Selective catalytic dehydration. Thoria-catalyzed dehydration of alcohols

Lundeen, Allan J.; VanHoozer, Robert

doi:10.1021/jo01286a024

Cited by 82 publications

(16 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Unclassified

Order By: Relevance

“…The same product selectivities have been reported over solid acid catalysts, such as Al 2 O 3 , SiO 2 , and ZnS, where 2-olefins were the major products rich in the cis-isomers when 2-hydroxyalkanes were dehydrated [75]. In contrast, solid base catalysts, such as ThO 2 , La 2 O 3 , and CeO 2 , mainly afford 1-olefins and 2-olefins are the by-products rich in the trans-isomer [76]. Consequently, the halide clusters showed the same product selectivity as the solid acid catalysts rather than the solid base catalysts.…”

Section: Reaction Of Alcohol (Equationsupporting

confidence: 64%

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Nagashima

Kamiguchi

Chihara

2014

Metals

View full text Add to dashboard Cite

Halide clusters of Group 5-7 metals develop catalytic activity above 150-250 °C, and the activity is retained up to 350-450 °C by taking advantage of their thermal stability, low vapor pressure, and high melting point. Two types of active site function: the solid Brønsted acid site and a coordinatively unsaturated site that catalyzes like the platinum metals do. Various types of catalytic reactions including new reactions and concerted catalyses have been observed over the clusters: hydrogenation, dehydrogenation, hydrogenolysis, isomerization of alkene and alkyne, and alkylation of toluene, amine, phenol, and thiol. Ring-closure reactions to afford quinoline, benzofuran, indene, and heterocyclic common rings are also catalyzed. Beckmann rearrangement, S-acylation of thiol, and dehydrohalogenation are also catalyzed. Although the majority of the reactions proceed over conventional catalysts, closer inspection shows some conspicuous features, particularly in terms of selectivity. Halide cluster catalysts are characterized by some aspects: cluster counter anion is too large to abstract counter cation from the protonated reactants, cluster catalyst is not poisoned by halogen and sulfur atoms. Among others, cluster catalysts are stable at high temperatures up to 350-450 °C. At high temperatures, apparent activation energy decreases, and hence weak acid can be a catalyst without decomposing reactants. OPEN ACCESSMetals 2014, 4 236

show abstract

Section: Reaction Of Alcohol (Equationsupporting

confidence: 64%

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Nagashima

Kamiguchi

Chihara

2014

Metals

View full text Add to dashboard Cite

show abstract

“…Vapor phase dehydration of diols is catalyzed by various metal oxides that include rare earth oxides . Dehydration of diol is an important reaction that generate unsaturated alcohols, a raw material used in the polymer and fine chemicals industry .…”

Section: Introductionmentioning

confidence: 93%

“…Vapor phase dehydration of diols is catalyzed by various metal oxides that include rare earth oxides. [1][2][3][4] Dehydration of diol is an important reaction that generate unsaturated alcohols, a raw material used in the polymer and fine chemicals industry. [5][6][7][8] In the past, however, selective conversion of the diols into unsaturated alcohol was achieved with 1,3-and 1,4diols.…”

Section: Introductionmentioning

confidence: 99%

Dehydration of 1,5‐Pentanediol over CeO₂‐MeOx Catalysts

et al. 2018

View full text Add to dashboard Cite

The dehydration reaction of 1,5‐pentanediol was performed over CeO2 and modified CeO2 (CeO2−MnOx, CeO2−ZnO, CeO2−MgO, CeO2−CaO, CeO2−Na2O) catalysts in a fixed‐bed tubular reactor at 350 °C and an atmospheric pressure. The undoped CeO2 produced a mixture of the products containing mainly 4‐penten‐1‐ol, 1‐pentanol, cyclopentanol, cyclopentanone and tetrahydropyran‐2‐one from 1,5‐pentanediol, while additions of MgO, MnOx, or ZnO to CeO2 was found to enhance the overall production rate of unsaturated alcohol. On the other hand, more basic metals like CaO or Na2O tend to decline the dehydration activity of CeO2. The porous structure of CeO2 did not change appreciably with the addition of metal oxides. Temperature programmed desorption of adsorbed CO2 on an activated catalyst suggest more CO2 remain on the catalyst surface, particularly CeO2−CaO and CeO2−Na2O indicating that fewer defect sites are only available for reaction. The defect sites or oxygen vacancy on CeO2 controls both activity and selectivity for the dehydration of 1,5‐pentanediol.

show abstract

“…CeO 2 shows specific catalytic activity in some reactions, such as the dehydration of secondary alcohols [21,22], the ortho-selective alkylation of phenol with alcohols [23][24][25], and the ketonization of alcohol [25,26], aldehyde, ester [27], and carboxylic acid [28]. We have already reported that 3-buten-2-ol and 2-buten-1-ol are formed from 1,3-butanediol over pure CeO 2 [1][2][3][4]7].…”

Section: Catalytic Properties Of Ceomentioning

confidence: 99%

Vapor-Phase Dehydration of 1,3-butanediol over CeO2–ZrO2 Catalysts

2009

View full text Add to dashboard Cite

The dehydration of 1,3-butanediol was investigated over CeO 2 -ZrO 2 catalysts prepared by impregnation at temperatures of 325-375°C. Pure CeO 2 selectively catalyzed the dehydration of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol, while pure ZrO 2 , which was less active than pure CeO 2 , catalyzed the dehydration to 3-buten-1-ol. In the CeO 2 /ZrO 2 catalyst in which CeO 2 was supported on zirconia, the presence of a small amount of CeO 2 suppressed the formation of 3-buten-1-ol and induced the dehydration of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol and the subsequent dehydrogenation of 3-buten-2-ol to form 3-buten-2-one and butanone. The activity would be related to the redox features of CeO 2 . The monoclinic phase of zirconia support decreased while the cubic CeO 2 phase increased as CeO 2 content was increased. In contrast, in the ZrO 2 /CeO 2 catalyst in which ZrO 2 was supported on cubic CeO 2 , only the cubic CeO 2 phase was observed and ZrO 2 species appeared in the form of a solid solution of CeO 2 -ZrO 2 with fluorite structure. Regardless of zirconia loading, ZrO 2 species did not affect the catalytic activity of ZrO 2 /CeO 2 , which was controlled by CeO 2 species.

show abstract

Selective catalytic dehydration. Thoria-catalyzed dehydration of alcohols

Cited by 82 publications

References 0 publications

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Dehydration of 1,5‐Pentanediol over CeO₂‐MeOx Catalysts

Vapor-Phase Dehydration of 1,3-butanediol over CeO2–ZrO2 Catalysts

Contact Info

Product

Resources

About

Selective catalytic dehydration. Thoria-catalyzed dehydration of alcohols

Cited by 82 publications

References 0 publications

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Catalytic Reactions over Halide Cluster Complexes of Group 5–7 Metals

Dehydration of 1,5‐Pentanediol over CeO2‐MeOx Catalysts

Vapor-Phase Dehydration of 1,3-butanediol over CeO2–ZrO2 Catalysts

Contact Info

Product

Resources

About

Dehydration of 1,5‐Pentanediol over CeO₂‐MeOx Catalysts