Conversion of 2,3-butanediol to butenes over bifunctional catalysts in a single reactor

Zheng, Qunhao; Wales, M.; Heidlage, Michael G.; Rezac, Mary E.; Wang, Hongwang; Bossmann, Stefan H.; Hohn, Keith L.

doi:10.1016/j.jcat.2015.07.004

Cited by 43 publications

(49 citation statements)

References 80 publications

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“…Alternatively, Zheng et al. recently reported a Cu/ZSM5 catalyst that could convert 2,3‐BDO into butene in the presence of an excess amount H 2 without further hydrogenation to butane …”

Section: N2 Physisorption Data Nh3‐tpd Data Acid Site Densities Ansupporting

confidence: 91%

“…This reaction mechanism is similar to that proposed by Zheng et al. for the conversion of 2,3‐butanediol into butene in the presence of an excess amount of H 2 , but the key difference here is that the vanadia catalyst is able to hydrogenate MEK intrinsically without requiring an external source of H 2 by transferring hydrogen from the 2,3‐BDO reactant to the MEK intermediate …”

Section: N2 Physisorption Data Nh3‐tpd Data Acid Site Densities Anmentioning

confidence: 99%

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Hydrogen‐Free Gas‐Phase Deoxydehydration of 2,3‐Butanediol to Butene on Silica‐Supported Vanadium Catalysts

et al. 2017

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The gas-phase deoxydehydration of 2,3-butanediol to butene was investigated in aplug flow reactor over SiO 2 -supported vanadium oxide, g-alumina, P/ZSM-5, andM gO catalysts with acid/bases ites of varying strengths. 5wt% vanadium on SiO 2 (i.e.,5V/SiO 2 )s howedt he best performance with 100 %conversion and up to 45.2 %b utene selectivity.T he combination of weak acid sites and polymericV O x surfaces peciesp rovided the 5V/SiO 2 catalystw ith bifunctional capabilities to achieve both dehydration and transfer hydrogenation, which allowed it to catalyze the deoxydehydration of 2,3-butanediol to butene even in the absence of H 2 .A s2 ,3-butanediol is ac ommon yet underutilized biomassp roduct, this reactionm ay provide av iable route for ab iomass-to-chemicals application for 2,3butanediol.Upgrading of biomass to fuels and chemicals is important for sustainable human development, and intense studiesa re being undertaken to find new technologiest oc onvert the large amount of availablebioderived oxygenates into fuels and chemicals. [1] The vicinal diol 2,3-butanediol (2,3-BDO) is ac ommon biomass product that is synthesized by using bacteria sugars derived from biomass feedstock such as corn starch. [1c] It has great potentialt or eplaces ynthetic 2,3-BDO in the market owing to its cost effectiveness relative to the chemical hydrolysis of 2,3-butene oxide. Whereas its other isomers such as 1,4-butanediola nd 1,3-butanediol have been widely studied for their conversion into other chemicals such as tetrahydrofuran and butyrolactone, [2] these cyclization reactions are not availablef or 2,3-BDO owing to the vicinal positiono fi ts OH groups.T hus, 2,3-BDO is much less studied than 1,4-and 1,3-butanediol, although it could follow multiple oxidation, reduction, and dehydration pathways. [1c,d] The dehydration of 2,3-BDO mainly produces butanone (also knowna sm ethyl ethyl ketone, MEK) and 2-methylpropanal (MPA) through aE 1/E2 mechanism followed by 1,2-rearrangement by hydride and methyl shifts, respectively. [2a] This is readily achieved on acid sites, such as those availablei np hosphate catalysts or zeolites. [3] However,t he doubled ehydration of 2,3-BDO to butadiene is more challenging than that of 1,4-butanediol because the carbonyl compounds MEK and MPAf ormed from 2,3-BDOa re more difficult to dehydrate further than enol compounds such as 3-buten-1-ol, whicha re typically formed from 1,4-butanediol. [4] Alternatively,Z heng et al. recently reported aC u/ZSM5 catalyst that could convert2 ,3-BDOi nto butene in the presence of an excess amount H 2 withoutf urther hydrogenation to butane. [5] In this study,t he gas-phase conversion of 2,3-BDO was performed over SiO 2 -supported vanadium oxide, g-alumina, P/ ZSM-5, and MgO catalysts with acid/base sites of varying strengths. We show that ad eoxydehydration pathway of 2,3-BDO to butene in the absence of H 2 exists that proceeds through ah ydrogen-donor mechanism from 2,3-BDO to MEK over vanadium oxide (VO x )s urfaces ites.The ammonia temperature-programmed d...

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“…Alternatively, Zheng et al. recently reported a Cu/ZSM5 catalyst that could convert 2,3‐BDO into butene in the presence of an excess amount H 2 without further hydrogenation to butane …”

Section: N2 Physisorption Data Nh3‐tpd Data Acid Site Densities Ansupporting

confidence: 91%

Section: N2 Physisorption Data Nh3‐tpd Data Acid Site Densities Anmentioning

confidence: 99%

Hydrogen‐Free Gas‐Phase Deoxydehydration of 2,3‐Butanediol to Butene on Silica‐Supported Vanadium Catalysts

et al. 2017

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“…Cu/ZSM‐5 catalysts have been found to be very active for the direct production of olefins from 2,3‐BDO since 71 % selectivity toward butenes at 100 % conversion was achieved . However, the zeolite catalysts suffer from rapid deactivation due to coking and regeneration has been found unsuccessful to regain the initial butenes selectivity due to the presence of hard coke . In addition, zeolites are likely to suffer from dealumination while operating with real BDO fermentation broth, product obtained from fermentation of sugars with microorganism species due to the high concentration of water in the broth.…”

Section: Introductionmentioning

confidence: 99%

Single‐step Conversion of Methyl Ethyl Ketone to Olefins over Zn_xZr_yO_z Catalysts in Water

Dagle

Kovařík

et al. 2019

ChemCatChem

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In this study we investigated the conversion of aqueous methyl‐ethyl‐ketone (MEK) to olefin fuel precursors over ZnxZryOz mixed oxide catalysts. Experiments were carried out in water as MEK is intended to be produced from the dehydration of 2,3‐butanediol in fermentation broth which is highly diluted in water. We demonstrated that ZnxZryOz catalysts are highly effective for converting aqueous MEK to C4−C5 olefins. High selectivity to olefins equal to 85 % was reached at 92 % per pass conversion when under H2 atmosphere. Catalyst stability was demonstrated for 60 hours’ time on stream, highlighting the potential for upgrading 2,3‐butanediol contained in fermentation broth without the need for energy‐intensive water separation. Increased concentration of MEK in the aqueous feed results in increased activity towards olefin production. However, water inhibits catalyst deactivation from coking. A mechanistic investigation revealed the impact of the reaction environment (inert or reducing atmosphere) on the reaction pathways. In an inert environment, the mechanism involves consecutive aldol condensation of MEK and 3‐pentanone intermediate. Under reducing conditions two reaction pathways compete with each other as MEK hydrogenation to butenes occurs concurrently with the aldol condensation/decomposition.

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“…However, the development of the biomass industry and the abundance of BDO as a by‐product have reignited interest in the catalytic conversion of BDO, in particular its dehydration to 1,3‐butadiene (BDE). At present, attempts to directly produce BDE with a high yield have failed and the reaction to methyl ethyl ketone, the thermodynamically preferred product, always predominates . The mechanism is well understood since the consecutive dehydration of the adjacent two hydroxyl groups leads to an enol which readily forms methyl ethyl ketone (MEK).…”

Section: Catalytic Performance Of Various Oxides Catalysts[a]mentioning

confidence: 82%

One‐Step Production of 1,3‐Butadiene from 2,3‐Butanediol Dehydration

Liu

Fabos

Taylor

et al. 2016

Chemistry A European J

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We report the direct production of 1,3-butadiene from the dehydration of 2,3-butandiol by using alumina as catalyst. Under optimized kinetic reaction conditions, the production of methyl ethyl ketone and isobutyraldehyde, formed via the pinacol-pinacolone rearrangement, was markedly reduced and almost 80 % selectivity to 1,3-butadiene and 1,3-butadiene could be achieved. The presence of water plays a critical role in the inhibition of oligomerization. The amphoteric nature of γ-Al2 O3 was identified as important and this contributed to the improved catalytic selectivity when compared with other acidic catalysts.

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Conversion of 2,3-butanediol to butenes over bifunctional catalysts in a single reactor

Cited by 43 publications

References 80 publications

Hydrogen‐Free Gas‐Phase Deoxydehydration of 2,3‐Butanediol to Butene on Silica‐Supported Vanadium Catalysts

Hydrogen‐Free Gas‐Phase Deoxydehydration of 2,3‐Butanediol to Butene on Silica‐Supported Vanadium Catalysts

Single‐step Conversion of Methyl Ethyl Ketone to Olefins over Zn_xZr_yO_z Catalysts in Water

One‐Step Production of 1,3‐Butadiene from 2,3‐Butanediol Dehydration

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Conversion of 2,3-butanediol to butenes over bifunctional catalysts in a single reactor

Cited by 43 publications

References 80 publications

Hydrogen‐Free Gas‐Phase Deoxydehydration of 2,3‐Butanediol to Butene on Silica‐Supported Vanadium Catalysts

Hydrogen‐Free Gas‐Phase Deoxydehydration of 2,3‐Butanediol to Butene on Silica‐Supported Vanadium Catalysts

Single‐step Conversion of Methyl Ethyl Ketone to Olefins over ZnxZryOz Catalysts in Water

One‐Step Production of 1,3‐Butadiene from 2,3‐Butanediol Dehydration

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Single‐step Conversion of Methyl Ethyl Ketone to Olefins over Zn_xZr_yO_z Catalysts in Water