Vapor-phase catalytic reactions of alcohols over bixbyite indium oxide

Segawa, Masaki; Sato, Satoshi; Kobune, Mika; Sodesawa, Toshiaki; Kojima, Takashi; Nishiyama, Shin; Ishizawa, Nobuo

doi:10.1016/j.molcata.2009.06.015

Cited by 31 publications

(27 citation statements)

References 34 publications

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“…Many researches dealing with the dehydration of BDO, PDO, and DEG to useful chemicals have been reported and it is found that acidic catalysts are generally effective for producing the cyclodehydration products. In particular, acidic solids such as TiO 2 -supported silicotungstic acid [2,3], diatomite-supported phosphotungstic acid [4], and ion exchange resin (Indion-130) [5] are efficient for THF formation from BDO in a liquid phase, while 3-buten-1-ol is mainly produced in a vapor phase over base-modified ZrO 2 [6,7], In 2 O 3 [8,9], and rare earth oxides with base property, such as CeO 2 and Er 2 O 3 [10,11]. Such solid catalysts as sulfated zirconia [1], H-ZSM-5 zeolite [12], tin(IV) phosphate [13], and alumina [14] have been reported to be effective for the liquid-phase formation of THP from PDO, while Na-modified monoclinic ZrO 2 [15] and rare earth oxides such as Yb 2 O 3 and Sc 2 O 3 [10,16] prefer the formation of 4-buten-1-ol in a vapor phase.…”

Section: Introductionmentioning

confidence: 99%

Cyclodehydration of diethylene glycol over Ag-modified Al2O3 catalyst

Sun

Wang

Yamada

et al. 2015

Applied Catalysis A: General

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Section: Introductionmentioning

confidence: 99%

Cyclodehydration of diethylene glycol over Ag-modified Al2O3 catalyst

Sun

Wang

Yamada

et al. 2015

Applied Catalysis A: General

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“…In 2 O 3 with the same bixbiyte structure 17 as Sc 2 O 3 also showed a high conversion of 2,3-BDO, whereas the highest selectivity was obtained when it was calcined at a low temperature of 400°C but not at 800°C. Figure 2 shows the effect of reaction temperature on the catalytic activity of Sc 2 O 3 and In 2 O 3 .…”

Section: ¹1mentioning

confidence: 94%

“…15,16 In this paper, we investigated the dehydration of 2,3-BDO over the REOs and bixbyite In 2 O 3 , which has catalytic activity in the dehydration of 1,4-butanediol to produce 3-buten-1-ol. 17,18 The catalytic reaction was performed in a fixed-bed downflow glass reactor at an atmospheric pressure. Prior to feeding the reactant, the catalyst bed has been preheated in an H 2 flow at 325°C for 1 h. The reactant was fed into the reactor at a rate of 1.06 g h…”

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confidence: 99%

Vapor-phase Catalytic Dehydration of 2,3-Butanediol into 3-Buten-2-ol over Sc2O3

Duan¹,

Yamada²,

Sato³

2014

Chemistry Letters

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Vapor-phase catalytic dehydration of 2,3-butanediol (2,3-BDO) was investigated over rare earth oxide (REO) catalysts as well as In 2 O 3 . In the dehydration of 2,3-BDO, 3-buten-2-ol (3B2OL) was produced together with 3-hydroxy-2-butanone (3H2BO), butanone (MEK), 2-methylpropanal (IBA), 2-methyl-1-propanol (IBO), etc. Sc 2 O 3 and In 2 O 3 showed higher 3B2OL selectivities than other REOs. In particular, Sc 2 O 3 converted 2,3-BDO into 3B2OL with an excellent selectivity of 85.0% at 99.9% conversion.With the development of biotechnology, 2,3-butanediol (2,3-BDO) can be produced from biomass via fermentation, and it is expected to be a chemical resource.14 The dehydration of 2,3-BDO to 1,3-butadiene (BD), butanone (MEK), and 3-buten-2-ol (3B2OL) (Scheme 1) has been investigated since the 1940s. 59 It seems that the dehydration of 2,3-BDO generally results in good yields of MEK over acidic catalysts. 69 In the pioneering work of Winfield, it was reported that ThO 2 catalyzed the dehydration of 2,3-BDO into 3B2OL with a yield of 70.3% at 350°C, and a BD yield of 62.1% was obtained with a 3B2OL yield of 8.4% at 500°C.5 It is also known that 3B2OL is used as an important intermediate in the synthesis of monomer esters and medicines.10,11 3B2OL production from bio-2,3-BDO is highly anticipated. Unfortunately, ThO 2 cannot be applied as an industrial catalyst due to its radioactivity.In order to find safe catalysts for the formation of 3B2OL from 2,3-BDO, we have investigated several possible metal oxide catalysts and found that highly crystallized monoclinic ZrO 2 exhibits high catalytic activity in the dehydration of 2,3-BDO to 3B2OL (Scheme 1).12 However, the catalytic activities of rare earth oxides (REOs), which have always performed well as catalysts for dehydration, have not been confirmed, except La 2 O 3 and Yb 2 O 3 .In our previous work, we have also reported several examples of the syntheses of unsaturated alcohols in the vapor-phase catalytic dehydration of alkanediols over REOs. 13 Catalytic activity of REOs depends on the position of OH groups of reactant diols: 1,3-diols are effectively dehydrated into 3B2OL and 2-buten-1-ol by CeO 2 ; 1,4-butanediol can be dehydrated to 3-buten-1-ol by Er 2 O 3 , Yb 2 O 3 , and Lu 2 O 3 ; 13 1,5-pentanediol to 4-penten-1-ol by Sc 0.5 Yb 1.5 O 3 .14 Lattice parameters of the cubic REOs seem to affect the adsorption and activation of alkanediols.14 Among all the REO catalysts, Sc 2 O 3 with the smallest cation radius always shows great selective catalytic activity in the dehydration of terminal diols with long carbon chain such as 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, and 1,12-dodecanediol to the corresponding unsaturated alcohols. 15,16 In this paper, we investigated the dehydration of 2,3-BDO over the REOs and bixbyite In 2 O 3 , which has catalytic activity in the dehydration of 1,4-butanediol to produce 3-buten-1-ol. 17,18The catalytic reaction was performed in a fixed-bed downflow glass reactor at an atmospheric pressure...

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“…In a similar way to the cubic CeO 2 (111) facet, oxygen defect sites are generated intrinsically on the (222) facet of the cubic bixbyite rare earth metal oxides (Ln 2 116 In 2 O 3 , which has the same crystal structure of Ln 2 O 3 with cubic bixbyite, resembled CeO 2 for its redox property to capture the 2-position hydrogen atom. 120 However, the cation Ln 3+ of Ln 2 O 3 shows no redox activity, which is different from CeO 2 . Thus, the mechanism of the UOLs formation from 1,3-BDO over those Ln 2 O 3 catalysts is different from that of CeO 2 and In 2 O 3 .…”

Section: ¹1mentioning

confidence: 98%

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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Vapor-phase catalytic reactions of alcohols over bixbyite indium oxide

Cited by 31 publications

References 34 publications

Cyclodehydration of diethylene glycol over Ag-modified Al2O3 catalyst

Cyclodehydration of diethylene glycol over Ag-modified Al2O3 catalyst

Vapor-phase Catalytic Dehydration of 2,3-Butanediol into 3-Buten-2-ol over Sc2O3

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

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