Catalytic reaction of 1,3-butanediol over rare earth oxides

Sato, Satoshi; Takahashi, Ryōji; Sodesawa, Toshiaki; Igarashi, Ai; Inoue, Hirotomo

doi:10.1016/j.apcata.2007.05.033

Cited by 61 publications

(23 citation statements)

References 31 publications

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“…The catalytic results of CeO 2 are essentially the same as those reported in our previous work [3,4]. The dependence of the catalytic activity on SA has been discussed in connection with the crystal facets of CeO 2 [3,4,12]. Figure 2 shows the dependence of conversion and selectivity on reaction temperature over pure m-ZrO 2 and CeO 2 .…”

Section: Characterizationsupporting

confidence: 68%

“…Pure CeO 2 catalyzes mainly the dehydration of 1,3-butanediol to form 3-buten-2-ol and 2-buten-1-ol, while the major product is 3-buten-1-ol over m-ZrO 2 and t-ZrO 2 . Since acidic and basic sites of CeO 2 are weaker than those of m-ZrO 2 [8,12], the active sites of CeO 2 in the dehydration of 1,3-butanediol are not acid-base sites. The catalytic activity of CeO 2 would originate from the redox property between Ce 4?…”

Section: Catalytic Properties Of Ceomentioning

confidence: 97%

“…On the other hand, 1,4-butanediol is readily dehydrocyclized into THF over ZrO 2 with tetragonal crystal phase [11] as well as acidic SiO 2 -Al 2 O 3 and Al 2 O 3 [9]. Although we have recently found that rare earth oxides, such as Sc 2 O 3 and Tm 2 O 3 , catalyze the dehydration of 1,3-butanediol into unsaturated alcohols [12], the selectivities to the unsaturated alcohols are inferior to those of CeO 2 . No such selective catalysts as CeO 2 have been found so far.…”

Section: Introductionmentioning

confidence: 99%

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

2009

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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.

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Section: Characterizationsupporting

confidence: 68%

Section: Catalytic Properties Of Ceomentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

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

2009

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“…[50][51][52][53][54][55][56] 1,3-Diols are more reactive than other diols and monoalcohols over CeO 2 . 2-Propen-1-ol was produced from 1,3-propanediol over pure CeO 2 with a maximum selectivity of 98.9 % at 325 8C.…”

Section: Dehydration Of Diolsmentioning

confidence: 96%

Ceria‐Based Solid Catalysts for Organic Chemistry

Vivier¹,

Duprez²

2010

ChemSusChem

363

244

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Ceria has been the subject of thorough investigations, mainly because of its use as an active component of catalytic converters for the treatment of exhaust gases. However, ceria‐based catalysts have also been developed for different applications in organic chemistry. The redox and acid–base properties of ceria, either alone or in the presence of transition metals, are important parameters that allow to activate complex organic molecules and to selectively orient their transformation. Pure ceria is used in several organic reactions, such as the dehydration of alcohols, the alkylation of aromatic compounds, ketone formation, and aldolization, and in redox reactions. Ceria‐supported metal catalysts allow the hydrogenation of many unsaturated compounds. They can also be used for coupling or ring‐opening reactions. Cerium atoms can be added as dopants to catalytic system or impregnated onto zeolites and mesoporous catalyst materials to improve their performances. This Review demonstrates that the exceptional surface (and sometimes bulk) properties of ceria make cerium‐based catalysts very effective for a broad range of organic reactions.

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“…111113 The important issue is that BD is scarcely formed over the catalysts at 325°C. 111,114 Dehydration of 1,3-BDO into UOLs such as 3B1OL, 2B1OL, and 3B2OL have been investigated over ZrO 2 , 81 solid acid metal oxides, 81 CeO 2 -ZrO 2 , 115 and all of the rare earth metal oxide catalysts. 116,117 In the rare earth oxides, CeO 2 is the most active and selective catalyst.…”

Section: Dehydration Of 13-bdo Into Uolsmentioning

confidence: 99%

Future Prospect of the Production of 1,3-Butadiene from Butanediols

Duan¹,

Yamada²,

Sato³

2016

Chem. Lett.

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Global supply of 1,3-butadiene (abbreviated as BD) is faced with problems such as unstable price of petrochemicals and variation of chemical feedstock in recent years. Many research works have been conducted to produce BD from some renewable resources instead of petroleum. Among them, biomass-derived C 4 alcohols such as 1,3-butanediol (1,3-BDO), 2,3-butanediol (2,3-BDO), and 1,4-butanediol (1,4-BDO) have been considered as alternative resources to produce BD. Direct dehydration of butanediols (BDOs) into BD, however, needs high reaction temperatures while the dehydration into their corresponding unsaturated alcohols (UOLs) such as 3-buten-2-ol (3B2OL), 2-buten-1-ol (2B1OL), and 3-buten-1-ol (3B1OL) proceeds at rather low temperatures over specific catalysts. The latter step of BDO dehydration, dehydration of UOLs to BD, is readily catalyzed by solid acids even at lower temperatures than those at which BDOs are dehydrated completely. Thus, efficient formation of UOLs from BDOs would be a key process to produce BD with high selectivity. We summarize the BD production from C 4 alcohols as well as the dehydration of BDOs to UOLs, in addition to the BD production via ethanol dimerization.

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Catalytic reaction of 1,3-butanediol over rare earth oxides

Cited by 61 publications

References 31 publications

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

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

Ceria‐Based Solid Catalysts for Organic Chemistry

Future Prospect of the Production of 1,3-Butadiene from Butanediols

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