C under He flow

Kinetic studies Power low expression

x% CO, 10%H2O, 20%H2, 6%CO2
1E-5
210 C O 230 C O 250 C O 270 C
O

3% CO, x%H2O, 20%H2, 6%CO2

1E-5

a b c d r = k PCO PH 2O PCO2 PH2

rCO(molgcat s )

-1 -1

rCO(mol.gcat s )

250 C O 230 C
1E-6

1E-6

-1 -1

k = k0 exp ( Ea / RT )
T=210 270 oC

1E-7

1E-7

1E-8 0,00

1E-8

0,02

0,04

0,06

0,04

0,08
2

0,12

0,16

0,20

a = 0.5 b=1 c0 d = 0.7

PCO = 0 6% PH2O = 0 18% PCO2 = 0 19% PH2 = 0 50%

PCO (atm)
3% CO, 10%H2O, 20%H2, x%CO2
1E-5

PH O (atm)
3% CO, 10%H2O, x%H2, 6%CO2
250 C O 230 C
O

rCO(mol.gcat s )

1E-6

rCO(mol.gcat s )

250 C O 230 C

1E-5

-1 -1

-1 -1

1E-6

1E-7

1E-7

k0 = 0.31 mol g -1 s 1 Ea = 10.8 kcal mol -1

0,0 0,1 0,2
2

1E-8 0,00 0,05

2

1E-8

0,10

0,15

0,20

0,3

0,4

0,5

PCO (atm)

PH (atm)

Kinetic studies Power low expression

1.5 - 3% CO 10 - 20%H2O 20 - 40%H2 6%CO2
a b c d r = k PCO PH 2O PCO2 PH2

k = k0 exp ( Ea / RT )
T=210 270 oC

rCO(molgcat s )

-1 -1

1E-5

3% CO, 10% H2O, 20% H2, 6% CO2 3% CO, 20% H2O, 20% H2, 6% CO2 3% CO, 10% H2O, 40% H2, 6% CO2 1.5% CO, 10% H2O, 20% H2, 6% CO2

a = 0.5 b=1

PCO = 0 6% PH2O = 0 18% PCO2 = 0 19% PH2 = 0 50%

1E-6

c0 d = 0.7
Ea=10.8kcal/mol

1E-7 1,3 1,4 1,5 1,6 1,7 1,8 1,9 2,0 2,1 2,2

k0 = 0.31 mol g -1 s 1 Ea = 10.8 kcal mol -1

1000/T (K )
Fitting of experimental data to the power-low expression

-1

Conclusions
The WGS technology is well established and widely used in large scale steadystate operations, including manufacture of ammonia, methanol, refinery hydrogen Fischer-Tropsch synthesis, etc. Conventional catalysts and reactors cannot be used in fuel cell applications, mainly due to restrictions in volume and weight. Noble metal catalysts with proper structural and morphological characteristics may be considered as promising candidates as WGS catalysts for fuel cell applications.

References
Effect of morphological characteristics of TiO2-supported noble metal catalysts on their activity for the water-gas shift reaction, P. Panagiotopoulou, D.I. Kondarides, J. Catal. 225 (2004) 327-336. Effect of the nature of the support on the catalytic performance of noble metal catalysts for the Water-Gas Shift Reaction, P. Panagiotopoulou, D.I. Kondarides, Catal. Today 112 (2006) 49-52. Particle size effects on the reducibility of titanium dioxide and its relation to the Water-Gas Shift activity of Pt/TiO2 catalysts, P. Panagiotopoulou, A. Christodoulakis, D.I. Kondarides, S. Boghosian, J. Catal. 240 (2006) 114-125. Water-gas shift activity of doped Pt/CeO2 catalysts, P. Panagiotopoulou, J. Papavasiliou, G. Avgouropoulos, T. Ioannides, D.I. Kondarides, Chem. Eng. J.134 (2007) 16-22. A comparative study of the water-gas shift activity of Pt catalysts supported on single (MOx) and composite (MOx/Al2O3, MOx/TiO2) metal oxide carriers, P. Panagiotopoulou, D.I. Kondarides, Catal. Today, 127 (2007) 319-329. Effects of alkali additives on the physicochemical characteristics and chemisorptive properties of Pt/TiO2 catalysts, P. Panagiotopoulou, D.I. Kondarides, J. Catal. 260 (2008) 141-149. Kinetic and mechanistic studies of the water-gas shift reaction over Pt/TiO2 catalyst, C.M. Kalamaras, P. Panagiotopoulou, D.I. Kondarides, A.M. Efstathiou J. Catal. 264 (2009) 117-129. Effects of alkali-promotion of TiO2 on the chemisorptive properties and water-gas shift activity of supported noble metal catalysts, P. Panagiotopoulou, D.I. Kondarides, J. Catal. 267 (2009) 57-66. Chemical reaction engineering and catalysis issues in distributed power generation systems, P. Panagiotopoulou, D.I. Kondarides, X.E. Verykios, Ind. Eng. Chem. Res. 50 (2011) 523-530. Effects of promotion of TiO2 with alkaline earth metals on the chemisorptive properties and water-gas shift activity of supported platinum catalysts, P. Panagiotopoulou, D.I. Kondarides, Appl. Catal. B 101 (2011) 738-746.

Thank you very much for your attention!!