Cobalt and ruthenium-cobalt catalysts in CO hydrogenation and hydroformylation

Dissertation

Research output: ThesisDissertationCollection of Articles

1 Citation (Scopus)

Abstract

Cobalt and ruthenium-cobalt catalysts prepared from various precursors were studied in the activation of CO using CO hydrogenation and vapour phase hydroformylation as test reactions. The characteristics and activity were related to the precursor, composition, promoters and the method of preparation. Catalysts prepared from carbonyls exhibited the highest activity in CO hydrogenation. In addition to hydrocarbons, Co2(CO)8/SiO2 had a high (20%) selectivity for oxygenates such as alcohols and esters. Likewise, the Co2(CO)8/SiO2 catalyst was active in the hydroformylation of ethene, whereas the conventional cobalt catalysts prepared from inorganic salts were virtually inactive in this reaction. Promotion by alkali or alkaline earth cations affected the performance of the Co2(CO)8/SiO2 catalyst significantly: the activity decreased in both CO hydrogenation and ethene hydroformylation, but at the same time the selectivity for oxygenates and oxo-products, respectively, was tremendously increased. An exceptionally high selectivity for propanoic acid (47%) was observed on an alkaline earth oxide promoted Co2(CO)8/SiO2. The results for ruthenium containing catalysts indicated that the precursor and/or the combination of metals significantly influenced the interaction of the catalytic species with the support. The method of preparation also had a profound effect on the attachment of catalytic species to the support and their reducibility. In addition, the pretreatment exerted a significant influence on the catalyst, since the surface was restructured during the pretreatment resulting in changes in/losses of the active sites. As a result of the sensitivity to preparation, the performance of the catalysts differed significantly in CO hydrogenation, both in terms of activity and selectivity. Interestingly, the Co-Ru/SiO2 catalyst prepared by ionic adsorption exhibited unique selectivity in the Fischer-Tropsch synthesis, pronounced formation of methanol, compared with similar catalyst compositions prepared by impregnation or reflux methods. In all, the work clearly demonstrated the strong interrelation of catalyst preparation and performance. It also indicated that catalysts with very unusual performance could be prepared, particularly from Co2(CO)8 precursor. The commercial applicability of all the carbonyl based catalysts is, however, limited by their air sensitive nature and by the losses occurring during the catalyst pretreatment. Thus, the catalysts with a less sensitive preparation method but nevertheless unique characteristics, such as Co-Ru/SiO2 prepared by ionic adsorption, appear more interesting in the light of further development work.
Original languageEnglish
QualificationDoctor Degree
Awarding Institution
  • Aalto University
Supervisors/Advisors
  • Krause, Outi, Supervisor, External person
Award date6 Nov 1998
Place of PublicationEspoo
Publisher
Print ISBNs951-38-5259-8
Electronic ISBNs951-38-5340-3
Publication statusPublished - 1998
MoE publication typeG5 Doctoral dissertation (article)

Fingerprint

Hydroformylation
Ruthenium
Cobalt
Hydrogenation
Catalysts
Catalyst selectivity
Earth (planet)
Adsorption
Fischer-Tropsch synthesis
Alkalies
Hydrocarbons
Chemical analysis

Keywords

  • carbon monoxide hydrogenation
  • hydroformylation
  • cobalt
  • ruthenium

Cite this

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title = "Cobalt and ruthenium-cobalt catalysts in CO hydrogenation and hydroformylation: Dissertation",
abstract = "Cobalt and ruthenium-cobalt catalysts prepared from various precursors were studied in the activation of CO using CO hydrogenation and vapour phase hydroformylation as test reactions. The characteristics and activity were related to the precursor, composition, promoters and the method of preparation. Catalysts prepared from carbonyls exhibited the highest activity in CO hydrogenation. In addition to hydrocarbons, Co2(CO)8/SiO2 had a high (20{\%}) selectivity for oxygenates such as alcohols and esters. Likewise, the Co2(CO)8/SiO2 catalyst was active in the hydroformylation of ethene, whereas the conventional cobalt catalysts prepared from inorganic salts were virtually inactive in this reaction. Promotion by alkali or alkaline earth cations affected the performance of the Co2(CO)8/SiO2 catalyst significantly: the activity decreased in both CO hydrogenation and ethene hydroformylation, but at the same time the selectivity for oxygenates and oxo-products, respectively, was tremendously increased. An exceptionally high selectivity for propanoic acid (47{\%}) was observed on an alkaline earth oxide promoted Co2(CO)8/SiO2. The results for ruthenium containing catalysts indicated that the precursor and/or the combination of metals significantly influenced the interaction of the catalytic species with the support. The method of preparation also had a profound effect on the attachment of catalytic species to the support and their reducibility. In addition, the pretreatment exerted a significant influence on the catalyst, since the surface was restructured during the pretreatment resulting in changes in/losses of the active sites. As a result of the sensitivity to preparation, the performance of the catalysts differed significantly in CO hydrogenation, both in terms of activity and selectivity. Interestingly, the Co-Ru/SiO2 catalyst prepared by ionic adsorption exhibited unique selectivity in the Fischer-Tropsch synthesis, pronounced formation of methanol, compared with similar catalyst compositions prepared by impregnation or reflux methods. In all, the work clearly demonstrated the strong interrelation of catalyst preparation and performance. It also indicated that catalysts with very unusual performance could be prepared, particularly from Co2(CO)8 precursor. The commercial applicability of all the carbonyl based catalysts is, however, limited by their air sensitive nature and by the losses occurring during the catalyst pretreatment. Thus, the catalysts with a less sensitive preparation method but nevertheless unique characteristics, such as Co-Ru/SiO2 prepared by ionic adsorption, appear more interesting in the light of further development work.",
keywords = "carbon monoxide hydrogenation, hydroformylation, cobalt, ruthenium",
author = "Matti Reinikainen",
year = "1998",
language = "English",
isbn = "951-38-5259-8",
series = "VTT Publications",
publisher = "VTT Technical Research Centre of Finland",
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address = "Finland",
school = "Aalto University",

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Cobalt and ruthenium-cobalt catalysts in CO hydrogenation and hydroformylation : Dissertation. / Reinikainen, Matti.

Espoo : VTT Technical Research Centre of Finland, 1998. 64 p.

Research output: ThesisDissertationCollection of Articles

TY - THES

T1 - Cobalt and ruthenium-cobalt catalysts in CO hydrogenation and hydroformylation

T2 - Dissertation

AU - Reinikainen, Matti

PY - 1998

Y1 - 1998

N2 - Cobalt and ruthenium-cobalt catalysts prepared from various precursors were studied in the activation of CO using CO hydrogenation and vapour phase hydroformylation as test reactions. The characteristics and activity were related to the precursor, composition, promoters and the method of preparation. Catalysts prepared from carbonyls exhibited the highest activity in CO hydrogenation. In addition to hydrocarbons, Co2(CO)8/SiO2 had a high (20%) selectivity for oxygenates such as alcohols and esters. Likewise, the Co2(CO)8/SiO2 catalyst was active in the hydroformylation of ethene, whereas the conventional cobalt catalysts prepared from inorganic salts were virtually inactive in this reaction. Promotion by alkali or alkaline earth cations affected the performance of the Co2(CO)8/SiO2 catalyst significantly: the activity decreased in both CO hydrogenation and ethene hydroformylation, but at the same time the selectivity for oxygenates and oxo-products, respectively, was tremendously increased. An exceptionally high selectivity for propanoic acid (47%) was observed on an alkaline earth oxide promoted Co2(CO)8/SiO2. The results for ruthenium containing catalysts indicated that the precursor and/or the combination of metals significantly influenced the interaction of the catalytic species with the support. The method of preparation also had a profound effect on the attachment of catalytic species to the support and their reducibility. In addition, the pretreatment exerted a significant influence on the catalyst, since the surface was restructured during the pretreatment resulting in changes in/losses of the active sites. As a result of the sensitivity to preparation, the performance of the catalysts differed significantly in CO hydrogenation, both in terms of activity and selectivity. Interestingly, the Co-Ru/SiO2 catalyst prepared by ionic adsorption exhibited unique selectivity in the Fischer-Tropsch synthesis, pronounced formation of methanol, compared with similar catalyst compositions prepared by impregnation or reflux methods. In all, the work clearly demonstrated the strong interrelation of catalyst preparation and performance. It also indicated that catalysts with very unusual performance could be prepared, particularly from Co2(CO)8 precursor. The commercial applicability of all the carbonyl based catalysts is, however, limited by their air sensitive nature and by the losses occurring during the catalyst pretreatment. Thus, the catalysts with a less sensitive preparation method but nevertheless unique characteristics, such as Co-Ru/SiO2 prepared by ionic adsorption, appear more interesting in the light of further development work.

AB - Cobalt and ruthenium-cobalt catalysts prepared from various precursors were studied in the activation of CO using CO hydrogenation and vapour phase hydroformylation as test reactions. The characteristics and activity were related to the precursor, composition, promoters and the method of preparation. Catalysts prepared from carbonyls exhibited the highest activity in CO hydrogenation. In addition to hydrocarbons, Co2(CO)8/SiO2 had a high (20%) selectivity for oxygenates such as alcohols and esters. Likewise, the Co2(CO)8/SiO2 catalyst was active in the hydroformylation of ethene, whereas the conventional cobalt catalysts prepared from inorganic salts were virtually inactive in this reaction. Promotion by alkali or alkaline earth cations affected the performance of the Co2(CO)8/SiO2 catalyst significantly: the activity decreased in both CO hydrogenation and ethene hydroformylation, but at the same time the selectivity for oxygenates and oxo-products, respectively, was tremendously increased. An exceptionally high selectivity for propanoic acid (47%) was observed on an alkaline earth oxide promoted Co2(CO)8/SiO2. The results for ruthenium containing catalysts indicated that the precursor and/or the combination of metals significantly influenced the interaction of the catalytic species with the support. The method of preparation also had a profound effect on the attachment of catalytic species to the support and their reducibility. In addition, the pretreatment exerted a significant influence on the catalyst, since the surface was restructured during the pretreatment resulting in changes in/losses of the active sites. As a result of the sensitivity to preparation, the performance of the catalysts differed significantly in CO hydrogenation, both in terms of activity and selectivity. Interestingly, the Co-Ru/SiO2 catalyst prepared by ionic adsorption exhibited unique selectivity in the Fischer-Tropsch synthesis, pronounced formation of methanol, compared with similar catalyst compositions prepared by impregnation or reflux methods. In all, the work clearly demonstrated the strong interrelation of catalyst preparation and performance. It also indicated that catalysts with very unusual performance could be prepared, particularly from Co2(CO)8 precursor. The commercial applicability of all the carbonyl based catalysts is, however, limited by their air sensitive nature and by the losses occurring during the catalyst pretreatment. Thus, the catalysts with a less sensitive preparation method but nevertheless unique characteristics, such as Co-Ru/SiO2 prepared by ionic adsorption, appear more interesting in the light of further development work.

KW - carbon monoxide hydrogenation

KW - hydroformylation

KW - cobalt

KW - ruthenium

M3 - Dissertation

SN - 951-38-5259-8

T3 - VTT Publications

PB - VTT Technical Research Centre of Finland

CY - Espoo

ER -