Improved processing stability in the hydrogenation of dimethyl maleate to γ-butyrolactone, 1,4-butanediol and tetrahydrofuran

Ohlinger, Christoph; Kraushaar‐Czarnetzki, Bettina

doi:10.1016/s0009-2509(02)00672-3

Cited by 39 publications

(41 citation statements)

References 8 publications

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“…Condensation can be prevented by applying high molar feed ratios of hydrogen to dimethyl maleate, i.e., by dilution of the organic reactants. We calculated the minimum H 2 /maleate feed ratios required for safe and stable processing in a wide range of reaction pressures and temperatures and validated these calculated limits by processing experiments [9]. Hence, the single-stage gas-phase hydrogenation of dimethyl maleate in a fixed-bed reactor is a feasible option.…”

Section: Introductionmentioning

confidence: 88%

“…In addition to the hydrogenating function, the catalysts comprise weakly acid sites which catalyze selectively the dehydration of BDO to THF. Because BDO is consumed, together with dimethyl succinate being the most critical compound with respect to capillary condensation, and because THF exhibits considerably lower Antoine constants than the other C 4 -reactants [9], it will be possible to apply much lower H 2 /maleate feed ratios without running into the regime of fouling by polymer formation. The other interesting aspect of this catalyst represents the possibility of producing THF from dimethyl maleate in a single rather than two stages, thereby using the most convenient, i.e., fixedbed, reactor technology.…”

Section: Introductionmentioning

confidence: 99%

“…At conversions of dimethyl succinate above ca. 80%, the temperature-and pressuredependent thermodynamic equilibrium in the hydrogenation of γ -butyrolactone (GBL) to BDO is attained over Cu/ZnO catalysts [8,9]. The subsequent dehydration of BDO to THF plays a minor role because Cu/ZnO does not exhibit sufficient acidity.…”

Section: Introductionmentioning

confidence: 99%

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Extrusion of Cu/ZnO catalysts for the single-stage gas-phase processing of dimethyl maleate to tetrahydrofuran

Müller

Kucher

Ohlinger

et al. 2003

Journal of Catalysis

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Bifunctional catalysts consisting of copper, zinc oxide, and γ -alumina have been produced by means of extrusion. The effects of formulation and forming conditions on morphology, pore texture, and copper surface area are discussed. These extruded catalysts have been employed in the fixed-bed gas-phase conversion of dimethyl maleate at temperatures between 453 and 493 K and space velocities ranging from 0.2 to 2.4 h −1 . Copper catalyzes the hydrogenation and hydrogenolysis reactions yielding γ -butyrolactone, and 1,4-butanediol. γ -Alumina provides weakly acidic sites which promote the subsequent dehydration of 1,4-butanediol to tetrahydrofuran. Coupled products are methanol and water. Through choice of composition and pore texture of the extrudates it is possible to achieve tetrahydrofuran yields of 100% (basis the C 4 -products) at a low pressure (2.5 MPa) in a single stage.

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Section: Introductionmentioning

confidence: 88%

Section: Introductionmentioning

confidence: 99%

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Extrusion of Cu/ZnO catalysts for the single-stage gas-phase processing of dimethyl maleate to tetrahydrofuran

Müller

Kucher

Ohlinger

et al. 2003

Journal of Catalysis

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“…The coupling process is an effective route to overcome the problems mentioned in the hydrogenation reactions and dehydrogenation reactions. We proposed a coupling process of MA hydrogenation and 1,4-butanediol dehydrogenation for simultaneous synthesis of c-BL to overcome the problems of single MA hydrogenation process [2,12], whereas MA, succinic anhydride, succinic acid, as well as their diethyl or dimethyl maleates, could react with 1,4-butandiol to form the polymers fouling and plugging of the unit [34][35][36]. So, it is necessary to find a suitable reactant, which can not react with MA to form the polymers.…”

Section: ∆H =mentioning

confidence: 99%

A New Process for Synthesis of γ‐Butyrolactone and Cyclohexanone

Zheng¹,

Zhu²,

Huang³

et al. 2007

Chem Eng & Technol

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A new process through the coupling of maleic anhydride hydrogenation and cyclohexanol dehydrogenation has been studied for the simultaneous synthesis of c-butyrolactone and cyclohexanone. The possibility of the coupling process has been investigated thermodynamically. The separated hydrogenation of maleic anhydride, the dehydrogenation of cyclohexanol, and the coupling process over the same Cu-Zn-Al catalyst have been carried out in a fixed-bed reactor. Compared to conventional processes, the coupling process has several advantages, e.g., improved c-butyrolactone and cyclohexanone yields, good energy efficiency, and optimal hydrogen utilization. The effects of reaction temperature, n(H 2 )/n (reactants) and liquid hourly space velocity on the coupling process are investigated. One thousand hours of stability testing shows that the Cu-based catalyst has relatively high activity and good stability in the coupling process.

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“…The major portion of GBL is currently being produced via the dehydrogenation of 1,4-butanediol (1,4-BD) [4][5][6], which is manufactured from the reaction of acetylene with formaldehyde; this reaction is known as the Reppe process [7]. New manufacturing routes of GBL are based on the two-stage hydrogenation of economically attractive raw materials such as dimethyl maleate [8] or maleic anhydride [9][10][11]. Tetrahydrofurane can also be used as a precursor to synthesize GBL following a single oxidation step [12].…”

Section: Introductionmentioning

confidence: 99%