Dimethyl ether synthesis via methanol dehydration: Effect of zeolite structure

Catizzone, Enrico; Aloise, A.; Migliori, Massimo; Giordano, G.

doi:10.1016/j.apcata.2015.06.017

Cited by 92 publications

(83 citation statements)

References 36 publications

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“…This provides an additional possibility to optimize the performance of a sorption catalyst that is complementary to the optimization of the metal (Cu) particles: because pore sizes may influence the product distribution, the formation of methanol and/or DME might be facilitated in a more selective fashion. The Brønsted acid centers in the zeolite, which are responsible for the condensation reaction of DME, can be modified, thereby enhancing or suppressing the formation of DME. However, both methanol and DME have the advantages of being a renewable energy carrier in the future.…”

Section: Discussionmentioning

confidence: 99%

“…Reaction may be interpreted as a subsequent reaction to reaction on the acid sites of the zeolite, i.e., the condensation of methanol to dimethyl ether (C 2 H 6 O, DME) by the removal of water …”

Section: Introductionmentioning

confidence: 99%

“…Reaction (5) may be interpreted as a subsequent reaction to reaction (1) on the acid sites of the zeolite, i.e., the condensation of methanol to dimethyl ether (C 2 H 6 O, DME) by the removal of water. [9,10,[25][26][27][28][29][30] However, reaction (4) is not necessarily a side reaction, but there is disagreement in the catalysis community about whether it is indeed the first reaction step of the reduction of CO 2 to MeOH, because CO can also be reduced to MeOH according to the following reaction. [2,7,9,11,12]…”

Section: Introductionmentioning

confidence: 99%

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Sorption‐Enhanced Methanol Synthesis

et al. 2019

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A small heat of reaction limits the efficiency of the catalytic hydrogenation of CO2 to form methanol; an improved efficiency can be achieved by shifting the thermodynamic equilibrium toward the formation of methanol. The exothermic adsorption of the products in sorption catalysts is shown to increase the reaction yield. The sorption catalysts consist of catalytically active Cu particles incorporated into a zeolite, which is known to strongly absorb water. In addition to high reaction yield of methanol, the sorption catalyst reduces CO2 to CO and dimethyl ether. An enhancement factor of up to 400% for CO and 130% for methanol and dimethyl ether at a relatively low pressure of 15 bar is shown. Furthermore, the following relevant parameters for future technical realization are derived: a high catalytic activity and the reversible adsorption of the products at reaction conditions. A key experiment that combines a catalytic reaction and a pressure swing desorption is presented and demonstrates the feasibility of sorption‐enhanced catalysis for efficient energy use in large‐scale reactors.

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Section: Discussionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Sorption‐Enhanced Methanol Synthesis

et al. 2019

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“…However, this would, in turn, lower dehydration rates, which are acid site-dependent. 16,21,22 It has previously been reported that PdZn alloy nanoparticles are active catalysts for the hydrogenation of CO 2 to methanol. Deposition of PdZn onto TiO 2 using solvent-free chemical vapor impregnation (CVI) formed PdZn nanoparticles with a narrow size distribution, which was shown to be beneficial for methanol productivities.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Modification of the pore size, acidity and microporous and/or mesoporous structures of zeolite catalysts has been shown to significantly impact upon rates of methanol dehydration. 13 H-ZSM-5 and γ-Al 2 O 3 have been used extensively as catalysts for this reaction, with H-ZSM-5 favored due to its relative stability in the presence of water. 14 The hydrophobic/hydrophilic properties of H-ZSM-5 are dependent on the SiO 2 /Al 2 O 3 ratio and are therefore controllable, with hydrophobic, siliceous isomorphs shown to be less prone to water-mediated deactivation.…”

Section: ■ Introductionmentioning

confidence: 99%

Hydrogenation of CO₂ to Dimethyl Ether over Brønsted Acidic PdZn Catalysts

Bahruji

Armstrong

Esquius

et al. 2018

Ind. Eng. Chem. Res.

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Eschewing the common trend toward use of catalysts composed of Cu, it is reported that PdZn alloys are active for CO 2 hydrogenation to oxygenates. It is shown that enhanced CO 2 conversion is achievable through the introduction of Brønsted acid sites, which promote dehydration of methanol to dimethyl ether. We report that deposition of PdZn alloy nanoparticles onto the solid acid ZSM-5, via chemical vapor impregnation affords catalysts for the direct hydrogenation of CO 2 to DME. This catalyst shows dual functionality; catalyzing both CO 2 hydrogenation to methanol and its dehydration to dimethyl in a single catalyst bed, at temperatures of >270°C. A physically mixed bed comprising 5% Pd 15% Zn/TiO 2 and H-ZSM-5 shows a comparably high performance, affording a dimethyl ether synthesis rate of 546 mmol kg cat −1 h −1 at a reaction temperature of 270°C . ■ INTRODUCTIONMethanol is ubiquitous within the chemical industry, with global demand exceeding 57 Mt/annum. The majority of this is met through a two-step process whereby synthesis gas is produced via methane steam reforming and then reacted over a Cu/ZnO/Al 2 O 3 catalyst to prepare methanol. The energy consumption of this process is estimated to exceed 1 exajoule (1 × 10 18 J)/annum globally, with a significant carbon footprint (ca. 88 Mt GHG eq). 1 In line with political and social pressure to decrease society's dependence on fossil fuels, there is growing interest in producing methanol through more sustainable routes. One promising route is catalytic CO 2 hydrogenation. The process, however, is restricted by thermodynamic equilibrium; with the reverse water gas shift reaction (RWGS) dominating the reaction at high temperatures. Indeed, methanol is thermodynamically favored at lower temperatures. Unfortunately, because of the relatively low reactivity of CO 2 , high reaction temperatures and/or pressures are required for its activation. To maximize yields of valueadded products, it is important that CO 2 hydrogenation be carried out near equilibrium. One approach toward circumventing RWGS at elevated reaction temperatures is removal of the product, methanol, from the catalytic system. This can be achieved through dehydration to dimethyl ether (DME), typically over a solid acid catalyst. DME is a key feedstock for production of methylating agents for organic synthesis. 2 DME has also been identified as an environmentally friendly fuel, with low associated emissions of NO x , hydrocarbons, CO and SO x . 3 Through the methanol to gasoline (MTG) process, methanol is catalytically converted to yield an equilibrium mixture containing methanol, DME and water. This is then converted to hydrocarbons. 4 Being both exothermic and reversible, methanol dehydration is subject to thermodynamic limitation, though effectively not so under methanol synthesis conditions. 4 Integrating methanol dehydration into CO 2 hydrogenation reaction systems might increase hydrogenation yields, by intercepting the methanol through dehydration to DME, therefore shifting the reactio...

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Recent Advances in Conversion of Carbon Dioxide into Value‐Added Product over the Solid Base Catalyst

Singh,

Pant

2024

Solid Base Catalysts

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Dimethyl ether synthesis via methanol dehydration: Effect of zeolite structure

Cited by 92 publications

References 36 publications

Sorption‐Enhanced Methanol Synthesis

Sorption‐Enhanced Methanol Synthesis

Hydrogenation of CO₂ to Dimethyl Ether over Brønsted Acidic PdZn Catalysts

Recent Advances in Conversion of Carbon Dioxide into Value‐Added Product over the Solid Base Catalyst

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Dimethyl ether synthesis via methanol dehydration: Effect of zeolite structure

Cited by 92 publications

References 36 publications

Sorption‐Enhanced Methanol Synthesis

Sorption‐Enhanced Methanol Synthesis

Hydrogenation of CO2 to Dimethyl Ether over Brønsted Acidic PdZn Catalysts

Recent Advances in Conversion of Carbon Dioxide into Value‐Added Product over the Solid Base Catalyst

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Product

Resources

About

Hydrogenation of CO₂ to Dimethyl Ether over Brønsted Acidic PdZn Catalysts