Direct Synthesis of Dimethyl Ether on Bifunctional Catalysts Based on Cu–ZnO(Al) and Supported H3PW12O40: Effect of Physical Mixing on Bifunctional Interactions and Activity
About: This article is published in Industrial & Engineering Chemistry Research.The article was published on 2021-11-18 and is currently open access. It has received 6 citations till now. The article focuses on the topics: Bifunctional & Dimethyl ether.
Citations
More filters
TL;DR: In this article , the authors highlight the recent advances in the development of heterogeneous catalysts and processes for CO2 hydrogenation to these products, including synthetic natural gas, methanol and DME, methane and higher hydrocarbons, higher alcohols.
1 citations
TL;DR: In this paper , the authors reviewed the literature from the last five years to assess the current best practices for CO2 capture and conversion into high value fuels, focusing on atmospheric CO 2 capture, photoconversion, and downstream purification of the final product using membrane-based technologies for a sustainable future.
Abstract: Globally, industrial production sectors have become increasingly concerned about reducing CO2 evolution, through planned carbonization with concurrent substitution of fossil fuels with renewable energy resources, since the release of the Paris climate accord regulations. CO2 is an inexpensive substrate used for the production of useful chemicals and fuels through various chemical and biological processes. As a result, reducing CO2 emissions while producing non-fossil fuels, such as methanol or its derivatives, could be an appealing solution to the global energy problems. The high cetane number, low autoignition temperature, and low extract pollutant value of dimethyl ether, one of the most valuable methanol derivatives, make it a clean and eco-friendly alternative to fossil fuels. Recent literature from the last five years is critically reviewed in the present study to assess the current best practices for CO2 capture and conversion into high value fuels. Particular emphasis has been placed on atmospheric CO2 capture, photoconversion, and the downstream purification of the final product using membrane-based technologies for a sustainable future. Currently, there is a compelling need for an impending transition away from fossil fuel-based technologies toward inventive new technologies using renewable energy sources through carbon management via CO2 conversion and utilization.
1 citations
TL;DR: In this paper , a generalized rational design for bifunctional catalysts with metal/metal oxide and zeolites is proposed based on literatures, where the metal and metal oxide component can be categorized into migrating and non-migrating species, which can be either beneficial or detrimental to the desired products.
1 citations
TL;DR: In this article , the authors present a review of the most recent research in the field of catalytic hydrogenation of captured CO2 by different industrial processes, focusing on the last five years, when research in this field has increased dramatically.
Abstract: The catalytic hydrogenation of captured CO2 by different industrial processes allows obtaining liquid biofuels and some chemical products that not only present the interest of being obtained from a very low-cost raw material (CO2) that indeed constitutes an environmental pollution problem but also constitute an energy vector, which can facilitate the storage and transport of very diverse renewable energies. Thus, the combined use of green H2 and captured CO2 to obtain chemical products and biofuels has become attractive for different processes such as power-to-liquids (P2L) and power-to-gas (P2G), which use any renewable power to convert carbon dioxide and water into value-added, synthetic renewable E-fuels and renewable platform molecules, also contributing in an important way to CO2 mitigation. In this regard, there has been an extraordinary increase in the study of supported metal catalysts capable of converting CO2 into synthetic natural gas, according to the Sabatier reaction, or in dimethyl ether, as in power-to-gas processes, as well as in liquid hydrocarbons by the Fischer-Tropsch process, and especially in producing methanol by P2L processes. As a result, the current review aims to provide an overall picture of the most recent research, focusing on the last five years, when research in this field has increased dramatically.
TL;DR: In this paper , a single-grain method with intensive intra-particular contact between CZZ and the dehydration catalyst generated by mixing in an agate mortar and a dual-grain approach relying on physical mixing with low contact was investigated.
Abstract: The direct synthesis of dimethyl ether (DME) via CO2 hydrogenation in a single step was studied using an improved class of bifunctional catalysts in a fixed bed reactor (TR: 210–270 °C; 40 bar; gas hourly space velocity (GHSV) 19,800 NL kgcat–1 h–1; ratio CO2/H2/N2 3:9:2). The competitive bifunctional catalysts tested in here consist of a surface-basic copper/zinc oxide/zirconia (CZZ) methanol-producing part and a variable surface-acidic methanol dehydration part and were tested in overall 45 combinations. As dehydration catalysts, zeolites (ferrierite and β-zeolite), alumina, or zirconia were tested alone as well as with a coating of Keggin-type heteropoly acids (HPAs), i.e., silicotungstic or phosphotungstic acid. Two different mixing methods to generate bifunctional catalysts were tested: (i) a single-grain method with intensive intra-particular contact between CZZ and the dehydration catalyst generated by mixing in an agate mortar and (ii) a dual-grain approach relying on physical mixing with low contact. The influence of the catalyst mixing method and HPA loading on catalyst activity and stability was investigated. From these results, a selection of best-performing bifunctional catalysts was investigated in extended measurements (time on stream: 160 h/7 days, TR: 250 and 270 °C; 40 bar; GHSV 19,800 NL kgcat–1 h–1; ratio CO2/H2/N2 3:9:2). Silicotungstic acid-coated bifunctional catalysts showed the highest resilience toward deactivation caused by single-grain preparation and during catalysis. Overall, HPA-coated catalysts showed higher activity and resilience toward deactivation than uncoated counterparts. Dual-grain preparation showed superior performance over single grain. Furthermore, silicotungstic acid coatings with 1 KU nm–2 (Keggin unit per surface area of carrier) on Al2O3 and ZrO2 as carrier materials showed competitive high activity and stability in extended 7-day measurements compared to pure CZZ. Therefore, HPA coating is found to be a well-suited addition to the CO2-to-DME catalyst toolbox.
References
More filters
TL;DR: Mise au point comportant des definitions generales et la terminologie, la methodologie utilisee, les procedes experimentaux, les interpretations des donnees d'adsorption, les determinations de l'aire superficielle, and les donnes sur la mesoporosite et la microporosite.
Abstract: Mise au point comportant des definitions generales et la terminologie, la methodologie utilisee, les procedes experimentaux, les interpretations des donnees d'adsorption, les determinations de l'aire superficielle, et les donnees sur la mesoporosite et la microporosite
20,347 citations
TL;DR: In an attempt to give an order of magnitude regarding CO2 valorization, the most important aspects of CO2 capture and green routes to produce H2 are summarized and economical aspects of the production of methanol and DME are critically assessed.
Abstract: The recent advances in the development of heterogeneous catalysts and processes for the direct hydrogenation of CO2 to formate/formic acid, methanol, and dimethyl ether are thoroughly reviewed, with special emphasis on thermodynamics and catalyst design considerations. After introducing the main motivation for the development of such processes, we first summarize the most important aspects of CO2 capture and green routes to produce H2. Once the scene in terms of feedstocks is introduced, we carefully summarize the state of the art in the development of heterogeneous catalysts for these important hydrogenation reactions. Finally, in an attempt to give an order of magnitude regarding CO2 valorization, we critically assess economical aspects of the production of methanol and DME and outline future research and development directions.
927 citations
TL;DR: In this paper, a comprehensive review of the technical feasibility of di-methyl ether (DME) as a candidate fuel for environmentally-friendly compression-ignition engines independent of size or application is provided.
879 citations
TL;DR: In this article, the most frequent problem in the study of heterogeneous catalysis is the determination of a quantity called "catalyst activity", the experimental procedures, and methods of interpretation leading to a proper description of this quantity.
Abstract: Publisher Summary This chapter discusses the interpretation of measurements in experimental catalysis. It focuses on the most frequent problem in the study of heterogeneous catalysis—that is, the determination of a quantity called “catalyst activity,” the experimental procedures, and methods of interpretation leading to a proper description of this quantity. Catalyst activity manifests itself in terms of a chemical reaction rate characteristic of the presence of the catalyst. It is always such a reaction velocity that is the subject of primary experimental data from which a description of the catalyst's activity must be derived. The reaction velocity under any particular operating condition may well be affected by a variety of more or less independent variables. For example, in many fundamental researches, relationships are sought with the composition, crystal lattice, and electronic structure of the catalyst solid, yet measured reaction velocities are often influenced by gas transport phenomena that are unrelated to any of these fundamental properties. Gas transport phenomena and diffusion effects have been described occasionally in the literature. The powerful role played by these in determining the nature of experimental data cannot be overemphasized. The chapter discusses the behavior of catalysts related to the design and the interpretation of catalytic experiments in the course of fundamental research.
484 citations
TL;DR: In this paper, the authors present an updated review of the recent progresses in the catalyst innovation, optimization of the reaction conditions, reaction mechanism, and catalyst performance in methanol synthesis.
Abstract: Since the start of last century, methanol synthesis has attracted great interests because of its importance in chemical industries and its potential as an environmentally friendly energy carrier. The catalyst for the methanol synthesis has been a key area of research in order to optimize the reaction process. In the literature, the nature of the active site and the effects of the promoter and support have been extensively investigated. In this updated review, the recent progresses in the catalyst innovation, optimization of the reaction conditions, reaction mechanism, and catalyst performance in methanol synthesis are comprehensively discussed. Key issues of catalyst improvement are highlighted, and areas of priority in R&D are identified in the conclusions.
453 citations