Zeolite-based bifunctional catalysts for the single step synthesis of dimethyl ether from CO-rich synthesis gas

Ahmad, R.; Schrempp, David Fridolin; Behrens, Silke; Sauer, Jörg; Döring, Manfred; Arnold, Ulrich

doi:10.1016/j.fuproc.2014.01.006

Cited by 43 publications

(36 citation statements)

References 36 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For instance, methods comprising impregnation, co-precipitation, or sol-gel steps (or their combinations) [7,14,15] and even more sophisticated approaches leading to core-shell catalyst structures [16,17,18] have been reported. The most widely applied procedure, however, involves the simple physical mixing of the Cu-based methanol synthesis and acid methanol dehydration components [8,19,20,21,22].…”

Section: Introductionmentioning

confidence: 99%

The influence of zeolite surface-aluminum species on the deactivation of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis

García‐Trenco

Martı́nez

2014

Catalysis Today

View full text Add to dashboard Cite

ElsevierGarcía Martinez Feliu, A. (2014). The influence of zeolite surface-aluminum species on the deactivationof CuZnAl/zeolite hybrid catalysts for the direct DME synthesis. Catalysis Today. 227:144-153. doi:10.1016Today. 227:144-153. doi:10. /j.cattod.2013 AbstractIn this work, an original approach for preparing Cu-ZnO+H-ZSM-5 (Si/Al=15, denoted as Z5) hybrid catalysts displaying enhanced stability during the direct DME synthesis from syngas is presented. The adopted preparation strategy was based on the effective confinement of the copper catalyst within the pores of an SBA-15 silica carrier (d pore = 7.0 nm) prior to mixing with the acid zeolite. In order to maximize the Cu-ZnO interface area (where active Cu 0 sites are likely located) the walls of the SBA-15 silica were coated with a near-monolayer of ZnO (17 wt% Zn) prior the incorporation of copper (in concentrations of 10, 15, and 20 wt%) by the so-called ammonia-driving deposition-precipitation (ADP) method. Copper nanoparticles sizing 5-6 nm after H 2 -reduction (HRTEM) were effectively confined inside the SBA-15 mesopores (as supported by HAADF-STEM) for Cu loadings of up to 15 wt%. Higher Cu loadings (20 wt%) lead to large, XRD-visible, CuO nanoparticles residing out of the SBA-15 pores. The confined catalyst loaded with 15 wt% Cu (15Cu/Zn@S15) displayed the highest Cu 0 surface area (determined by N 2 O-RFC) and methanol synthesis activity. Then, hybrid catalysts based on this methanol synthesis function (15Cu/Zn@S15+Z5) were prepared in a 15Cu/Zn@S15:Z5 mass ratio of 2:1 by two methods: a) grinding the mixture of powders prior to pelletizing (method G), and b) mixing the pre-pelletized components (method M). Equivalent hybrids comprising a conventional coprecipitated Cu-ZnO-Al 2 O 3 (CZA) catalyst were also prepared for comparative purposes (CZA+Z5). The catalysts were evaluated for direct DME synthesis (533 K, 4.0 MPa) in runs lasting ca. 24 h. It was found that the confined 15Cu/Zn@S15+Z5 hybrids deactivated at a much lower rate than those based on CZA regardless the method of preparation. In turn, while conventional CZA+Z5 catalysts prepared by grinding (G) experienced a higher deactivation than that obtained by mixing (M) due to the contribution of detrimental interactions between the copper and zeolite components in the former, no differences in the deactivation rate were observed for the 15Cu/Zn@S15+Z5 hybrids prepared by grinding and mixing. The improved stability of these hybrid catalysts is accounted for by the inhibition of both detrimental interactions (by avoiding the direct contact of copper active sites and the zeolite surface) and extensive metal sintering (by limiting the extent of Cu 0 crystal growth) induced by the effective confinement of the Cu-based catalyst within the SBA-15 pores.

show abstract

Section: Introductionmentioning

confidence: 99%

The influence of zeolite surface-aluminum species on the deactivation of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis

García‐Trenco

Martı́nez

2014

Catalysis Today

View full text Add to dashboard Cite

show abstract

“…The gasification and synthesis unit can be designed on the required industrial scale at the same site to achieve commercial operation. The concept allows for different products, ranging from drop-in fuels to specialized fuel additives and bulk chemicals [2][3][4][5] . This paper presents the first step in which fast pyrolysis is used to convert residual biomass to the intermediate bioslurry.…”

Section: Introductionmentioning

confidence: 99%

Fast Pyrolysis of Biomass Residues in a Twin-screw Mixing Reactor

Funke

Richter

Niebel

et al. 2016

JoVE

Self Cite

View full text Add to dashboard Cite

Fast pyrolysis is being increasingly applied in commercial plants worldwide. They run exclusively on woody biomass, which has favorable properties for conversion with fast pyrolysis. In order to increase the synergies of food production and the energetic and/or material use of biomass, it is desirable to utilize residues from agricultural production, e.g., straw. The presented method is suitable for converting such a material on an industrial scale. The main features are presented and an example of mass balances from the conversion of several biomass residues is given. After conversion, fractionated condensation is applied in order to retrieve two condensates -an organic-rich and an aqueousrich one. This design prevents the production of fast pyrolysis bio-oil that exhibits phase separation. A two phase bio-oil is to be expected because of the typically high ash content of straw biomass, which promotes the production of water of reaction during conversion.Both fractionated condensation and the use of biomass with high ash content demand a careful approach for establishing balances. Not all kind of balances are both meaningful and comparable to other results from the literature. Different balancing methods are presented, and the information that can be derived from them is discussed.

show abstract

“…Methanol can be used as a source for the production of several fuels and chemicals. Another promising strategy is the production of dimethyl ether (DME), either by dehydration of methanol or by direct synthesis from synthesis gas (synthesis gas-to-DME, STD), which is favorable in the case of CO-rich synthesis gases [17]. Furthermore, gasoline and diesel can be synthesized from methanol in so-called methanol-to-gasoline (MTG) [15] and methanol-to-synfuel (MTS) processes [16].…”

Section: Introductionmentioning

confidence: 99%

Conversion of Carbon Monoxide‐Rich Synthesis Gas to Hydrocarbons and Alcohols over Cu/Co/ZnO/SiO₂ Catalysts

Schröder

Arnold

Abeln

et al. 2015

Chemie Ingenieur Technik

Self Cite

View full text Add to dashboard Cite

Catalysts of the type Cu/Co/ZnO/SiO 2 were prepared by impregnation, subsequent calcination and reduction with hydrogen. Characterization of the catalysts was carried out by ICP-AES, BET measurements and powder X-ray diffraction analyses. Furthermore, temperature programmed reduction was employed to investigate their reduction behavior. The catalysts were tested in the conversion of synthesis gas to hydrocarbons and alcohols. High CO conversions could be reached in a single reactor pass. Selectivity was highest for methane, and short-chain hydrocarbons, but alcohols were also formed.

show abstract

Zeolite-based bifunctional catalysts for the single step synthesis of dimethyl ether from CO-rich synthesis gas

Cited by 43 publications

References 36 publications

The influence of zeolite surface-aluminum species on the deactivation of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis

The influence of zeolite surface-aluminum species on the deactivation of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis

Fast Pyrolysis of Biomass Residues in a Twin-screw Mixing Reactor

Conversion of Carbon Monoxide‐Rich Synthesis Gas to Hydrocarbons and Alcohols over Cu/Co/ZnO/SiO₂ Catalysts

Contact Info

Product

Resources

About

Zeolite-based bifunctional catalysts for the single step synthesis of dimethyl ether from CO-rich synthesis gas

Cited by 43 publications

References 36 publications

The influence of zeolite surface-aluminum species on the deactivation of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis

The influence of zeolite surface-aluminum species on the deactivation of CuZnAl/zeolite hybrid catalysts for the direct DME synthesis

Fast Pyrolysis of Biomass Residues in a Twin-screw Mixing Reactor

Conversion of Carbon Monoxide‐Rich Synthesis Gas to Hydrocarbons and Alcohols over Cu/Co/ZnO/SiO2 Catalysts

Contact Info

Product

Resources

About

Conversion of Carbon Monoxide‐Rich Synthesis Gas to Hydrocarbons and Alcohols over Cu/Co/ZnO/SiO₂ Catalysts