Reactions of synthesis gas on silica supported transition metal catalysts

Dissertation

Marita Niemelä

Research output: ThesisDissertationCollection of Articles

Abstract

The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO2 catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO2 considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO2 appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO2, ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO2 catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh4(CO)12/SiO2 from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes.
Original languageEnglish
QualificationDoctor Degree
Awarding Institution
  • Aalto University
Supervisors/Advisors
  • Krause, Outi, Supervisor, External person
Award date13 Jun 1997
Place of PublicationEspoo
Publisher
Print ISBNs951-38-5056-0
Electronic ISBNs951-38-5057-9
Publication statusPublished - 1997
MoE publication typeG5 Doctoral dissertation (article)

Fingerprint

Synthesis gas
Silicon Dioxide
Transition metals
Carbon Monoxide
Catalysts
Cobalt
Rhodium
Ruthenium
Hydrogen
Adsorption
Regain
Catalyst selectivity
Aldehydes
Nitrates
Hydrogenation
Ethanol
Chemical activation
Decomposition
Chemical analysis

Keywords

  • synthesis gases
  • transition metal catalysts
  • silicon dioxide
  • hydrogenation

Cite this

Niemelä, M. (1997). Reactions of synthesis gas on silica supported transition metal catalysts: Dissertation. Espoo: VTT Technical Research Centre of Finland.
Niemelä, Marita. / Reactions of synthesis gas on silica supported transition metal catalysts : Dissertation. Espoo : VTT Technical Research Centre of Finland, 1997. 44 p.
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author = "Marita Niemel{\"a}",
year = "1997",
language = "English",
isbn = "951-38-5056-0",
series = "VTT Publications",
publisher = "VTT Technical Research Centre of Finland",
number = "310",
address = "Finland",
school = "Aalto University",

}

Niemelä, M 1997, 'Reactions of synthesis gas on silica supported transition metal catalysts: Dissertation', Doctor Degree, Aalto University, Espoo.

Reactions of synthesis gas on silica supported transition metal catalysts : Dissertation. / Niemelä, Marita.

Espoo : VTT Technical Research Centre of Finland, 1997. 44 p.

Research output: ThesisDissertationCollection of Articles

TY - THES

T1 - Reactions of synthesis gas on silica supported transition metal catalysts

T2 - Dissertation

AU - Niemelä, Marita

PY - 1997

Y1 - 1997

N2 - The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO2 catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO2 considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO2 appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO2, ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO2 catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh4(CO)12/SiO2 from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes.

AB - The effect of catalyst precursor and composition on the activation of CO was investigated using CO hydrogenation as a test reaction. The interrelations of preparation, pretreatment, characteristics and activity were clarified. For Co/SiO2 catalyst, MgO promotion increased the CO adsorption capacity and the hydrogen uptake, although the extent of reduction for cobalt remained the same or decreased. The conversion per active metallic cobalt site consequently increased in conjunction with MgO promotion, while the effect on overall performance per 1 g of catalyst remained moderate. The precursor affected the performance of Co/SiO2 considerably. CO was more strongly adsorbed on catalysts of carbonyl origin than on those derived from cobalt nitrate, the activity thus being higher. Although the nitrate derived Co/SiO2 appeared both to retain its activity and to regain its adsorption capacity better than the catalysts of carbonyl origin, the performance of the latter was superior with time on stream. For tetranuclear cluster based Co-Ru and Co-Rh catalysts, rhodium or ruthenium was in contact with the support and cobalt was enriched on top. On Co-Ru/SiO2, ruthenium enhanced deactivation, and no benefits in activity or oxygenate selectivity were achieved relative to the monometallic catalysts of cluster origin. The Co-Rh/SiO2 catalysts were also less active than those derived from monometallic clusters, but they exhibited higher selectivities to oxygenated compounds due to the presence of active sites on the perimeter of the cobalt particles located on rhodium. The highest selectivity to oxygenates was achieved by changing the decomposition atmosphere of Rh4(CO)12/SiO2 from hydrogen to carbon monoxide. The results also showed two types of active sites to be operative in the formation of oxygenates - one for ethanol and another for aldehydes.

KW - synthesis gases

KW - transition metal catalysts

KW - silicon dioxide

KW - hydrogenation

M3 - Dissertation

SN - 951-38-5056-0

T3 - VTT Publications

PB - VTT Technical Research Centre of Finland

CY - Espoo

ER -

Niemelä M. Reactions of synthesis gas on silica supported transition metal catalysts: Dissertation. Espoo: VTT Technical Research Centre of Finland, 1997. 44 p.