Activation of catalysts

29th April 2013 Daniel Casas Orozco Preparation of Catalysts Environmental Catalysis Group Engineering Faculty Universidad de Antioquia

Outline
1. Objectives 2. Introduction 3. Active-phase/support interactions
a) Types of solid reactions b) Types of interactions

4. 5. 6. 7. 8.

Activation by calcination Activation by reduction Reduction-sulfidation Conclusions References

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Objectives
Describe the most used methods of catalyst activation Identify the differences and the aplicability of the available methods Ilustrate the effect of activation procedure on the activity and morphological characteristics of the final catalyst

Activation of catalysts

Introduction
Activation1*
defined as the

Transformation of a solid precursor to the material immediately active for the desired reaction

With impact on

Activity Selectivity Resistance to deactivation

1. Ertl, G., Knozinger, H., Schuth, F., & Weitkamp, J. (2008). Handbook of Heterogeneous Catalysis (2nd Edition., p. 4270). Wiley-VCH * If not specified, all the information taken from this reference Activation of catalysts

Typical examples

Transformation of hydroxides to oxides Reduction of metal oxides to dispersed metal particles

Activation of catalysts

Running-in period:

Supported phase has to catalyze the desired reaction for a certain time in order to reach stable activity and selectivity
In situ transformation for reactions such as:
Vanadium phospate catalysts: Oxidation of benzene or butane to maleic acid Hydrodesulfurization (HDS) catalysts: Supported oxides sulfides (caused by H2/H2S feed)
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Active-phase/support interactions
FACTORS AFFECTING ACTIVATION PROCESS

Dispersion state of the precursor

Interaction with the active phase

Solid-state reactions

Activation of catalysts

Activation of catalysts

Change in reactivity is expected if the supported phase reacts with the carrier Formation of new, less reactive compounds Hindering of active species

Activation of catalysts

Weak forces
Van der Waals hydrogen bonds interactions Graphite and silica exhibit weak forces with some supported materials

Electronic interaction
Electronic junction (not chemical bonds involved) Electron density can enhance selectivity

Transition layer (I)

Formation of crystallites Formation of patches or monolayers (Mo) Formation of a bi-layer (Co-Mo, Ni-Mo oxide on alumina)

Transition layer (II)

Solid solutions of supported elements Compounds with illdefined sthoichiometry

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MoO3 surface interaction (evaluating support)

Low interaction
-Sb2O4

Medium interaction
Co3O4 SiO2 TiO2

High interaction
-alumina

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MoO3 surface interaction (on SiO2)

Low interaction Low load (0-8%wt) MoO3 crystallites Medium interaction Medium load (8-13% wt) High interaction

High loading (13-20 Polymolibdates (PMA) %wt) on the surface as Silicomolybdic acid patched monolayers (SMA)

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Activation by calcination
High-temperature treatment in air is often2
The last step in producing oxide catalysts The next to the last step in producing metal or metal sulfide catalysts

Used to decompose and volatilize the various catalyst precursors formed in preparation
Hydroxides Nitrates carbonates
2. Farrauto, Robert; Barholomew, Calvin. (1997). Fundamentals of Industrial Catalytic Processes. Blackie Academic & Professional. New Jersey. 754 p.
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 Typically conducted in air at2

300 500 C for inorganic carriers <200 C or carbon supports

Special care with:

H2O trapped in the pores: structure cracking Decomposing of salt precursors: exothermic reactions Solid state reactions of metal oxides with the oxide carrier
2. Farrauto, Robert; Barholomew, Calvin. (1997). Fundamentals of Industrial Catalytic Processes. Blackie Academic & Professional. New Jersey. 754 p. Activation of catalysts 14

 2+ + 2 3
400 500 C

Bulk nickel aluminates

>500 C

Reduction conditions

Very high temperatures Sintering of support or metal species

Catalyst properties

Loss of porosity Loss of surface area Higher thermal stability

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Preparation method

Co-deposition of Pt and Fe salts on carbon carrier

400 C air oxidation Poorly dispersed, separate Pt and Fe metallic phases (segregation)

Activation treatment

Final characteristcs

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Knowledge about interaction between active phase and support allows the control the calcination step, e.g.: Favoring the spreading of precursors Use of additives Inhibiting promoting the formation of solid solutions doping the support Choosing temperature ramps or modified calcination atmospheres
Desired oxidation state Oxide structures

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Activation by reduction2
Final step of unsupported and supported catalyst preparation Converts oxides and/or catalyst precursor salts to the corresponding metal H2, CO, syn gas and hidrazine environments Sometimes, reduction from oxychloride complexes takes place (platinum and some noble metals) Direct reduction without intermediate oxide can lead to a higher dispersion
2. Farrauto, Robert; Barholomew, Calvin. (1997). Fundamentals of Industrial Catalytic Processes. Blackie Academic & Professional. New Jersey. 754 p.
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Special concerns in reduction procedures2

Purity of reducing agents: removal of oxygen, sulfur, water and hydrocarbons.

Removal of oxygen: high-surface area Pt catalyst Drying and hydrocarbon removal: molecuar sieves De-sulfuring: ZnO catalysts
2. Farrauto, Robert; Barholomew, Calvin. (1997). Fundamentals of Industrial Catalytic Processes. Blackie Academic & Professional. New Jersey. 754 p.

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 Temperature:
Optimization for high metal dispersion, surface area and extent of reduction (given a metal loading and support) Typical ranges are
250- 350 C: noble metals (2-6 h) 350-500 C: base metals (350 500 C)

Calcination temperature prior to reduction

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 Precursor loading
Supported base metals :High metal loading (15 25 %): more easily reduced catalysts than low loading (<10 %) materials

Support
Alumina-supported base metals (d) vs. Silicatitania supported materials

Preparation method
Impregnation-prepared materials (e) vs. Precipitation or ion exchange prepared

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 Heating rate and hydrogen space velocity:

Lower heating rates: 1-5 C/min Space velocity: 2000-3000 h-1 Allow water withdrawal (inhibit reduction and facilitate metal species transport

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Reduction-sulfidation
Catalyst preparation method for hydrotreating reactions
Hydrodesulfurization Hydrogenation Hydrodeoxygenation Hydrodemetillation Hydrocracking

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 Main active species

Group VI metals: molybdenum, tungsten Nickel and/or cobalt, iron Environmental concerns make mandatory the use of noble metals for complete hydrodesulfurization and de-aromatization of gasolines

Formation of active sulfided species necessitates a reduction and a sulfidation of oxide precursor

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 Typically, involves exposing the catalyst to and H2S/H2 mixture at high temperature Used conditions: previously calcined catalysts subjected to
350-400 C in 10 % H2S/H2 mixture (1 atm): laboratory applications 2-3 % H2S/H2 mixture (higher pressure) for industrial catalysts Industrial practice: hydrogen and sulfur-containing feed (spiked petroleum fraction)
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Role of procedure parameters Activation temperature and sequence steps

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 Catalyst preparation: deposition-precipitation method with urea Metal precursor: HAuCl4.3H2O (Gold Trichloride Trihydrate) Catalyst activation
U reactor 2 C/min, 1mL/min/mgprecursor (hydrogen or air)

Catalysts tested on CO oxidation reaction

100 mL/min gas (1% CO, 1% O2, 98% N2)
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Titanium butoxide Water Nitric acid Heating to 90 C and reflux for 15 h

4 Stirring for 1 h Stirring for 30 min Centrifugation, washing and drying

Titania (rutile) Water HAuCl4.3H2 sltn Urea sltn Stirring for 1 h Heating to 80 C mantained for 15 h Centrifugation, washing and drying
FINAL CATALYST

Activation

Air or H2

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Results Average particle size does not increase in hydrogen treated materials: reduction of neigboring support sites (oxygen and titanium as pinning centers) In air-treated materials, poor interaction between gold particles and support leads to growing gold particles. Conversion is diminished in these materials

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 Catalytic activity in CO oxidation reaction and deactivation of catalysts

Caused by carbonatepoisoning Aging in atmospheric conditions Typical carbonate bands followed by infrared spectroscopy (1710 cm-1 peaks)

Samples activated in H2

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Hydrogen-treated

Air-treated

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Conclusions
Interactions between active phase and support are a key concept in choosing an appropriate method of activation Several parameters must be adjusted in activation procedure in order to increase final catalyst activity. Design of experiments can be an important tool to systematically apporach the study of activation conditions A compromise between catalyst stability and activity is found in the reviewed methods, factor which must be taken into account in the final design of the material

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 Calcination method is usually not as a unique activation procedure but in conjunction with other activation steps Reduction-sulfurization methods are one of the most applied activation methods in petrochemical and large industrial catalytic processes

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References
1. 2. 3. Ertl, G., Knozinger, H., Schuth, F., & Weitkamp, J. (2008). Handbook of Heterogeneous Catalysis (2nd Edition., p. 4270). Wiley-VCH. Farrauto, Robert; Barholomew, Calvin. (1997). Fundamentals of Industrial Catalytic Processes. Blackie Academic & Professional. New Jersey. 754 p. Bokhimi, X., Zanella, R., Morales, A., Maturano, V., & Carlos, A. (2011). Au / Rutile Catalysts: Effect of the Activation Atmosphere on the Gold- Support Interaction. Journal of Physical Chemistry C, 115, 58565862. Bokhimi, X., & Zanella, R. (2007). Crystallite Size and Morphology of the Phases in Au/TiO2 and Au/Ce-TiO 2 Catalysts. Journal of Physical Chemistry C, 111, 25252532.

4.

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