Mesoporous H‐ZSM‐5 for the Conversion of Dimethyl Ether to Hydrocarbons

Zimmermann, Michael; Otto, T.N.; Wodarz, S.; Zevaco, Thomas A.; Pitter, Stephan

doi:10.1002/cite.201800217

Cited by 10 publications

(6 citation statements)

References 58 publications

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“…In the future, options for combining those processes with the chemical utilisation of CO 2 could gain greater relevance, especially if CO 2 conversion can be efficiently linked to H 2 production from electrolysis processes operated with renewable electrical energy [4]. Besides methanol (MeOH), dimethyl ether (DME) is one key intermediate in PtL processes [5,6]. Technically, DME can be produced from syngas in a two-step (indirect) process by the separate dehydration of MeOH or in a one-step (direct) process [7].…”

Section: Introductionmentioning

confidence: 99%

Enhanced Direct Dimethyl Ether Synthesis from CO2-Rich Syngas with Cu/ZnO/ZrO2 Catalysts Prepared by Continuous Co-Precipitation

et al. 2020

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The manufacturing of technical catalysts generally involves a sequence of different process steps, of which co-precipitation is one of the most important. In this study, we investigate how continuous co-precipitation influences the properties of Cu/ZnO/ZrO2 (CZZ) catalysts and their application in the direct synthesis of dimethyl ether (DME) from CO2/CO/H2 feeds. We compare material characteristics investigated by means of XRF, XRD, N2 physisorption, H2-TPR, N2O-RFC, TEM and EDXS as well as the catalytic properties to those of CZZ catalysts prepared by a semi-batch co-precipitation method. Ultra-fast mixing in continuous co-precipitation results in high BET and copper surface areas as well as in improved metal dispersion. DME synthesis performed in combination with a ferrierite-type co-catalyst shows correspondingly improved productivity for CZZ catalysts prepared by the continuous co-precipitation method, using CO2-rich as well as CO-rich syngas feeds. Our continuous co-precipitation approach allows for improved material homogeneity due to faster and more homogeneous solid formation. The so-called “chemical memory” stamped during initial co-precipitation is kept through all process steps and is reflected in the final catalytic properties. Furthermore, our continuous co-precipitation approach may be easily scaled-up to industrial production rates by numbering-up. Hence, we believe that our approach represents a promising contribution to improve catalysts for direct DME synthesis.

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Section: Introductionmentioning

confidence: 99%

Enhanced Direct Dimethyl Ether Synthesis from CO2-Rich Syngas with Cu/ZnO/ZrO2 Catalysts Prepared by Continuous Co-Precipitation

et al. 2020

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“…The so-called biosyncrude ® is then transported and fed to a centralized entrained flow gasifier where syngas free of tar is produced [50]. After several gas conditioning steps, the syngas is fed to a direct DME synthesis [51,52], followed by a DTG reactor [53].…”

Section: Methanol and Dimethyl Ether To Gasolinementioning

confidence: 99%

Standard-Compliant Gasoline by Upgrading a DTG-Based Fuel through Hydroprocessing the Heavy-Ends and Blending of Oxygenates

Graf

Neuner

Rauch

2023

Fuels

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Methanol-to-gasoline (MTG) and dimethyl ether-to-gasoline (DTG) fuels are rich in heavy aromatics such as 1,2,4,5-tetramethylbenzene, resulting in low volatilities due to a lack of light ends, increased emission tendencies and drivability problems due to crystallization. Approaches addressing these issues mainly focus on single aspects or are optimized for petroleum-based feedstocks. This research article introduces an upgrading strategy for MTG and DTG fuels through hydroprocessing (HP) heavy-ends and applying a sophisticated blending concept. Different product qualities were prepared by HP heavy gasoline (HG) and Fischer-Tropsch wax using commercially available Pt/HZSM-5 and Pt/SAPO-11 catalysts in a fixed-bed reactor. The products were used for blending experiments, focusing on gasoline volatility characteristics. Accordingly, methanol, ethanol, methyl tert-butyl ether (MTBE), and ethyl tert-butyl ether (ETBE) were evaluated in a second blending experiment. The results were finally considered for preparing blends meeting EN 228. HP of HG was found to improve the amount of light-ends and the vapor pressure of the DTG fuel with increasing reaction temperature without, however, satisfying EN 228. The front-end volatility was further improved by blending methanol due to the formation of near-azeotropic mixtures, while ethyl tert-butyl ether (ETBE) considerably supported the mid-range volatility. A final blend with an alcohol content of less than 3 vol.%, mostly meeting EN 228, could be provided, making it suitable even for older vehicles.

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“…An obvious reason for this observation would be its moderate acidity in combination with intraparticle mesoporosity and high crystallinity of the zeolite component (Table , Figure d). This is in line with previous results from our group on powdered hierarchical H-ZSM-5 catalysts for DTG where Z40.05 also showed significantly increased deactivation resistance. , In comparison, the silica-bound counterpart Z40.05-S shows lower DME conversion values that also decline faster when WHSV is increased despite having higher crystallinity and micropore volume (Table , Table S4). An analogous behavior is observed when comparing Z28.05-S with Z28.05-A, although Z28.05-S seems to be more active initially.…”

Section: Catalytic Performancementioning

confidence: 99%

“…Hierarchically structured zeolites have attracted considerable interest as heterogeneous catalysts due to the potential enhancement of catalytic activity and shape selectivity compared to standard microporous zeolites. The current major opinion is that complementary meso- and/or macropores favor mass transport and accessibility of acid sites. − For MTH processes, improved conversion in relation to the catalyst volume, increased catalyst lifetime, and enhanced selectivity to gasoline-range products has been observed. − For DTG conversion, we have shown that the application of powdered hierarchical H-ZSM-5 catalysts enhanced DME conversion capacity by up to 695% with respect to microporous H-ZSM-5. , …”

Section: Introductionmentioning

confidence: 99%

“…43−50 For DTG conversion, we have shown that the application of powdered hierarchical H-ZSM-5 catalysts enhanced DME conversion capacity by up to 695% with respect to microporous H-ZSM-5. 51,52 One common approach to generate such hierarchically structured zeolite materials is alkaline treatment, which removes silicon from the zeolite structure ("desilication"). 42,53 Although other concepts have been developed, such as the use of hard or soft templates, 54 this approach is technically straightforward 37,38 due to the good transferability to technical production.…”

Section: ■ Introductionmentioning

confidence: 99%

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Shaped Hierarchical H-ZSM-5 Catalysts for the Conversion of Dimethyl Ether to Gasoline

Wodarz

Slaby

Zimmermann

et al. 2020

Ind. Eng. Chem. Res.

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Hierarchical H-ZSM-5 zeolites are a promising class of heterogeneous catalysts that have shown encouraging results in lab-scale studies for the production of gasoline from dimethyl ether (DTG conversion). However, the influences of mesopore formation and shaping on various catalyst properties are still under debate. In this study, a series of H-ZSM-5 zeolites with hierarchical pore structures were prepared by modifying commercially available zeolites via alkaline treatment (“desilication”). The powdered zeolites were shaped into technical catalyst bodies by wet extrusion using either silica or alumina binders. All materials were extensively characterized. The different interactions during alkaline treatment were related to the observed modifications in the zeolite properties of the materials obtained. Although many properties of modified and untreated zeolite powders remained predominantly unchanged in their shaped catalyst equivalents, both binders affected certain material characteristics, particularly those related to their acidity. Finally, preliminary tests showed enhanced catalytic performance of hierarchical ZSM-5 catalysts in DTG conversion.

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Mesoporous H‐ZSM‐5 for the Conversion of Dimethyl Ether to Hydrocarbons

Cited by 10 publications

References 58 publications

Enhanced Direct Dimethyl Ether Synthesis from CO2-Rich Syngas with Cu/ZnO/ZrO2 Catalysts Prepared by Continuous Co-Precipitation

Enhanced Direct Dimethyl Ether Synthesis from CO2-Rich Syngas with Cu/ZnO/ZrO2 Catalysts Prepared by Continuous Co-Precipitation

Standard-Compliant Gasoline by Upgrading a DTG-Based Fuel through Hydroprocessing the Heavy-Ends and Blending of Oxygenates

Shaped Hierarchical H-ZSM-5 Catalysts for the Conversion of Dimethyl Ether to Gasoline

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